技术领域technical field
本发明涉及一种处理亚甲基蓝染料废水的方法，具体是在水热固化的硅藻土基多孔吸附剂上负载酵母处理亚甲基蓝染料废水，属于染料废水处理技术领域。The invention relates to a method for treating methylene blue dye wastewater, in particular loading yeast on a hydrothermally solidified diatomite-based porous adsorbent to treat methylene blue dye wastewater, and belongs to the technical field of dye wastewater treatment.
背景技术Background technique
随着染料与印染工业的不断发展，有机染料废水已经成为主要的水体污染源之一。染料废水成分复杂，有机物含量大，且大多数是以苯、萘、蒽、醌等芳香基团为母体的形式存在，具有色度深、毒性强、难降解等特点，对水环境构成了日益严重的威胁。同时，当含有染料的废水进入自然界水域中时由于染料的色度深，因此很少的含量也会产生非常显著的颜色，导致水体色泽污染，不但会对人类或动物的视觉系统造成冲击，而且会降低阳光到达水中或水底的强度，影响水体中绿色植物的光合作用，最终导致水体生态系统恶化，造成生物大量死亡。因此染料废水的综合治理已经成为当前亟待解决的问题之一。With the continuous development of dye and dyeing industry, organic dye wastewater has become one of the main sources of water pollution. Dye wastewater has complex components and a large content of organic matter, and most of them exist in the form of aromatic groups such as benzene, naphthalene, anthracene, and quinone. They have the characteristics of deep color, strong toxicity, and refractory degradation. serious threat. At the same time, when the dye-containing wastewater enters natural waters, due to the deep color of the dye, a very small content will produce a very significant color, resulting in color pollution of the water body, which will not only have an impact on the visual system of humans or animals, but also It will reduce the intensity of sunlight reaching the water or the bottom, affect the photosynthesis of green plants in the water body, and eventually lead to the deterioration of the water body ecosystem and cause a large number of biological deaths. Therefore, the comprehensive treatment of dye wastewater has become one of the problems to be solved urgently.
亚甲基蓝（MB）是一种硫氮杂苯染料，广泛用于棉花，木头及丝绸着色，是最为常见的染料，但它很难被一些常规的方法所降解，易引起严重的环境污染问题。目前有机染料废水包括亚甲基蓝染料废水的处理主要有氧化法、光催化法、混凝法、膜分离法及吸附法等。以上处理方法中，氧化技术成本高，常用氧化剂存在氧化能力差、存在选择性氧化等特点；光催化法最大的不足是需要光源照射体系、在应用中受到光源和天气影响。混凝法的运行费用较高，处理泥渣量大且处理困难。膜分离法在染料处理中去除率高，工艺简单，但是目前膜的生产成本非常高，操作压力大，很难进行大规模的工业化应用。吸附法所需吸附剂用量大，部分吸附剂如活性炭的成本很高，很难进行大规模的污水处理。因此，开发一种简单而且高效处理亚甲基蓝染料废水的方法具有重要的意义。Methylene blue (MB) is a thiazepine dye widely used in the coloring of cotton, wood and silk. It is the most common dye, but it is difficult to be degraded by some conventional methods, and it is easy to cause serious environmental pollution problems. At present, the treatment of organic dye wastewater including methylene blue dye wastewater mainly includes oxidation method, photocatalysis method, coagulation method, membrane separation method and adsorption method. Among the above treatment methods, the cost of oxidation technology is high, and commonly used oxidants have the characteristics of poor oxidation ability and selective oxidation; the biggest disadvantage of photocatalytic method is that it requires a light source irradiation system and is affected by light source and weather in application. The operating cost of the coagulation method is high, and the amount of sludge to be processed is large and difficult to handle. Membrane separation method has a high removal rate and simple process in dye treatment, but the current membrane production cost is very high and the operating pressure is high, so it is difficult to carry out large-scale industrial application. The adsorption method requires a large amount of adsorbents, and some adsorbents such as activated carbon are very expensive, making it difficult to carry out large-scale sewage treatment. Therefore, it is of great significance to develop a simple and efficient method for treating methylene blue dye wastewater.
