CN110773134A

Movatterモバイル変換

Info

Publication number: CN110773134A
Application number: CN201911216553.XA
Authority: CN
Inventors: 李运; 姜晨辉; 丁海燕
Original assignee: Yantai University
Current assignee: Yantai University
Priority date: 2019-12-02
Filing date: 2019-12-02
Publication date: 2020-02-11

Abstract

The invention discloses a montmorillonite-collagen composite hydrogel adsorption material and a preparation method thereof, wherein hazardous waste chromium-containing leather scraps are used as raw materials, and montmorillonite-collagen composite hydrogel is prepared by hydrolysis, modification and crosslinking. The bentonite-collagen composite gel of the invention not only can fix or adsorb dye and has good swelling performance, but also overcomes the technical problem that the montmorillonite adsorbent in the prior art is difficult to recover.

Description

Translated fromChinese

蒙脱土-胶原蛋白复合水凝胶吸附材料及其制备方法Montmorillonite-collagen composite hydrogel adsorption material and preparation method thereof

技术领域technical field

本发明涉及染料纺织和皮革废水治理领域，具体的涉及一种蒙脱土-胶原蛋白复合水凝胶的制备方法，进一步涉及一种以含铬废革屑为原料制备新型蒙脱土-胶原蛋白复合水凝胶吸附材料的方法。The invention relates to the field of dye textile and leather wastewater treatment, in particular to a preparation method of a montmorillonite-collagen composite hydrogel, and further relates to a new type of montmorillonite-collagen prepared by using chromium-containing waste leather scraps as raw materials Methods of composite hydrogel adsorbent materials.

背景技术Background technique

水凝胶是一类由高分子主链和亲水性官能团通过共价键、离子键、氢键或者是物理缠绕交联等方式形成的三维网络结构高分子聚合物，能吸收大量的水而溶胀，并不被溶解。水凝胶作为一种有吸水性但不溶于水的功能高分子材料，溶胀量高且溶胀速率较快，具有高吸水性和保水性、韧性与粘性，对温度、pH、离子强度、电场等条件的刺激响应性以及生物相容性和生物可降解性等诸多优越性能。水凝胶含有大量官能团，如羟基，氨基，羧基和酰胺基，对阳离子染料具有很强的结合能力。然而皮革印染行业废水成分复杂，pH变化大，其中还含有各种有机物及干扰离子，造成水凝胶不稳定，吸附效果不尽人意。Hydrogel is a kind of polymer with a three-dimensional network structure formed by the polymer main chain and hydrophilic functional groups through covalent bonds, ionic bonds, hydrogen bonds or physical entanglement and cross-linking. swelled, not dissolved. As a functional polymer material with water absorption but insoluble in water, hydrogel has high swelling capacity and fast swelling rate, high water absorption and water retention, toughness and viscosity, and is sensitive to temperature, pH, ionic strength, electric field, etc. Stimuli responsiveness to conditions, as well as many superior properties such as biocompatibility and biodegradability. The hydrogels contain a large number of functional groups, such as hydroxyl, amino, carboxyl and amide groups, which have strong binding ability for cationic dyes. However, the wastewater in the leather printing and dyeing industry is complex in composition, with large pH changes, and also contains various organic substances and interfering ions, resulting in unstable hydrogels and unsatisfactory adsorption effects.

皮革工业是一个与人们生活密切相关的传统行业。据统计，全世界每年生皮和皮革的总量约一千五百万吨，其中，制革生产过程中每年产生的固体废弃物约六百万吨，其主要成分是胶原蛋白，如不加以治理和利用会造成大量的污染及资源的浪费。因此，皮革固体废弃物的回收和再循环对制革行业的可持续发展具有重要意义。通过物理、化学或生物的方法，将皮革中的胶原蛋白水解成胶原蛋白水解液，从而实现了皮革废弃物的有效利用。胶原蛋白是一种天然的两性高分子，具有大量的活性基团，亲水性强，对pH具有一定响应作用，作为水凝胶的骨架，具有良好的吸附潜力。然而胶原蛋白水凝胶机械性能较差，易碎，循环使用性能差。Leather industry is a traditional industry closely related to people's lives. According to statistics, the total amount of raw hides and leathers in the world is about 15 million tons each year, of which, the annual solid waste generated in the tanning production process is about 6 million tons, the main component of which is collagen. And utilization will cause a lot of pollution and waste of resources. Therefore, the recovery and recycling of leather solid waste is of great significance to the sustainable development of the tanning industry. Through physical, chemical or biological methods, the collagen in leather is hydrolyzed into collagen hydrolyzate, thereby realizing the effective utilization of leather waste. Collagen is a natural amphiphilic polymer with a large number of active groups, strong hydrophilicity, and a certain response to pH. As the backbone of hydrogels, it has good adsorption potential. However, collagen hydrogels have poor mechanical properties, are brittle, and have poor recycling performance.

蒙脱土作为一种硅铝酸盐的天然矿物，蒙脱土由于其成本低、无毒、比表面积大、化学和机械稳定性、负荷能力强和阳离子交换容量高而被广泛单独或作为复合吸附剂的成分之一使用。但是，由于蒙脱土为粉体材料，在吸附完成后通过沉降或过滤将蒙脱土的回收既耗时又昂贵，而且很难回收彻底，这进一步制约了蒙脱土在吸附领域的广泛利用。现有技术中，通常将蒙脱土通过酸活化、煅烧、磁化、表面活性剂和聚合物等方法进行改性制备含蒙脱土的吸附材料去除溶液中的染料，但是，用于吸附的材料由于颗粒较小，回收比较困难，只能通过传统的方法(沉降或过滤)分离吸附材料和水溶液。As a natural mineral of aluminosilicate, montmorillonite is widely used alone or as a compound due to its low cost, non-toxicity, large specific surface area, chemical and mechanical stability, strong loading capacity and high cation exchange capacity. One of the components of the adsorbent is used. However, since montmorillonite is a powder material, the recovery of montmorillonite by sedimentation or filtration after adsorption is time-consuming and expensive, and it is difficult to recover completely, which further restricts the widespread utilization of montmorillonite in the field of adsorption. . In the prior art, montmorillonite is usually modified by methods such as acid activation, calcination, magnetization, surfactant and polymer to prepare montmorillonite-containing adsorption materials to remove dyes in the solution, but the materials used for adsorption are Due to the small size of the particles, the recovery is more difficult, and the adsorption material and the aqueous solution can only be separated by traditional methods (sedimentation or filtration).

