WO2020000510A1 - 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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WO2020000510A1
WO2020000510A1 PCT/CN2018/095255 CN2018095255W WO2020000510A1 WO 2020000510 A1 WO2020000510 A1 WO 2020000510A1 CN 2018095255 W CN2018095255 W CN 2018095255W WO 2020000510 A1 WO2020000510 A1 WO 2020000510A1
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starch
transition metal
carbon skeleton
amylase
reinforced
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French (fr)
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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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Jiangnan University
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Priority to US16/475,126 priority Critical patent/US20200406227A1/en
Priority to RU2019126009A priority patent/RU2745023C1/ru
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    • C—CHEMISTRY; METALLURGY
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    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/22—Preparation of compounds containing saccharide radicals produced by the action of a beta-amylase, e.g. maltose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/28002—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 physical properties
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    • B01J20/28054—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 surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
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    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
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    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/20—Preparation of compounds containing saccharide radicals produced by the action of an exo-1,4 alpha-glucosidase, e.g. dextrose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

Definitions

  • the invention relates to a starch-based porous material, in particular to a porous starch prepared by using a transition metal ion to strengthen a carbon skeleton.
  • Porous starch is a new type of modified starch, that is, the particle structure of the original starch is changed by biological, chemical or physical methods to form a porous. Porous starch has greater porosity and specific surface area than raw starch; lower bulk density; better adsorption capacity, etc., has been widely used in agriculture, medical, environmental protection, food, papermaking, printing, detergent, Cosmetics and many other fields.
  • the most commonly used method is the biological method, which uses amylase to hydrolyze the surface of starch to produce small pores.
  • the biological method since raw starch is less sensitive to enzymes when it is below the gelatinization temperature, and gelatinization of high-temperature starch destroys the support structure (ie, the skeleton structure) of the pores, the biological method is basically prepared at low temperatures, which often requires Increase the amount of enzyme or extend the reaction time to improve yield.
  • the overall structure of the porous starch produced by this method has been damaged to a certain degree, and its physical and chemical properties and anti-dissolution, mechanical and other effects are poor.
  • the single function has limitations, and it often needs to be significantly modified during application (such as chemical Coupling, surface functional group modification, etc.), time-consuming and labor-intensive.
  • porous starch In addition to the biological method for preparing porous starch, it is a chemical method, such as acid hydrolysis, solvent exchange, and emulsion cross-linking. However, in addition to the complicated preparation process, it also introduces a large number of chemical reagents. There are certain aspects in terms of production cost and sustainable development. problem. In addition, after the starch is treated with chemical reagents, the structure is more fragile than porous starch made by biological methods, so its application is limited.
  • the physical method is the least used. Although many methods such as extrusion, ultrasound, alcohol denaturation, spraying, and mechanical impact have been tried, it is basically difficult to form effective porosity (mostly concave surface and poor uniformity). It is generally only prepared as an auxiliary biological method. Pre-processing steps.
  • the applicant of the present invention provides a carbon skeleton-reinforced porous starch and a preparation method thereof.
  • the present invention utilizes transition metal ions to strengthen the starch structure, and non-transition metal ions assist the stable performance of the enzyme effect, making physical extrusion and synergistic enzyme action an effective means for preparing porous starch, on the one hand, reducing the amount of enzyme and the action time of the biological method To improve the mechanical strength of its products; on the other hand, it changes the status quo that physical methods can only be used as pretreatment, merging and simplifying the original process.
  • a carbon skeleton-reinforced porous starch is: combining starch with transition metal ions, and then processing the starch with the transition metal ions and amylase through extrusion equipment to form a high-strength recombination structure.
  • Starch-based porous material that is, the carbon skeleton-reinforced porous starch.
  • the preparation method of the porous starch includes the following specific steps:
  • step (3) Pre-humidify the transition metal ion-reinforced starch prepared in step (1) with the non-transition metal ion-amylase complex solution prepared in step (2) to obtain a premix, and then feed the premix into The system is extruded to produce the carbon skeleton-reinforced porous starch.
  • the starch in step (1) is one or more of corn starch, rice starch, potato starch, and cassava starch; and the transition metal is one of manganese, iron, cobalt, nickel, copper, zinc, zirconium, and palladium.
  • the added form is a soluble metal salt.
  • the ion concentration of the aqueous transition metal solution in step (1) is 0.1-5 mol / L; and the mass-volume ratio of the starch to the aqueous transition metal solution is 50-250: 1 g / L.
  • the amylase in step (2) is one or more of moderate-temperature ⁇ -amylase, high-temperature-resistant ⁇ -amylase, ⁇ -amylase, and saccharifying enzyme; the non-transition metal ions are sodium, potassium, and magnesium One or more of calcium.
  • the ion concentration of the non-transition metal ion aqueous solution in step (2) is 0.001-0.01 mol / L; the mass-volume ratio of the amylase to the non-transition metal ion aqueous solution is 0.2-2: 1 g / L.
  • the mass-volume ratio of the transition metal ion-reinforced starch and the non-transition metal ion-amylase complex solution in step (3) is 800-2500: 1 g / L.
