CN109136306A - 一种碳骨架强化型多孔淀粉及其制备方法 - Google Patents

一种碳骨架强化型多孔淀粉及其制备方法 Download PDF

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CN109136306A
CN109136306A CN201810670327.8A CN201810670327A CN109136306A CN 109136306 A CN109136306 A CN 109136306A CN 201810670327 A CN201810670327 A CN 201810670327A CN 109136306 A CN109136306 A CN 109136306A
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金征宇
徐恩波
吴正宗
焦爱权
周星
田耀旗
王金鹏
柏玉香
赵建伟
谢正军
徐学明
杨哪
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Jiangnan University
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Abstract

本发明公开了一种碳骨架强化型多孔淀粉及其制备方法，该多孔淀粉的制备方法为：将淀粉与过渡金属离子结合，之后将附有过渡金属离子的淀粉与淀粉酶经过挤压设备处理，最后形成高强度重组结构的淀粉基多孔材料，即所述碳骨架强化型多孔淀粉。本发明降低了生物法的酶用量与作用时间，也改变了物理法仅能作为预处理的现状，在药物控释、水污染净化、包埋与替代目标物以及其他医疗、化工、环境与材料领域具有广泛应用前景。

Description

一种碳骨架强化型多孔淀粉及其制备方法
技术领域
本发明涉及淀粉基多孔材料，尤其是涉及一种采用过渡金属离子强化碳骨架，制得的多孔淀粉。
背景技术
多孔淀粉是一种新型变性淀粉，即通过生物、化学或物理方法改变原淀粉的颗粒结构从而形成多孔。多孔淀粉的相比原淀粉具有更大的孔隙率、比表面积；较低的堆积密度；更好的吸附能力等，已广泛地应用于农业、医疗、环保、食品、造纸、印刷、洗涤剂、化妆品等诸多领域。
目前，最常用的是生物法，即利用淀粉酶水解淀粉部分表面产生小孔。但由于生淀粉在低于糊化温度时对酶的敏感性较低，而高温淀粉糊化则破坏了孔洞的支撑结构(即骨架结构)，故生物法基本是在低温下制得，往往需要加大酶量或延长反应时间以提高产率。此外，该法制得的多孔淀粉其整体结构遭到一定程度的破坏，各理化性能与抗溶解、机械等作用较差，功能单一具有局限性，在应用时往往还需大幅改性(如化学交联、表面官能团改性等)，耗时耗力。
其次是化学法，如酸水解、溶剂交换、乳液交联等，但该法除制备流程复杂外，还引入大量化学试剂，在生产成本与可持续发展方面均存在一定的问题。此外，淀粉经化学试剂处理后，结构比生物法制得的多孔淀粉更脆弱，故应用受限。
物理法运用最少，虽然挤压、超声波、醇变性、喷雾、机械撞击等诸多方法被尝试，但基本均难以形成有效的多孔(大多为表面凹陷且均匀性差)，一般仅作为辅助生物法制备的前处理步骤。
发明内容
针对现有技术存在的上述问题，本发明申请人提供了一种碳骨架强化型多孔淀粉及其制备方法。本发明利用过渡金属离子强化淀粉结构、非过渡金属离子辅助酶效稳定发挥，使得物理挤压协同酶作用成为一种有效的制备多孔淀粉的手段，一方面降低了生物法的酶用量与作用时间、提高其产品机械强度；另一方面改变了物理法仅能作为预处理的现状，合并与简化了原有工艺。
本发明的技术方案如下：