发明内容SUMMARY OF THE INVENTION

为解决现有技术染料吸附后吸附材料不易分离的技术问题，本发明提出了一种利用危险废弃物含铬废革屑生产能够用于阳离子型染料吸附的蒙脱土-胶原蛋白复合水凝胶的制备方法，具体为一种蒙脱土-胶原蛋白复合水凝胶及其制备方法和应用。In order to solve the technical problem that the adsorption material is difficult to separate after dye adsorption in the prior art, the present invention proposes a montmorillonite-collagen composite hydrogel that can be used for cationic dye adsorption by using hazardous waste chromium-containing waste leather scraps The preparation method is specifically a montmorillonite-collagen composite hydrogel and its preparation method and application.

本发明对蒙脱土-胶原蛋白复合水凝胶吸附亚甲基蓝进行了应用研究，并取得了良好的效果。In the present invention, application research is carried out on the adsorption of methylene blue on the montmorillonite-collagen composite hydrogel, and good results are obtained.

为实现发明目的之一，提供制备方法的技术方案：In order to realize one of the purposes of the invention, the technical scheme of the preparation method is provided:

一种蒙脱土-胶原蛋白复合水凝胶的制备方法，以危险废弃物含铬废革屑为原料，通过水解、改性、交联的过程，包括以下步骤：A method for preparing a montmorillonite-collagen composite hydrogel comprises the following steps:

1）胶原蛋白水解液的制备：含铬废革屑在100-105℃烘至绝干，含铬废革屑、蔗糖、氧化钙、水按照质量比(100~150):(1~2):(4~8):(600~1000)添加，在70~90℃下搅拌5~8h后趁热抽滤，得到胶原蛋白水解液；1) Preparation of collagen hydrolyzate: Bake chromium-containing waste leather scraps at 100-105°C to dryness, and chromium-containing scrap leather scraps, sucrose, calcium oxide, and water are in a mass ratio (100~150):(1~2) :(4~8):(600~1000) add, stir at 70~90°C for 5~8h and filter while hot to obtain collagen hydrolyzate;

2）蒙脱土-胶原蛋白复合水凝胶的制备：将蒙脱土和胶原蛋白水解液在40~60℃下混合并搅拌20~50min，以10s/d的速度滴加浓度为20%的戊二醛溶液，滴加完后再搅拌5~20min后于40~70℃下烘干，即得固体蒙脱土-胶原蛋白复合水凝胶，2) Preparation of montmorillonite-collagen composite hydrogel: Mix montmorillonite and collagen hydrolyzate at 40-60 °C and stir for 20-50 min, and dropwise add 20% of montmorillonite at a speed of 10s/d. The glutaraldehyde solution is added dropwise and then stirred for 5-20 minutes and then dried at 40-70°C to obtain a solid montmorillonite-collagen composite hydrogel.

其中，蒙脱土、胶原蛋白水解液中的胶原蛋白、戊二醛溶液的质量比为(5~30):(10~25):(0.1~1.0)。Wherein, the mass ratio of montmorillonite, collagen in the collagen hydrolyzate, and glutaraldehyde solution is (5~30):(10~25):(0.1~1.0).

优选，步骤（2）中通过超声、电刺激、剪切或涡旋振荡的方式提高搅拌效果加快成凝胶的速度。Preferably, in step (2), the stirring effect is improved by means of ultrasound, electrical stimulation, shearing or vortex oscillation, and the speed of gel formation is accelerated.

为实现发明目的之二，提供产物的技术方案：In order to achieve the second purpose of the invention, the technical solution of the product is provided:

上述述制备方法所得的一种蒙脱土-胶原蛋白复合水凝胶。A montmorillonite-collagen composite hydrogel obtained by the above preparation method.

为实现发明目的之三，提供产物用途的技术方案：In order to achieve the third purpose of the invention, a technical solution for product use is provided:

上述蒙脱土-胶原蛋白复合水凝胶作为染料废水吸附剂的应用。The application of the above-mentioned montmorillonite-collagen composite hydrogel as an adsorbent for dye wastewater.

优选，所述复合水凝胶应用于染料废水中阳离子染料亚甲基蓝的吸附。Preferably, the composite hydrogel is applied to the adsorption of cationic dye methylene blue in dye wastewater.

有益效果：Beneficial effects:

本发明制备的蒙脱土-胶原蛋白复合水凝胶制备工艺简单，能够有效的对染料废水中的亚甲基蓝进行吸附，吸附前后的溶液中的亚甲基蓝的浓度从70.0mg/L变成5.4mg/L，吸附了64.6mg/L，吸附效率达到92.3%以上。而文献（Olusegun S J, Lima L F D, Mohallem ND. Enhancement of adsorption capacity of clay through spray drying andsurface modification process for wastewater treatment[J]. ChemicalEngineering Journal, 2018, 334: 1719-1728.）中单独采用蒙脱土的吸附仅为30mg/L，本专利制备出的蒙脱土-胶原蛋白复合水凝胶吸附性能更好，且复合水凝胶吸附染料后吸附剂与染料溶液更易分离。The montmorillonite-collagen composite hydrogel prepared by the invention has a simple preparation process, can effectively adsorb methylene blue in dye wastewater, and the concentration of methylene blue in the solution before and after adsorption changes from 70.0 mg/L to 5.4 mg/L , adsorbed 64.6 mg/L, and the adsorption efficiency reached more than 92.3%. In the literature (Olusegun S J, Lima L F D, Mohallem ND. Enhancement of adsorption capacity of clay through spray drying and surface modification process for wastewater treatment[J]. Chemical Engineering Journal, 2018, 334: 1719-1728.), montmorillonite was used alone. The adsorption is only 30mg/L, the montmorillonite-collagen composite hydrogel prepared by this patent has better adsorption performance, and the adsorbent and the dye solution are easier to separate after the composite hydrogel adsorbs the dye.