发明内容Contents of the invention
本发明的目的在于提供一种无需光照、无二次污染、常温下可达到吸附、降解、除去亚甲基蓝废水污染的方法，具体是利用水热技术固化硅藻土基吸附材料并负载酵母处理染料污水的方法。The purpose of the present invention is to provide a method that does not require light, has no secondary pollution, and can achieve adsorption, degradation, and removal of methylene blue wastewater pollution at room temperature. Specifically, it uses hydrothermal technology to solidify diatomite-based adsorption materials and load yeast to treat dye wastewater. Methods.
为实现上述目的，本发明观察发现，自然界水田中土壤的多孔结构中存在数量众多的土壤微生物和土壤酶，它们有助于污染物的吸附与降解，对于水田中的田间水有着优越的净化功能，这种水田土壤对水的自净化功能实际上是一种矿物和微生物相互作用，是无机界与有机界相互交叉渗透的结果。但这种土壤作为水净化剂在实际应用中仍存在很大的局限性，并且土壤的自净化能力也远不如某些无机矿物材料，例如硅藻土、沸石、海泡石等。但在环境工程中，它们吸附污染物后难以与净化水分离，使得体系的吸附剂和污水一起转化为污泥，使得污泥产生量大大增加。很明显，将这些矿物材料造粒成为具有一定性质的材料是解决泥化问题的方法之一。因此，我们使用具有自净化性能的矿物材料为原料，制备成具有优越自净化性能的多孔吸附材料颗粒载体，并在该吸附剂的多孔结构中引入具有特殊功能的酶等，使得这种生物亲和的环境材料作为多孔微生物载体在污水处理方面发挥重要作用。In order to achieve the above object, the present invention finds that there are a large number of soil microorganisms and soil enzymes in the porous structure of the soil in the paddy fields in nature, which contribute to the adsorption and degradation of pollutants, and have a superior purification function for the field water in the paddy fields , the self-purification function of this paddy field soil to water is actually a kind of interaction between minerals and microorganisms, which is the result of the cross-penetration of inorganic and organic realms. However, this kind of soil still has great limitations in practical application as a water purifier, and the self-purification ability of soil is far inferior to some inorganic mineral materials, such as diatomaceous earth, zeolite, sepiolite, etc. However, in environmental engineering, it is difficult to separate them from purified water after adsorbing pollutants, so that the adsorbent and sewage in the system are converted into sludge together, which greatly increases the amount of sludge produced. Obviously, granulating these mineral materials into materials with certain properties is one of the methods to solve the problem of mudification. Therefore, we use mineral materials with self-purification properties as raw materials to prepare porous adsorption material particle carriers with superior self-purification properties, and introduce enzymes with special functions into the porous structure of the adsorbent, making this biological affinity And environmental materials play an important role in sewage treatment as porous microbial carriers.
水热固化/合成技术是一种低温合成技术，在合成过程中可以尽可能的保留原料无机矿物的原有结构，同时合成如C-S-H凝胶、托勃莫来石、方沸石等新矿物相，这些矿物相不仅能够提高了吸附载体的强度，也可以提高载体的多孔性能，有利于引入固定微生物，提高污水处理效率。Hydrothermal curing/synthesis technology is a low-temperature synthesis technology. During the synthesis process, the original structure of the raw inorganic minerals can be preserved as much as possible, and new mineral phases such as C-S-H gel, tober mullite, and analcite can be synthesized at the same time. These mineral phases can not only improve the strength of the adsorption carrier, but also improve the porous performance of the carrier, which is conducive to the introduction of immobilized microorganisms and the improvement of sewage treatment efficiency.