一种碳骨架强化型多孔淀粉，所述多孔淀粉的制备方法为：将淀粉与过渡金属离子结合，之后将附有过渡金属离子的淀粉与淀粉酶经过挤压设备处理，最后形成高强度重组结构的淀粉基多孔材料，即所述碳骨架强化型多孔淀粉。
所述多孔淀粉的制备方法包括如下具体步骤：
(1)将淀粉与过渡金属水溶液混合，在20-40℃条件下，搅拌、浸泡1-12h，之后倾倒筛出淀粉并清洗1-3次，置于烘箱中，30-50℃下烘干，得到过渡金属离子强化淀粉；
(2)将淀粉酶与非过渡金属离子水溶液混合，在20-40℃条件下搅拌、混合1-4h，得到非过渡金属离子—淀粉酶复合液；
(3)将步骤(1)制得的过渡金属离子强化淀粉与步骤(2)制得的非过渡金属离子—淀粉酶复合液混合预调湿，得到预混料，之后将预混料喂入挤压系统，出料，制得所述碳骨架强化型多孔淀粉。
步骤(1)中所述淀粉为玉米淀粉、大米淀粉、马铃薯淀粉、木薯淀粉中的一种或多种；所述过渡金属为锰、铁、钴、镍、铜、锌、锆、钯中的一种或多种，添加形式为可溶性金属盐。
步骤(1)中所述过渡金属水溶液的离子浓度为0.1-5mol/L；所述淀粉与过渡金属水溶液的质量体积比为50-250:1g/L。
步骤(2)中所述淀粉酶为中温α-淀粉酶、耐高温α-淀粉酶、β-淀粉酶、糖化酶中的一种或多种；所述非过渡金属离子为钠、钾、镁、钙中的一种或多种。
步骤(2)中所述非过渡金属离子水溶液的离子浓度为0.001-0.01mol/L；所述淀粉酶与非过渡金属离子水溶液的质量体积比为0.2-2:1g/L。
步骤(3)中所述过渡金属离子强化淀粉与非过渡金属离子—淀粉酶复合液的质量体积比为800-2500:1g/L。
步骤(3)中所述预混料的含水量为28.5-55.5wt％；所述预混料的酶活大于12U/g，所述酶活定义为每克淀粉加入的酶后，使体系酶活大于12U。
步骤(3)中所述挤压系统的系统参数为：物料温度35-105℃，压强＜5MPa，机械能＜300kJ/kg；捏合或反向元件区的数量小于或等于两组，从进料口到出料口的温度设置范围为30-100℃，螺杆转速设置为50-250rpm，出口处装配或不装配模头。
本发明有益的技术效果在于：
本发明的过渡金属离子在水溶液中被吸收到淀粉表面或内部，发生共价结合，从而改变淀粉的理化、热学性质与抗酶解能力。由于这些过渡态金属离子与淀粉不同部位的结合具有选择性，故淀粉未结合区域相对地弱化，在剧烈的挤压过程中，淀粉相对弱化部位可被淀粉酶快速降解形成多孔空间，而淀粉的强化部位则可保持一定的混合、重组结构，作为骨架支撑多孔空间，最终形成“多孔状基质”。
本发明考虑到某些过渡金属离子对淀粉酶的结合抑制作用，可预先将酶活促进离子引入淀粉酶的活性中心，再一同进入挤压过程。对于酶而言，挤压机筒是“高底物”环境，这些金属盐会在挤压过程中释放阳离子并保护淀粉酶，从而使淀粉酶在周围包裹的喂料里从中心向四周辐射水解淀粉底物(避开强化的淀粉部分)，逐步形成多孔结构。
本发明利用过渡金属离子强化淀粉结构、非过渡金属离子辅助酶效稳定发挥，使得物理挤压协同酶作用成为一种有效的制备多孔淀粉的手段。基于不同原料、金属离子、酶制剂与操作条件的选择，该多孔淀粉的孔径范围分布广(1-30μm)、重组结构强度高、吸水/吸油能力强、生物可降解性好；将挤压机作为反应容器，具有连续化、无溶剂、产品功能与形状多样化等优点。
与现有技术相比，本发明将物理法预处理与生物法相结合，其生产步骤简单，所得多孔淀粉的平均孔径范围与整体尺寸可控、结构强度高、吸水与吸油性良好、生物可降解性好，且该法以挤压机作为反应容器，具有连续化、无溶剂、可持续等生产优势。
具体实施方式
下面结合实施例，对本发明进行具体描述。
实施例1
一种碳骨架强化型多孔淀粉，制备方法包括如下步骤：