本发明制备的蒙脱土-胶原蛋白复合水凝胶具有非常好的机械性能，能够解决在吸附过程中面临不同的机械应力条件，如振动和碰撞等。The montmorillonite-collagen composite hydrogel prepared by the invention has very good mechanical properties, and can solve different mechanical stress conditions, such as vibration and collision, in the adsorption process.

本发明制备的复合水凝胶能够在广泛的pH条件下，以及非极性溶液（葡萄糖溶液）和离子型溶液（氯化钠溶液）中均能稳定的存在均能具有良好的溶胀性能，能够满足工业废水典型复杂性的多功能处理的需求。特别是在处理阳离子染料废水时，蒙脱土-胶原蛋白复合水凝胶的便利性和化学性质的稳定性都是处理然染料废水的重要优势，而且烘干后的蒙脱土-胶原蛋白水凝胶能够根据其物理特性，可以容易的制备适合大小，用于处理厂的狭窄，小或更大的角落或空间中分层或开槽等。The composite hydrogel prepared by the invention can stably exist in a wide range of pH conditions, as well as in non-polar solution (glucose solution) and ionic solution (sodium chloride solution), has good swelling performance, and can Meets the needs of multifunctional treatment of the typical complexity of industrial wastewater. Especially in the treatment of cationic dye wastewater, the convenience of montmorillonite-collagen composite hydrogel and the stability of chemical properties are important advantages for the treatment of natural dye wastewater, and the dried montmorillonite-collagen water Gels can be easily sized to suit their physical properties, layered or slotted in narrow, small or larger corners or spaces of treatment plants, etc.

本发明采用以废治废的方法，既减少了制革固体废物的污染，又制备出能够用于处理染料污染的水凝胶，对环境保护和皮革废弃物资源化利用提供了有效途径。The invention adopts the method of treating waste with waste, which not only reduces the pollution of leather-making solid waste, but also prepares a hydrogel that can be used to deal with dye pollution, and provides an effective way for environmental protection and leather waste resource utilization.

附图说明Description of drawings

附图用来提供对本发明技术方案的进一步理解，并且构成说明书的一部分，与本申请的具体实施方式一起用于解释本发明的技术方案，并不构成对本发明技术方案的限制。The accompanying drawings are used to provide a further understanding of the technical solutions of the present invention, and constitute a part of the specification. They are used to explain the technical solutions of the present invention together with the specific embodiments of the present application, and do not limit the technical solutions of the present invention.

图1为实施例1不同pH值下蒙脱土-胶原蛋白复合水凝胶的溶胀性能。Figure 1 shows the swelling properties of the montmorillonite-collagen composite hydrogel at different pH values in Example 1.

图2为实施例1不同溶液中蒙脱土-胶原蛋白复合水凝胶的溶胀性能。Figure 2 shows the swelling properties of montmorillonite-collagen composite hydrogels in different solutions of Example 1.

图3为实施例1对亚甲基蓝溶液的循环吸附结果。Fig. 3 is the cycle adsorption result of the methylene blue solution of Example 1.

图4为实施例2对亚甲基蓝溶液的循环吸附结果。Figure 4 is the cyclic adsorption result of Example 2 on methylene blue solution.

图5为实施例3对亚甲基蓝溶液的循环吸附结果。Figure 5 is the cyclic adsorption result of Example 3 on methylene blue solution.

图6为实施例4对亚甲基蓝溶液的循环吸附结果。FIG. 6 is the cyclic adsorption result of Example 4 on methylene blue solution.

图7为蒙脱土(a) 与本发明烘干后的蒙脱土-胶原蛋白复合水凝胶(b)的SEM图片。FIG. 7 is a SEM picture of the montmorillonite (a) and the montmorillonite-collagen composite hydrogel (b) after drying according to the present invention.

具体实施方式Detailed ways

下面将参照附图对本发明进行更详细的描述，其中表示了本发明的优选实施例，应该理解本领域技术人员可以修改在此描述的本发明而仍然实现本发明的有益效果。因此，下列描述应当被理解为对于本领域技术人员的广泛知道，而并不作为对本发明的限制。The present invention will be described in more detail below with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it should be understood that those skilled in the art can modify the invention described herein and still achieve the beneficial effects of the invention. Therefore, the following description should be construed as widely known to those skilled in the art and not as a limitation of the present invention.

为使本发明的目的、特征更明显易懂，下面结合附图对本发明的具体实施方式作进一步的说明。需要说明的是，附图均采用非常简化的形式且均使用非精准的比率，仅用于方便、清晰地辅助说明本发明实施例的目的。In order to make the objects and features of the present invention more clearly understood, the specific embodiments of the present invention will be further described below with reference to the accompanying drawings. It should be noted that, the accompanying drawings are all in a very simplified form and use inaccurate ratios, and are only used for the purpose of assisting in explaining the embodiments of the present invention conveniently and clearly.