本发明的技术方案为：首先利用水热技术将硅藻土原料固化为可处理亚甲基蓝染料废水的高强度多孔吸附载体，然后经过培养和固定化技术将酵母负载到吸附载体上，从而提高处理亚甲基蓝染料废水的效率。具体工艺如下：The technical scheme of the present invention is as follows: firstly, the diatomite raw material is solidified into a high-strength porous adsorption carrier capable of treating methylene blue dye wastewater by using hydrothermal technology, and then the yeast is loaded on the adsorption carrier through culture and immobilization technology, thereby improving the efficiency of methylene blue treatment. Efficiency of dye wastewater. The specific process is as follows:
第一步，高强度硅藻土基多孔吸附剂的制备The first step, preparation of high-strength diatomite-based porous adsorbent
先将市售的硅藻土原土研磨，过80目筛并烘干；接着，将钙质原料、碱激发剂、水加入烘干的硅藻土中，混合均匀，在5～40MPa的压力下压制成型，得到成型后的样品；最后，将成型后的样品放入高压水热反应釜中，控制反应温度为100～200℃，反应时间1～48h，得到具有较高力学强度（简称高强度）硅藻土基多孔吸附剂；经检测，制得的高强度硅藻土基多孔吸附剂具有良好的抗水力剪切效果，其成分为反应后保留的硅藻土，以及水热反应合成的水化硅酸钙凝胶（C-S-H）、托勃莫来石（Tobermorite）、方沸石(ANA)中的一种或按任意比例组成的2种或3种。Grind the commercially available diatomite raw soil first, pass it through a 80-mesh sieve and dry it; then, add the calcareous raw material, alkali activator, and water into the dried diatomite, mix evenly, Press down to form a molded sample; finally, put the molded sample into a high-pressure hydrothermal reactor, control the reaction temperature to 100-200°C, and the reaction time to 1-48 hours to obtain a product with high mechanical strength (referred to as high Strength) diatomite-based porous adsorbent; after testing, the prepared high-strength diatomite-based porous adsorbent has good hydraulic shear resistance, and its composition is diatomite retained after reaction, and hydrothermal reaction synthesis Calcium silicate hydrate gel (C-S-H), Tobermorite (Tobermorite), analcime (ANA), or two or three of them in any proportion.
上述钙质原料、碱激发剂、水的加入质量分别为硅藻土质量的10～50%，5～20%，5～50%质量百分比；The added mass of the above-mentioned calcium raw material, alkali activator and water are respectively 10-50%, 5-20%, and 5-50% of the mass of diatomite;
上述钙质原料选自消石灰、石灰石、生石灰、白云石、钙长石中的一种或按任意比例组成的2-5种：The above-mentioned calcareous raw materials are selected from one of slaked lime, limestone, quicklime, dolomite and anorthite, or 2-5 kinds composed of any proportion:
上述碱激发剂选自氢氧化钠、偏铝酸钠、硅酸钠、偏硅酸钠、粉煤灰中的一种或按任意比例组成的2-5种：The above-mentioned alkali activator is selected from one of sodium hydroxide, sodium metaaluminate, sodium silicate, sodium metasilicate, fly ash or 2-5 kinds composed in any proportion:
第二步，硅藻土基多孔吸附剂负载酵母的制备The second step, the preparation of diatomaceous earth-based porous adsorbent loaded yeast
将第一步得到的高强度硅藻土基多孔吸附剂放入盛有液体培养基的锥形瓶，加入酵母粉，酵母粉的加入量为高强度硅藻土基多孔吸附剂质量的5%～20%质量百分比，调节pH值为5～8，在速度60rpm～120rpm的往复摇床上，15～35℃的恒温条件培养2h～48h，即得到负载酵母的硅藻土基多孔吸附剂；Put the high-strength diatomite-based porous adsorbent obtained in the first step into an Erlenmeyer flask filled with liquid medium, add yeast powder, and the addition of yeast powder is 5% of the quality of the high-strength diatomite-based porous adsorbent ～20% by mass, adjust the pH value to 5～8, and culture on a reciprocating shaker with a speed of 60rpm～120rpm at a constant temperature of 15～35°C for 2h～48h to obtain a diatomite-based porous adsorbent loaded with yeast;