(1)将500g玉米淀粉与2L 5mol/L的硫酸锆(Zr(SO4)2)水溶液混合，在40℃下搅拌、浸泡12h，之后倾倒筛出玉米淀粉并清洗3次，置于烘箱中50℃下烘干，得到锆离子强化淀粉；
(2)将2g中温α-淀粉酶与1L 0.01mol/L的氯化钙(CaCl2)水溶液混合，40℃条件下搅拌、混合4h，得到钙-淀粉酶复合液；
(3)取450g锆离子强化淀粉(制备损失率小于3％，淀粉湿基含量93.7％)与0.56L钙-淀粉酶复合液混合，预调湿达到含水量为55％，制得含酶预混料，之后将调湿后的含酶预混料，以2kg/h的喂料速度添加进入双螺杆挤压机中，挤出物经冷却、干燥后，可保持整体形状，也可通过切割(或粉碎)、过筛后制得不同颗粒尺寸大小的淀粉基多孔材料。所述挤压机的挤压槽内配置一处捏合元件以及邻近的一处反向元件，螺杆转速设置为250rpm，进料口温度为30℃，中间温度为45℃，出料口温度为60℃，出口处装配孔径2mm的模头，挤压过程中，压力为2.7MPa，机械能为145kJ/kg。
本实施例制得的多孔淀粉，其孔径大小分布范围在1-10μm，具有良好的吸水性、结构强度和生物可降解性，其吸水率可达到446％，强度为27.6MPa。
实施例2
一种碳骨架强化型多孔淀粉，制备方法包括如下步骤：
(1)将500g木薯淀粉与10L 0.1mol/L的硫酸锰(MnSO4)水溶液混合，在室温下搅拌、浸泡1h，之后倾倒筛出木薯淀粉并清洗1次，置于烘箱中30℃下烘干，得到锰离子强化淀粉；
(2)将0.04g耐高温α-淀粉酶与0.2L 0.001mol/L的氯化钾(KCl)水溶液混合，30℃条件下搅拌、混合4h，得到钾-淀粉酶复合液；
(3)取450g锰离子强化淀粉(制备损失率小于3％，淀粉湿基含量95.2％)与0.18L的钾-淀粉酶复合液混合，预调湿达到含水量为29％，制得含酶预混料，之后将调湿后的含酶预混料，以2kg/h的喂料速度添加进入双螺杆挤压机中，挤出物经冷却、干燥后，可保持整体形状，也可通过切割(或粉碎)、过筛后制得不同颗粒尺寸大小的淀粉基多孔材料。所述挤压机的挤压槽内配置一处捏合元件而无反向元件，螺杆转速设置为50rpm，进料口温度为50℃，中间温度为60-80℃，出料口温度为95℃，出口处装配孔径2mm的模头；挤压过程中，物料温度为56-103℃，压力为4.8MPa，机械能为275kJ/kg。
本实施例制得的多孔淀粉，其孔径大小分布范围在5-20μm，具有良好的吸水性、结构强度和生物可降解性，其吸水率可达到238％，强度为19.2MPa。
实施例3
一种碳骨架强化型多孔淀粉，制备方法包括如下步骤：
(1)将500g大米淀粉与5L 2.5mol/L的氯化铁(FeCl3)水溶液混合，在30℃下搅拌、浸泡6h，之后倾倒筛出大米淀粉并清洗2次，置于烘箱中40℃下烘干，得到铁离子强化淀粉；
(2)将0.5gβ-淀粉酶与0.5L 0.005mol/L的氯化钠(NaCl)混合，在30℃条件下搅拌、混合4h，得到钠-淀粉酶复合液；
(3)取450g铁离子强化淀粉(制备损失率小于3％，淀粉湿基含量93.9％)与0.30L钠-淀粉酶复合液混合，预调湿达到含水量为43％，制得含酶预混料，之后将调湿后的含酶预混料，以2kg/h的喂料速度添加进入双螺杆挤压机中，挤出物经冷却、干燥后，可保持整体形状，也可通过切割(或粉碎)、过筛后制得不同颗粒尺寸大小的淀粉基多孔材料。所述挤压机的挤压槽内配置两处捏合元件而无反向元件，螺杆转速设置为150rpm，进料口温度为40℃，中间温度为40-50℃，出料口温度为60℃，出口处装配孔径2mm的模头；挤压过程中，物料温度为42-63℃，压力为3.4MPa，机械能为183kJ/kg。
本实施例制得的多孔淀粉，其孔径大小分布范围在10-30μm，具有良好的吸水性、结构强度和生物可降解性，其吸水率可达到286％，强度为26.5MPa。