在举例对本发明说明之前，阐述本发明所制备的蒙脱土-胶原蛋白复合水凝胶的实质性特点在于将含铬皮革额废弃物中的胶原蛋白水解成大分子的胶原蛋白水解液，通过钙离子与胶原蛋白多肽的螯合得到低温下直接变成胶状的可逆胶原蛋白水凝胶，然后通过可逆胶原蛋白水凝胶与戊二醛和蒙脱土进行交联得到具有吸附性的不可逆的蒙脱土-胶原蛋白复合凝胶。而且，本发明的脱土-胶原蛋白复合凝胶不仅能够将染料固定或吸附（吸附效率达到92.3%以上）且具有良好的溶胀性能，克服了现有技术中蒙脱土吸附剂难以回收的技术问题。Before explaining the present invention by way of example, the essential feature of the montmorillonite-collagen composite hydrogel prepared by the present invention is that the collagen in the chromium-containing leather waste is hydrolyzed into a macromolecular collagen hydrolyzate, and the The chelation of calcium ions and collagen polypeptides leads to reversible collagen hydrogels that directly become gelatinous at low temperature, and then cross-linking of reversible collagen hydrogels with glutaraldehyde and montmorillonite to obtain irreversible adsorbents montmorillonite-collagen composite gel. Moreover, the de-soil-collagen composite gel of the present invention can not only fix or adsorb dyes (the adsorption efficiency reaches more than 92.3%) but also has good swelling performance, which overcomes the difficulty in recovering the montmorillonite adsorbent in the prior art. question.

实施例1Example 1

(1)胶原蛋白水解液的制备：首先，含铬废革屑在105℃左右烘至质量不在变化。依次将将100g含铬废革屑、1g蔗糖、4g氧化钙、750g水加入三口烧瓶中，在90℃下搅拌6h。趁热抽滤，得到可逆的胶原蛋白水凝胶。(1) Preparation of collagen hydrolyzate: First, the chrome-containing waste leather scraps are baked at about 105°C until the quality does not change. Add 100 g of chromium-containing waste leather scraps, 1 g of sucrose, 4 g of calcium oxide, and 750 g of water into a three-necked flask in turn, and stir at 90° C. for 6 hours. Filter while hot to obtain reversible collagen hydrogels.

(2)胶原蛋白水解液中游离氨基的测定：用电子天平称量0.32795g L-亮氨酸于烧杯中，加入蒸馏水搅拌将其全部溶解，并转移至1000mL容量瓶中定容。再分别移取0、0.2、0.4、0.6、0.8、1.0mL该溶液于6支25mL比色皿中并定容；用电子天平称取1.9068g四硼酸钠、0.1g十二烷基硫酸钠（SDS）、0.088g二硫代苏糖醇（DTT）于烧杯中，加入水并将其放在电炉上加热并用玻璃棒不断搅拌直至全部溶解。再精确地称量0.080g邻苯二甲醛（OPA）于烧杯中，在避光处用移液管移取2mL无水乙醇至烧杯中，避光搅拌溶解，在避光处将全部的溶解液依次转移到100mL的棕色容量瓶中并定容；开紫外可见分光光度计波长调至340nm，移取0.4 mL蒸馏水、3mLOPA溶液于比色皿中，作为空白对照组，调吸光度0，透射比100%。移取0.4mL的胶原蛋白、3mL的OPA溶液到比色皿中，同时用秒表开始计时，2 min后，记录数据，测定胶原蛋白水解液中游离氨基的浓度为2.602×10^-7mol/mL，通过测定可逆水凝胶中游离氨基的含量确定下一步中蒙脱土和戊二醛的用量。(2) Determination of free amino groups in collagen hydrolyzate: Weigh 0.32795g of L-leucine into a beaker with an electronic balance, add distilled water and stir to dissolve it all, and transfer it to a 1000mL volumetric flask to constant volume. Thenpipette 0, 0.2, 0.4, 0.6, 0.8, 1.0 mL of this solution into 6 25 mL cuvettes and dilute to volume; weigh 1.9068 g of sodium tetraborate, 0.1 g of sodium dodecyl sulfate ( SDS), 0.088g dithiothreitol (DTT) in a beaker, add water and heat it on an electric stove with constant stirring with a glass rod until all dissolved. Then accurately weigh 0.080g o-phthalaldehyde (OPA) in a beaker, pipette 2mL of absolute ethanol into the beaker in a dark place, stir to dissolve in the dark place, and put all the solution in a dark place. Transfer to a 100mL brown volumetric flask in turn and set the volume; turn on the UV-Vis spectrophotometer and adjust the wavelength to 340nm, pipette 0.4mL of distilled water and 3mLOPA solution into a cuvette, as a blank control group, adjust the absorbance to 0 and the transmittance to 100 %. Pipette 0.4 mL of collagen and 3 mL of OPA solution into the cuvette, and start timing with a stopwatch. After 2 minutes, record the data and determine the concentration of free amino groups in the collagen hydrolyzate solution to be 2.602×10^-7 mol/mL , and determine the amount of montmorillonite and glutaraldehyde in the next step by measuring the content of free amino groups in the reversible hydrogel.

(3)蒙脱土-胶原蛋白复合水凝胶的制备：将0.5g蒙脱土和10mL固含量为20%的胶原蛋白水解液于50℃下搅拌20分钟，使蒙脱土与胶原蛋白水解液充分混合均匀。将体积为0.2mL的戊二醛（20%溶液），逐滴加入蒙脱土与胶原蛋白水解液的混合溶液中，边滴加边搅拌，滴加完后再搅拌10分钟，于60℃下烘干。(3) Preparation of montmorillonite-collagen composite hydrogel: 0.5 g of montmorillonite and 10 mL of collagen hydrolyzate with a solid content of 20% were stirred at 50°C for 20 minutes to hydrolyze the montmorillonite and collagen. The liquid is thoroughly mixed. Add 0.2 mL of glutaraldehyde (20% solution) dropwise to the mixed solution of montmorillonite and collagen hydrolyzate, stir while adding dropwise, and then stir for 10 minutes after the dropwise addition, at 60°C drying.