所用的酵母粉为市售面包啤酒酵母粉，或市售用于处理染料废水的酵母粉；The yeast powder used is commercially available bread beer yeast powder, or commercially available yeast powder for treating dye wastewater;
第三步，亚甲基蓝染料废水处理The third step, methylene blue dye wastewater treatment
在每升浓度为100～1000mg/L的亚甲基蓝染料废水中加入第二步的负载酵母的硅藻土基多孔吸附剂1～10g，将pH调节到4～10，并在速度为60rpm～120rpm的往复摇床上，25～45℃下处理1h～48h，通过分光光度计法测量处理后亚甲基蓝废水的浓度，结果表明，亚甲基蓝染料的去除率超过90%，单位吸附量超过80mg/g。Add 1 to 10 g of the diatomite-based porous adsorbent loaded with yeast in the second step to the methylene blue dye wastewater with a concentration of 100 to 1000 mg/L per liter, adjust the pH to 4 to 10, and add it at a speed of 60 to 120 rpm. On a reciprocating shaker, treat at 25-45°C for 1h-48h, measure the concentration of methylene blue wastewater after treatment by spectrophotometer, the results show that the removal rate of methylene blue dye exceeds 90%, and the unit adsorption capacity exceeds 80mg/g.
与现有技术相比，本发明具有如下显著的优点和效果：Compared with the prior art, the present invention has the following significant advantages and effects:
1．由于本发明用水热反应制得的高强度硅藻土基多孔吸附剂，与传统烧结成型工艺相比，既能保留硅藻土原料本身固有的微孔结构，又能控制孔隙率、孔径大小、孔径分布以及比表面积，因此得到的高强度硅藻土基多孔吸附剂比原料硅藻土对亚甲基蓝染料的吸附、分解和降解等效果更佳。1. Due to the high-strength diatomite-based porous adsorbent prepared by the hydrothermal reaction of the present invention, compared with the traditional sintering molding process, it can not only retain the inherent microporous structure of the diatomite raw material itself, but also control the porosity, pore size, Pore size distribution and specific surface area, so the obtained high-strength diatomite-based porous adsorbent has better adsorption, decomposition and degradation effects on methylene blue dye than raw diatomite.
2．本发明水热合成的高强度硅藻土基多孔吸附剂在保留硅藻土良好吸附性的基础上，又生成了比表面积得到一定程度提升的水化硅酸钙凝胶（C-S-H）、托勃莫来石（Tobermorite）、方沸石(ANA)，说明吸附剂强度增加的同时，吸附性能也得到了提升，而且阳离子交换量也得到了明显提升，亚甲基蓝染料分子为阳离子型染料，因此，高强度硅藻土基多孔吸附剂对亚甲基蓝吸附有着不仅有利于染料分子的吸附处理，也有利于微生物（酵母）的负载的天然优势。2. The hydrothermally synthesized high-strength diatomite-based porous adsorbent of the present invention, on the basis of retaining the good adsorption properties of diatomite, also generates calcium silicate hydrate gel (C-S-H) with a specific surface area improved to a certain extent. Mullite (Tobermorite) and analcite (ANA) indicate that the adsorption performance has also been improved while the strength of the adsorbent has increased, and the cation exchange capacity has also been significantly improved. The methylene blue dye molecule is a cationic dye, so the high-strength Diatomaceous earth-based porous adsorbent has a natural advantage in the adsorption of methylene blue, which is not only beneficial to the adsorption treatment of dye molecules, but also beneficial to the loading of microorganisms (yeast).
3．本发明的高强度硅藻土基多孔吸附剂制备方法简单、节约能源，有很好的力学强度，在处理污水后不会生成污泥而造成二次污染，可重复使用多次。3. The high-strength diatomite-based porous adsorbent of the invention has a simple preparation method, saves energy, has good mechanical strength, does not generate sludge to cause secondary pollution after sewage treatment, and can be reused for many times.