  • the water content of the premix in step (3) is 28.5-55.5wt%; the enzyme activity of the premix is greater than 12 U / g, and the enzyme activity is defined as the enzyme added per gram of starch to make the system enzyme Live greater than 12U.
  • the system parameters of the extrusion system described in step (3) are: material temperature 35-105 ° C, pressure ⁇ 5MPa, mechanical energy ⁇ 300kJ / kg; the number of kneading or reverse element zones is less than or equal to two groups, from the feed inlet
  • the temperature setting range to the discharge port is 30-100 ° C, the screw speed is set to 50-250rpm, and the die is equipped with or without an outlet.
  • the transition metal ions of the present invention are absorbed to the surface or inside of starch in an aqueous solution, and covalent bonding occurs, thereby changing the physicochemical, thermal properties and resistance to enzymatic hydrolysis of starch. Due to the selective binding of these transition state metal ions to different parts of starch, the unbound areas of starch are relatively weakened. During the intense extrusion process, the relatively weakened parts of starch can be rapidly degraded by amylase to form a porous space. The reinforced part can maintain a certain mixed and reorganized structure, which serves as a skeleton to support the porous space, and finally forms a "porous matrix".
  • the enzyme activity-promoting ions can be introduced into the active center of the amylase before entering the extrusion process together.
  • the extruder barrel is a "high substrate” environment.
  • These metal salts will release cations during the extrusion process and protect the amylase, so that the amylase is radiated and hydrolyzed from the center to the surroundings in the surrounding feed.
  • Starch substrate (avoid the fortified starch part), gradually forming a porous structure.
  • the present invention utilizes transition metal ions to strengthen the starch structure, and non-transition metal ions assist the stable performance of the enzyme effect, so that physical extrusion and synergistic enzyme action become an effective method for preparing porous starch.
  • the porous starch Based on the selection of different raw materials, metal ions, enzyme preparations and operating conditions, the porous starch has a wide pore size distribution (1-30 ⁇ m), high restructuring structure strength, strong water / oil absorption capacity, and good biodegradability; As a reaction vessel, it has the advantages of continuous, solvent-free, and diversified product functions and shapes.
  • the present invention combines physical method pretreatment with biological method, and its production steps are simple.
  • the average pore size range and overall size of the obtained porous starch are controllable, high structural strength, good water and oil absorption, and biodegradable. Good performance, and the method uses an extruder as a reaction vessel, which has the advantages of continuous, solvent-free and sustainable production.
  • a carbon skeleton reinforced porous starch the preparation method comprises the following steps:
  • a kneading element and an adjacent reverse element are arranged in the extrusion groove of the extruder, the screw speed is set to 250 rpm, the inlet temperature is 30 ° C, the intermediate temperature is 45 ° C, and the outlet temperature is 60 °C, a die with a hole diameter of 2mm is assembled at the exit.
  • the pressure is 2.7MPa and the mechanical energy is 145kJ / kg.
  • the porous starch prepared in this embodiment has a pore size distribution in the range of 1-10 ⁇ m, has good water absorption, structural strength, and biodegradability, and its water absorption rate can reach 446% and the strength is 27.6 MPa.
  • a carbon skeleton reinforced porous starch the preparation method comprises the following steps:
  • (1) 500 g of cassava starch is mixed with 10 L of a 0.1 mol / L manganese sulfate (MnSO 4 ) aqueous solution, stirred and soaked at room temperature for 1 h, and then the cassava starch is decanted and sieved once, and then dried in an oven at 30 ° C. Dried to obtain manganese ion-fortified starch;
  • MnSO 4 manganese sulfate
  • the screw speed is set to 50 rpm, the inlet temperature is 50 ° C, the intermediate temperature is 60-80 ° C, and the discharge temperature is 95 ° C.
  • a die with a diameter of 2mm is assembled; during the extrusion process, the material temperature is 56-103 ° C, the pressure is 4.8MPa, and the mechanical energy is 275kJ / kg.
  • the porous starch prepared in this embodiment has a pore size distribution ranging from 5 to 20 ⁇ m, and has good water absorption, structural strength and biodegradability. Its water absorption can reach 238% and the strength is 19.2. MPa.
  • a carbon skeleton reinforced porous starch the preparation method comprises the following steps:
  • the screw speed is set to 150 rpm
  • the inlet temperature is 40 ° C
  • the intermediate temperature is 40-50 ° C
  • the outlet temperature is 60 ° C.
  • a die with a diameter of 2mm is assembled; during the extrusion process, the material temperature is 42-63 ° C, the pressure is 3.4MPa, and the mechanical energy is 183kJ / kg.
  • the porous starch prepared in this embodiment has a pore size distribution ranging from 10 to 30 ⁇ m, and has good water absorption, structural strength and biodegradability. Its water absorption rate can reach 286% and the strength is 26.5. MPa.

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Abstract

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。其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。
 技术问题
生物法制备多孔淀粉外，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。
 技术解决方案
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1-4 h，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50-250:1 g/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0.2-2:1 g/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800-2500:1 g/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。
 有益效果
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。
 本发明的实施方式
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(SO 4) 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（CaCl 2）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（MnSO 4）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19.2 MPa。
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（FeCl 3）水溶液混合，在30℃下搅拌、浸泡6 h，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0.5g β-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26.5 MPa。

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1-4 h，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50-250:1 g/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0.2-2:1 g/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800-2500:1 g/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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