(4)亚甲基蓝的吸附实验：将150mg烘干后的蒙脱土-胶原蛋白复合水凝胶加入50mL pH为3.0(柠檬酸-磷酸氢二钠缓冲溶液)，70.0mg/L的亚甲基蓝溶液，在30℃于振荡床中振荡吸附60分钟，离心过滤，取上清液通过紫外-可见光分光光度计于665nm处测定溶液的吸光度。如表1所示，亚甲基蓝吸附前后的浓度从70.0mg/L变成8.4mg/L，吸附率为88%。(4) Adsorption experiment of methylene blue: 150 mg of dried montmorillonite-collagen composite hydrogel was added to 50 mL of methylene blue solution with a pH of 3.0 (citric acid-disodium hydrogen phosphate buffer solution) and 70.0 mg/L. The solution was shaken and adsorbed in a shaking bed at 30°C for 60 minutes, filtered by centrifugation, and the supernatant was taken to measure the absorbance of the solution at 665 nm by a UV-Vis spectrophotometer. As shown in Table 1, the concentration of methylene blue before and after adsorption changed from 70.0 mg/L to 8.4 mg/L, and the adsorption rate was 88%.

（5）通过不同时间吸水率的变化对本例的蒙脱土-胶原蛋白复合水凝胶的溶胀性进行测试。测试结果如图1所示：本例的蒙脱土-胶原蛋白复合水凝胶在不同pH值下均具有良好的溶胀性，表明制备的水凝胶能够应用于酸碱条件下。(5) The swelling property of the montmorillonite-collagen composite hydrogel of this example was tested by changing the water absorption rate at different times. The test results are shown in Figure 1: the montmorillonite-collagen composite hydrogel of this example has good swelling properties at different pH values, indicating that the prepared hydrogel can be applied to acid-base conditions.

进一步的，在不同溶液中（生理盐水、葡萄糖、蒸馏水）对本例的蒙脱土-胶原蛋白复合水凝胶溶胀性能测试。测试结果如图2所示：与蒸馏水的溶液相比，蒙脱土-胶原蛋白复合水凝胶在氯化钠和葡萄糖溶液中具有更好的溶胀性，说明本发明的蒙脱土-胶原蛋白复合水凝胶能够在复杂体系中的应用。Further, the swelling properties of the montmorillonite-collagen composite hydrogel of this example were tested in different solutions (physiological saline, glucose, distilled water). The test results are shown in Figure 2: Compared with the solution of distilled water, the montmorillonite-collagen composite hydrogel has better swelling properties in sodium chloride and glucose solutions, indicating that the montmorillonite-collagen of the present invention Composite hydrogels can be used in complex systems.

（6）对本例的蒙脱土-胶原蛋白复合水凝胶的循环吸附性进行测试。本例的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝溶液的循环吸附结果如图3所示，在使用四次循环之后吸附率为80%，说明该材料具有良好的重复使用性能，原因在于蒙脱土的加入提高了整个蒙脱土-胶原蛋白复合水凝胶的器械强度，因此本发明的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝溶液的吸附可以循环使用。(6) Test the cyclic adsorption of the montmorillonite-collagen composite hydrogel of this example. The cyclic adsorption results of the montmorillonite-collagen composite hydrogel to the methylene blue solution in this example are shown in Figure 3. After four cycles of use, the adsorption rate is 80%, indicating that the material has good reusability. The reason is that The addition of montmorillonite improves the device strength of the entire montmorillonite-collagen composite hydrogel, so the adsorption of the methylene blue solution by the montmorillonite-collagen composite hydrogel of the present invention can be recycled.

实施例二Embodiment 2

(1)胶原蛋白水解液的制备：首先，含铬废革屑在105℃左右烘至质量不在变化。依次将将110g含铬废革屑、1.5g蔗糖、6g氧化钙、800g水加入三口烧瓶中，在80℃下搅拌6h。趁热抽滤，得到胶原蛋白水解液。(1) Preparation of collagen hydrolyzate: First, the chrome-containing waste leather scraps are baked at about 105°C until the quality does not change. Add 110 g of chromium-containing waste leather scraps, 1.5 g of sucrose, 6 g of calcium oxide, and 800 g of water into a three-necked flask in turn, and stir at 80° C. for 6 hours. Suction filtration while hot to obtain collagen hydrolyzate.

(2)胶原蛋白水解液中游离氨基的测定方法同实例一。(2) The method for measuring free amino groups in the collagen hydrolyzate is the same as that in Example 1.

(3)蒙脱土-胶原蛋白复合水凝胶的制备：将1.5g蒙脱土和10mL固含量为15%胶原蛋白水解液于50℃下搅拌40分钟，使蒙脱土与胶原蛋白水解液充分混合均匀。将体积为0.4mL的戊二醛（20%溶液），逐滴加入蒙脱土与胶原蛋白水解液的混合溶液中，边滴加边搅拌，滴加完后再搅拌15分钟，于50℃下烘干。(3) Preparation of montmorillonite-collagen composite hydrogel: 1.5 g of montmorillonite and 10 mL of collagen hydrolyzed solution with a solid content of 15% were stirred at 50 °C for 40 minutes to make the montmorillonite and collagen hydrolyzed solution Mix well. Add 0.4 mL of glutaraldehyde (20% solution) dropwise to the mixed solution of montmorillonite and collagen hydrolyzate, stir while adding dropwise, and then stir for 15 minutes after the dropwise addition, at 50°C drying.