4．本发明的高强度硅藻土基多孔吸附剂通过负载酵母后，结合酵母细胞的吸附和降解作用，大大提高了对染料污水的处理效果，该负载酵母的硅藻土基固体吸附剂的制备方法具有操作简单、无需复杂步骤、易大量生产、成本低廉的特点，因而适宜于对亚甲基蓝染料废水处理进行大规模工业化应用。4. After the high-strength diatomite-based porous adsorbent of the present invention is loaded with yeast, combined with the adsorption and degradation of yeast cells, the treatment effect on dye sewage is greatly improved. The preparation method of the diatomite-based solid adsorbent loaded with yeast The method has the characteristics of simple operation, no complicated steps, easy mass production and low cost, and thus is suitable for large-scale industrial application of methylene blue dye wastewater treatment.
5．本发明的亚甲基蓝染料的去除操作简单，能够在常温常压下、无需复杂步骤、无二次污染产生、运行费用低，亚甲基蓝染料去除率超过90%，有很高的实际应用价值。5. The removal operation of the methylene blue dye of the present invention is simple, can be performed at normal temperature and pressure, without complex steps, without secondary pollution, and low operating costs. The removal rate of the methylene blue dye exceeds 90%, and has high practical application value.
附图说明Description of drawings
图1为本发明的原料硅藻土的扫描电镜照片Fig. 1 is the scanning electron micrograph of raw material diatomite of the present invention
图2为本发明的水热合成的C-S-H硅藻土基多孔吸附剂与反应后保留的硅藻土的XRD图Fig. 2 is the XRD pattern of the C-S-H diatomite-based porous adsorbent of the present invention and the diatomite retained after the reaction
图3为本发明的水热合成的托勃莫来石硅藻土基多孔吸附剂与反应后保留的硅藻土的XRD图Fig. 3 is the XRD pattern of the tobermullite diatomite-based porous adsorbent and the diatomite retained after the reaction of the hydrothermal synthesis of the present invention
图4为本发明的水热合成的方沸石硅藻土基多孔吸附剂与反应后保留的硅藻土的XRD图Fig. 4 is the XRD pattern of the diatomite-based porous adsorbent of hydrothermal synthesis of the present invention and the diatomite retained after the reaction
图5为实施例1的水热合成的C-S-H为薄板板状结构的扫描电镜图Fig. 5 is the scanning electron micrograph of the C-S-H of the hydrothermal synthesis of embodiment 1 is the sheet-like structure
图6为实施例2的水热合成的托勃莫来为石针状结构的扫描电镜图Fig. 6 is the scanning electron micrograph of the hydrothermally synthesized tobermolite of embodiment 2 as stone needle-like structure
图7为实施例3的水热合成的方沸石为圆球状结构的扫描电镜图Fig. 7 is the scanning electron microscope picture that the analcime of the hydrothermal synthesis of embodiment 3 is spherical structure
图8为原料硅藻土及水热合成的不同硅藻土基多孔吸附剂的孔径分布图Figure 8 is the pore size distribution diagram of raw diatomite and different diatomite-based porous adsorbents synthesized by hydrothermal
图9为水热合成的C-S-H负载酵母与未负载酵母对亚甲基蓝吸附效果比较Figure 9 is a comparison of the adsorption effect of C-S-H loaded yeast and unloaded yeast on methylene blue by hydrothermal synthesis
图10为水热合成的托勃莫来石负载酵母与未负载酵母对亚甲基蓝吸附效果比较Figure 10 is a comparison of the adsorption effect of tobermullite-loaded yeast and unloaded yeast on methylene blue by hydrothermal synthesis
图11为水热合成的方沸石负载酵母与未负载酵母对亚甲基蓝的吸附效果比较Figure 11 is a comparison of the adsorption effect of hydrothermally synthesized analcite-loaded yeast and unloaded yeast on methylene blue