Claims (9)

1.一种碳骨架强化型多孔淀粉，其特征在于，所述多孔淀粉的制备方法为：将淀粉与过渡金属离子结合，之后将附有过渡金属离子的淀粉与淀粉酶经过挤压设备处理，最后形成高强度重组结构的淀粉基多孔材料，即所述碳骨架强化型多孔淀粉。
2.根据权利要求1所述的碳骨架强化型多孔淀粉，其特征在于，所述多孔淀粉的制备方法包括如下具体步骤：
(1)将淀粉与过渡金属水溶液混合，在20-40℃条件下，搅拌、浸泡1-12h，之后倾倒筛出淀粉并清洗1-3次，置于烘箱中，30-50℃下烘干，得到过渡金属离子强化淀粉；
(2)将淀粉酶与非过渡金属离子水溶液混合，在20-40℃条件下搅拌、混合1-4h，得到非过渡金属离子—淀粉酶复合液；
(3)将步骤(1)制得的过渡金属离子强化淀粉与步骤(2)制得的非过渡金属离子—淀粉酶复合液混合预调湿，得到预混料，之后将预混料喂入挤压系统，出料，制得所述碳骨架强化型多孔淀粉。
3.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(1)中所述淀粉为玉米淀粉、大米淀粉、马铃薯淀粉、木薯淀粉中的一种或多种；所述过渡金属为锰、铁、钴、镍、铜、锌、锆、钯中的一种或多种，添加形式为可溶性金属盐。
4.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(1)中所述过渡金属水溶液的离子浓度为0.1-5mol/L；所述淀粉与过渡金属水溶液的质量体积比为50-250:1g/L。
5.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(2)中所述淀粉酶为中温α-淀粉酶、耐高温α-淀粉酶、β-淀粉酶、糖化酶中的一种或多种；所述非过渡金属离子为钠、钾、镁、钙中的一种或多种。
6.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(2)中所述非过渡金属离子水溶液的离子浓度为0.001-0.01mol/L；所述淀粉酶与非过渡金属离子水溶液的质量体积比为0.2-2:1g/L。
7.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(3)中所述过渡金属离子强化淀粉与非过渡金属离子—淀粉酶复合液的质量体积比为800-2500:1g/L。
8.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(3)中所述预混料的含水量为28.5-55.5wt％；所述预混料的酶活大于12U/g，所述酶活定义为每克淀粉加入的酶后，使体系酶活大于12U。
9.根据权利要求2所述的碳骨架强化型多孔淀粉，其特征在于，步骤(3)中所述挤压系统的系统参数为：物料温度35-105℃，压强＜5MPa，机械能＜300kJ/kg；捏合或反向元件区的数量小于或等于两组，从进料口到出料口的温度设置范围为30-100℃，螺杆转速设置为50-250rpm，出口处装配或不装配模头。
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