(4)亚甲基蓝的吸附实验方法同实例一，亚甲基蓝吸附前后的浓度变化如表1所示。(4) The adsorption experiment method of methylene blue is the same as that of Example 1, and the concentration changes before and after the adsorption of methylene blue are shown in Table 1.

(5)通过不同时间吸水率的变化对本例的蒙脱土-胶原蛋白复合水凝胶的溶胀性进行测试。测试结果显示：本例的蒙脱土-胶原蛋白复合水凝胶在pH=3-12的范围内时在50-300min内溶胀性均保持在160-330%以内，表明本发明的蒙脱土-胶原蛋白复合水凝胶在酸碱条件下均能应用。(5) The swelling property of the montmorillonite-collagen composite hydrogel of this example was tested by changing the water absorption rate at different times. The test results show that the swellability of the montmorillonite-collagen composite hydrogel of this example is kept within 160-330% within 50-300min in the range of pH=3-12, indicating that the montmorillonite of the present invention -Collagen composite hydrogel can be applied under both acid and alkali conditions.

进一步的，在不同溶液中（生理盐水、葡萄糖、蒸馏水）对本例的蒙脱土-胶原蛋白复合水凝胶溶胀性能测试。测试结果与实施例1的测试结果类似：与蒸馏水的溶液相比，蒙脱土-胶原蛋白复合水凝胶在氯化钠和葡萄糖溶液中具有更好的溶胀性，说明本发明的蒙脱土-胶原蛋白复合水凝胶能够在复杂体系中的应用。Further, the swelling properties of the montmorillonite-collagen composite hydrogel of this example were tested in different solutions (physiological saline, glucose, distilled water). The test results are similar to the test results of Example 1: compared with the solution of distilled water, the montmorillonite-collagen composite hydrogel has better swelling properties in sodium chloride and glucose solutions, indicating that the montmorillonite of the present invention has better swelling properties. -Collagen composite hydrogels can be used in complex systems.

（6）对本例的蒙脱土-胶原蛋白复合水凝胶的循环吸附性进行测试。本例的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝溶液的循环吸附结果如图4所示，在使用四次循环之后吸附率为78%，说明该材料具有良好的重复使用性能。(6) Test the cyclic adsorption of the montmorillonite-collagen composite hydrogel of this example. The cyclic adsorption results of the montmorillonite-collagen composite hydrogel to the methylene blue solution in this example are shown in Figure 4. After four cycles of use, the adsorption rate is 78%, indicating that the material has good reuse performance.

实施例三Embodiment 3

(1)胶原蛋白水解液的制备：首先，含铬废革屑在105℃左右烘至质量不在变化。依次将将140g含铬废革屑、2g蔗糖、8g氧化钙、1000g水加入三口烧瓶中，在90℃下搅拌5h。趁热抽滤，得到胶原蛋白水解液。(1) Preparation of collagen hydrolyzate: First, the chrome-containing waste leather scraps are baked at about 105°C until the quality does not change. 140g of chromium-containing waste leather scraps, 2g of sucrose, 8g of calcium oxide, and 1000g of water were sequentially added to the three-necked flask, and stirred at 90° C. for 5h. Suction filtration while hot to obtain collagen hydrolyzate.

(3)蒙脱土-胶原蛋白复合水凝胶的制备：将1.0g蒙脱土和10mL固含量为25%的胶原蛋白水解液于60℃下搅拌25分钟，使蒙脱土与胶原蛋白水解液充分混合均匀。将体积为0.25mL的戊二醛（20%溶液），逐滴加入蒙脱土与胶原蛋白水解液的混合溶液中，边滴加边搅拌，滴加完后再搅拌10分钟，于60℃下烘干。(3) Preparation of montmorillonite-collagen composite hydrogel: 1.0 g of montmorillonite and 10 mL of collagen hydrolyzate with a solid content of 25% were stirred at 60°C for 25 minutes to hydrolyze the montmorillonite and collagen. The liquid is thoroughly mixed. Add 0.25mL of glutaraldehyde (20% solution) dropwise to the mixed solution of montmorillonite and collagen hydrolyzate, stir while adding dropwise, and then stir for 10 minutes after the dropwise addition, at 60°C drying.

(5)通过不同时间吸水率的变化对本例的蒙脱土-胶原蛋白复合水凝胶的溶胀性进行测试。测试结果显示：本例的蒙脱土-胶原蛋白复合水凝胶在pH=3-12的范围内时在50-300min内溶胀性均保持在170-350%以内，表明本发明的蒙脱土-胶原蛋白复合水凝胶在酸碱条件下均能应用。(5) The swelling property of the montmorillonite-collagen composite hydrogel of this example was tested by changing the water absorption rate at different times. The test results show that the swellability of the montmorillonite-collagen composite hydrogel of this example is maintained within 170-350% within 50-300 min in the range of pH=3-12, indicating that the montmorillonite of the present invention -Collagen composite hydrogel can be applied under both acid and alkali conditions.

进一步的，在不同溶液中（生理盐水、葡萄糖、蒸馏水）对本例的蒙脱土-胶原蛋白复合水凝胶溶胀性能测试。测试结果显示：50-300min内，蒙脱土-胶原蛋白复合水凝胶在氯化钠、葡萄糖溶液和蒸馏水的溶胀性分别为260-300%、260-380%和220-300%，说明本发明的蒙脱土-胶原蛋白复合水凝胶能够在复杂体系中的应用。Further, the swelling properties of the montmorillonite-collagen composite hydrogel of this example were tested in different solutions (physiological saline, glucose, distilled water). The test results show that within 50-300min, the swelling properties of montmorillonite-collagen composite hydrogel in sodium chloride, glucose solution and distilled water are 260-300%, 260-380% and 220-300%, respectively. The invented montmorillonite-collagen composite hydrogel can be used in complex systems.