具体实施方式Detailed ways
实施例1Example 1
第一步，将3g烘干、过80目筛的硅藻土、1g市售工业级氢氧化钙、1ml去离子水混合均匀，将混合物用天津市思创精实科技发展有限公司W270×D200×H450规格的压片机，以20MPa压制成型，脱模，得到成型后的样品。将样品放入高压水热釜中，控制反应温度为200℃，反应时间为24h，水热反应后得到的样品用X射线衍射分析方法检测如图2所示：图2中（1）为硅藻土原料的XRD图，（2）为水热合成后的C-S-H的XRD图，从图中可以看出，硅藻土原料的主要成分为石英（Quartz）和蒙脱石（Montomorillonite），经过水热合成后，得到的硅藻土基多孔吸附剂的成分在保留了原硅藻土（石英）的基础上，又生成了优化矿物C-S-H。扫描电镜看到的C-S-H的结构如图5所示，C-S-H为薄板板状结构。检测该硅藻土基多孔吸附剂C-S-H的抗折强度为18.5Mpa，比表面积为43.08m2/g，请看后面所列的表1和表2。表1为硅藻土及水热合成的不同的硅藻土基多孔吸附剂的比表面积，表2为硅藻土及水热合成的不同的硅藻土基多孔吸附剂的阳离子交换量。In the first step, mix 3g of diatomite dried and passed through a 80-mesh sieve, 1g of commercially available industrial grade calcium hydroxide, and 1ml of deionized water. ×H450 specification tablet press, press molding at 20MPa, demould, obtain the sample after molding. Put the sample into a high-pressure hydrothermal kettle, control the reaction temperature to 200°C, and the reaction time to 24h. The sample obtained after the hydrothermal reaction is detected by X-ray diffraction analysis method as shown in Figure 2: (1) in Figure 2 is silicon The XRD pattern of diatomite raw material, (2) is the XRD pattern of CSH after hydrothermal synthesis. It can be seen from the figure that the main components of diatomite raw material are quartz (Quartz) and montmorillonite (Montomorillonite). After thermal synthesis, the composition of the obtained diatomite-based porous adsorbent is based on the retention of the original diatomite (quartz), and the optimized mineral CSH is generated. The structure of CSH seen by the scanning electron microscope is shown in Figure 5, and the CSH is a thin plate structure. The flexural strength of the diatomite-based porous adsorbent CSH is 18.5Mpa, and the specific surface area is 43.08m2 /g. Please see Table 1 and Table 2 below. Table 1 shows the specific surface area of diatomite and different diatomite-based porous adsorbents synthesized by hydrothermal method, and Table 2 shows the cation exchange capacity of diatomite and different diatomite-based porous adsorbents synthesized by hydrothermal method.
表1Table 1
表2Table 2
第二步，取1g上述方法制备得到的C-S-H硅藻土基多孔吸附剂，放入盛有液体培养基的150ml锥形瓶，加入0.3g上海安琪酵母股份有限公司生产的高活性面包啤酒酵母粉，调节pH值为7，并在速度为120rpm的往复摇床上，以25℃的恒温条件培养24h，用去离子水冲洗去除酵母的代谢产物、残余培养基，最终得到负载酵母的C-S-H硅藻土基多孔吸附剂。In the second step, take 1g of the C-S-H diatomite-based porous adsorbent prepared by the above method, put it into a 150ml Erlenmeyer flask filled with liquid medium, and add 0.3g of high-activity bread beer yeast produced by Shanghai Angel Yeast Co., Ltd. powder, adjusted the pH value to 7, and cultured on a reciprocating shaker at a speed of 120rpm at a constant temperature of 25°C for 24 hours, washed with deionized water to remove yeast metabolites and residual medium, and finally obtained C-S-H diatoms loaded with yeast Soil-based porous adsorbent.