（6）对本例的蒙脱土-胶原蛋白复合水凝胶的循环吸附性进行测试。本例的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝溶液的循环吸附结果如图5所示，在使用四次循环之后吸附率为80%，说明该材料具有良好的重复使用性能。(6) Test the cyclic adsorption of the montmorillonite-collagen composite hydrogel of this example. The cyclic adsorption results of the montmorillonite-collagen composite hydrogel to the methylene blue solution in this example are shown in Figure 5. After four cycles of use, the adsorption rate is 80%, indicating that the material has good reuse performance.

实施例四Embodiment 4

(1)胶原蛋白水解液的制备：首先，含铬废革屑在105℃左右烘至质量不在变化。依次将将120g含铬废革屑、1.5g蔗糖、7g氧化钙、900g水加入三口烧瓶中，在85℃下搅拌8h。趁热抽滤，得到胶原蛋白水解液。(1) Preparation of collagen hydrolyzate: First, the chrome-containing waste leather scraps are baked at about 105°C until the quality does not change. 120g of chromium-containing waste leather scraps, 1.5g of sucrose, 7g of calcium oxide, and 900g of water were sequentially added to the three-necked flask, and stirred at 85° C. for 8h. Suction filtration while hot to obtain collagen hydrolyzate.

(3)蒙脱土-胶原蛋白复合水凝胶的制备：将2.0g蒙脱土和10mL固含量为20%胶原蛋白水解液于60℃下搅拌30分钟，使蒙脱土与胶原蛋白水解液充分混合均匀。将体积为0.3mL的戊二醛（20%溶液），逐滴加入蒙脱土与胶原蛋白水解液的混合溶液中，边滴加边搅拌，滴加完后再搅拌20分钟，于50℃下烘干。(3) Preparation of montmorillonite-collagen composite hydrogel: 2.0 g of montmorillonite and 10 mL of collagen hydrolyzed solution with a solid content of 20% were stirred at 60 °C for 30 minutes to make the montmorillonite and collagen hydrolyzed solution Mix well. Add 0.3 mL of glutaraldehyde (20% solution) dropwise to the mixed solution of montmorillonite and collagen hydrolyzate, stir while adding dropwise, and then stir for 20 minutes after the dropwise addition, at 50°C drying.

(5)通过不同时间吸水率的变化对本例的蒙脱土-胶原蛋白复合水凝胶的溶胀性进行测试。测试结果显示：本例的蒙脱土-胶原蛋白复合水凝胶在pH=3-12的范围内时在50-300min内溶胀性均保持在210-350%以内，表明本发明的蒙脱土-胶原蛋白复合水凝胶在酸碱条件下均能应用。(5) The swelling property of the montmorillonite-collagen composite hydrogel of this example was tested by changing the water absorption rate at different times. The test results show that the swellability of the montmorillonite-collagen composite hydrogel of this example is maintained within 210-350% within 50-300 min in the range of pH=3-12, indicating that the montmorillonite of the present invention -Collagen composite hydrogel can be applied under both acid and alkali conditions.

进一步的，在不同溶液中（生理盐水、葡萄糖、蒸馏水）对本例的蒙脱土-胶原蛋白复合水凝胶溶胀性能测试。测试结果显示：50-300min内，蒙脱土-胶原蛋白复合水凝胶在氯化钠、葡萄糖溶液和蒸馏水的溶胀性分别为280-330%、310-460%和220-280%，说明本发明的蒙脱土-胶原蛋白复合水凝胶能够在复杂体系中的应用。Further, the swelling properties of the montmorillonite-collagen composite hydrogel of this example were tested in different solutions (physiological saline, glucose, distilled water). The test results show that within 50-300min, the swelling properties of montmorillonite-collagen composite hydrogel in sodium chloride, glucose solution and distilled water are 280-330%, 310-460% and 220-280%, respectively. The invented montmorillonite-collagen composite hydrogel can be used in complex systems.

（6）对本例的蒙脱土-胶原蛋白复合水凝胶的循环吸附性进行测试。本例的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝溶液的循环吸附结果如图6所示，在使用四次循环之后吸附率为81%，说明该材料具有良好的重复使用性能。(6) Test the cyclic adsorption of the montmorillonite-collagen composite hydrogel of this example. The cyclic adsorption results of the montmorillonite-collagen composite hydrogel to the methylene blue solution in this example are shown in Figure 6. After four cycles of use, the adsorption rate is 81%, indicating that the material has good reuse performance.

表1实施例1-4对蒙脱土-胶原蛋白复合水凝胶吸附效果Table 1 Examples 1-4 on the adsorption effect of montmorillonite-collagen composite hydrogel

实施例一至四证明本发明的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝具有优良吸附效果，吸附效果相比现有技术提高了1倍以上，而且吸附效率达到92.3%以上。分析原因在于本发明的蒙脱土-胶原蛋白复合水凝胶中富含大量活性位点能够用于吸附溶液中的亚甲基蓝，包括蒙脱土的表面电荷、胶原蛋白中氨基质子化的基团和胶原蛋白中羧基等官能团共同作用通过静电作用和范德华力来吸附溶液中的亚甲基蓝，并且，当溶液中亚甲基蓝的数量超过水凝胶所提供的活性位点时复合水凝胶不再具有吸附性能，表现为随着亚甲基蓝体积增加复合水凝胶的吸附能力不再变化。同时，如图7（a）也可以发现蒙脱土原为呈半细鳞片状集合体，颗粒大小均匀、片状且边缘呈卷曲状态，而本发明的蒙脱土-胶原蛋白复合水凝胶突出的结构特征在于胶原蛋白水凝胶与蒙脱土的交联使得胶原蛋白穿插于蒙脱土片层之间，如图7(b)所示，胶原蛋白吸附在蒙脱土颗粒表面包裹蒙脱土颗粒改善其疏水性，使的蒙脱土的边界光滑且没有明显的棱角，说明部分胶原蛋白插层在蒙脱土片层中增加了蒙脱土的层间距提高了吸附效果。Examples 1 to 4 prove that the montmorillonite-collagen composite hydrogel of the present invention has excellent adsorption effect on methylene blue, the adsorption effect is more than doubled compared with the prior art, and the adsorption efficiency reaches more than 92.3%. The reason for the analysis is that the montmorillonite-collagen composite hydrogel of the present invention is rich in a large number of active sites that can be used to adsorb methylene blue in solution, including the surface charge of montmorillonite, the protonated group of amino groups in collagen and Functional groups such as carboxyl groups in collagen work together to adsorb methylene blue in solution through electrostatic interaction and van der Waals force, and when the amount of methylene blue in solution exceeds the active sites provided by the hydrogel, the composite hydrogel no longer has adsorption properties. It is shown that the adsorption capacity of the composite hydrogel does not change with the increase of methylene blue volume. At the same time, as shown in Figure 7(a), it can also be found that the montmorillonite was originally a semi-fine scaly aggregate with uniform particle size, flaky and curled edges, while the montmorillonite-collagen composite hydrogel of the present invention The prominent structural feature is that the cross-linking of collagen hydrogel and montmorillonite makes collagen interspersed between montmorillonite sheets. As shown in Figure 7(b), collagen is adsorbed on the surface of montmorillonite particles and wraps montmorillonite. The exfoliated particles improved its hydrophobicity, making the boundary of the montmorillonite smooth and without obvious edges and corners, indicating that part of the collagen intercalation in the montmorillonite sheet increased the interlayer spacing of the montmorillonite and improved the adsorption effect.

此外，实施例一至四也证明本发明的蒙脱土-胶原蛋白复合水凝胶具有良好的溶胀性能且能稳定的存在于各种pH值酸碱条件，同时，本发明的蒙脱土-胶原蛋白复合水凝胶对亚甲基蓝溶液的吸附可以循环使用。In addition, Examples 1 to 4 also prove that the montmorillonite-collagen composite hydrogel of the present invention has good swelling properties and can stably exist in various pH values and acid-base conditions. At the same time, the montmorillonite-collagen of the present invention The adsorption of methylene blue solution by protein composite hydrogel can be recycled.

总之，将蒙脱土与胶原蛋白复合制备蒙脱土-胶原蛋白复合水凝胶的特点在于（1）两性高分子结构的胶原蛋白骨架能够在广泛的pH条件下进行吸附，大幅度拓展了其应用范围；（2）蒙脱土的成本低，表面积高，阳离子交换能力高，水凝胶解决了蒙脱土粉体材料难以回收的缺点；（3）蒙脱土对胶原蛋白水凝胶还存在增强增韧作用，可以提高水凝胶的物理机械性能；（4）蒙脱土-胶原蛋白复合水凝胶在吸附过程中能够有效抵抗离子和有机物的干扰，在复杂环境下不降低吸附效率。因此，本发明制备的蒙脱土-胶原蛋白复合水凝胶复合材料结合了两者的优点是一种高效经济的吸附材料，具有抗离子干扰、耐酸碱、可回收等优势。In conclusion, the characteristics of montmorillonite-collagen composite hydrogel prepared by compounding montmorillonite and collagen are that (1) the collagen skeleton of amphiphilic polymer structure can be adsorbed under a wide range of pH conditions, which greatly expands its Scope of application; (2) The cost of montmorillonite is low, the surface area is high, and the cation exchange capacity is high, and the hydrogel solves the disadvantage that the powder material of montmorillonite is difficult to recover; (3) The montmorillonite is also effective for collagen hydrogel. There is a strengthening and toughening effect, which can improve the physical and mechanical properties of the hydrogel; (4) The montmorillonite-collagen composite hydrogel can effectively resist the interference of ions and organic substances during the adsorption process, and does not reduce the adsorption efficiency in a complex environment . Therefore, the montmorillonite-collagen composite hydrogel composite material prepared by the present invention combines the advantages of both and is an efficient and economical adsorption material, which has the advantages of anti-ion interference, acid and alkali resistance, and recyclability.

最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, it should be noted that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, the The technical solutions described in the foregoing embodiments may be modified, or some technical features thereof may be equivalently replaced. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of montmorillonite-collagen composite hydrogel is characterized in that hazardous waste chromium-containing waste leather scraps are used as raw materials, and the montmorillonite-collagen composite hydrogel is prepared through hydrolysis, modification and crosslinking, and comprises the following steps:

preparing collagen hydrolysate: drying the chromium-containing waste leather scraps at 105 ℃ in a temperature range of 100-;

preparing montmorillonite-collagen composite hydrogel: mixing montmorillonite and collagen hydrolysate prepared in the step (1) at 40-60 ℃, stirring for 20-50 min, dripping 20% glutaraldehyde solution at the speed of 10s/d, stirring for 5-20 min after dripping, drying at 40-70 ℃ to obtain solid montmorillonite-collagen composite hydrogel,

wherein the mass ratio of the montmorillonite to the collagen in the collagen hydrolysate to the glutaraldehyde solution is (5-30): (10-25): 0.1-1).

2. The method for preparing montmorillonite-collagen composite hydrogel according to claim 1, wherein the stirring in step (2) is performed by ultrasonic, electrical stimulation, shearing or vortex oscillation to accelerate the gelation speed.

3. A montmorillonite-collagen composite hydrogel obtained by the preparation method of claim 1 or 2.

4. The use of the montmorillonite-collagen composite hydrogel as claimed in claim 3 as an adsorbent for dye wastewater.

5. The application of the montmorillonite-collagen composite hydrogel according to claim 4, wherein the composite hydrogel is applied to adsorption of a cationic dye methylene blue in dye wastewater.