第三步，将负载酵母的C-S-H硅藻土基多孔吸附剂放入盛有100ml浓度为1000mg/L的亚甲基蓝水溶液的锥形瓶中，在速度为120rpm的往复摇床上，以25℃的室温条件处理，间隔60分钟固定时间取样，放在离心机中，在15000r/min下离心10分钟取上清液，采用分光光度计，在亚甲基蓝最大吸收波长处（665nm）测量吸光度。按吸光度-浓度工作曲线换算成亚甲基蓝水溶液浓度。当吸附时间为48h，亚甲基蓝去除率为90%，单位吸附量为89.75mg/g。以未负载酵母的C-S-H硅藻土基多孔吸附剂的吸附实验比较，负载酵母后吸附量提高了62%，请看图9。In the third step, put the C-S-H diatomite-based porous adsorbent loaded with yeast into an Erlenmeyer flask filled with 100ml of methylene blue aqueous solution with a concentration of 1000mg/L. For processing, take samples at regular intervals of 60 minutes, place them in a centrifuge, and centrifuge at 15,000 r/min for 10 minutes to take the supernatant, and use a spectrophotometer to measure the absorbance at the maximum absorption wavelength of methylene blue (665nm). According to the absorbance-concentration working curve, it was converted into the concentration of methylene blue aqueous solution. When the adsorption time is 48h, the removal rate of methylene blue is 90%, and the unit adsorption capacity is 89.75mg/g. Compared with the adsorption experiment of C-S-H diatomite-based porous adsorbent without yeast loading, the adsorption capacity increased by 62% after loading yeast, please see Figure 9.
实施例2Example 2
第一步，将实施例1的硅藻土、2.15g氢氧化钙、0.5g氢氧化钠、1.5ml去离子水混合均匀，将混合物在压片机下以15MPa压制成型；将脱模后的样品放入高压水热釜中反应。控制反应温度为175℃，反应时间为12h，水热反应后得到的样品经检测如图3，其中（1）为硅藻土原料的XRD图，（2）为水热合成后的硅藻土基多孔吸附剂的XRD图，从图3中可以看出，硅藻土原料的主要成分为石英和蒙脱石，经过水热合成后，得到的硅藻土基吸附剂，其成分在保留了原硅藻土（石英）的基础上，生成了优化矿物托勃莫来石。扫描电镜看到的结构如图6所示，托勃莫来石为针状结构，其抗折强度为26.4Mpa，比表面积为52.78m2/g，请看表1和表2。The first step, the diatomite of embodiment 1, 2.15g calcium hydroxide, 0.5g sodium hydroxide, 1.5ml deionized water are mixed evenly, and the mixture is compressed with 15MPa under the tablet press; The samples were placed in a high-pressure hydrothermal kettle for reaction. The reaction temperature is controlled at 175°C, and the reaction time is 12 hours. The samples obtained after the hydrothermal reaction are tested as shown in Figure 3, where (1) is the XRD pattern of diatomite raw materials, and (2) is the diatomite after hydrothermal synthesis It can be seen from Figure 3 that the main components of the diatomite-based porous adsorbent are quartz and montmorillonite. After hydrothermal synthesis, the obtained diatomite-based adsorbent has its components retained On the basis of raw diatomaceous earth (quartz), the optimized mineral tobermullite is generated. The structure seen by the scanning electron microscope is shown in Figure 6. Tobermullite is a needle-like structure with a flexural strength of 26.4Mpa and a specific surface area of 52.78m2 /g. Please see Table 1 and Table 2.
第二步，除了取3g上述方法制备得到的托勃莫来石硅藻土基多孔吸附剂外，其余工艺条件与实施例1相同，最终得到负载酵母的托勃莫来石硅藻土基多孔吸附剂。In the second step, except that 3 g of the tober mullite diatomite-based porous adsorbent prepared by the above method was taken, the rest of the process conditions were the same as in Example 1, and finally the yeast-loaded tober mullite diatomite-based porous adsorbent was obtained.
第三步，除了将负载酵母的托勃莫来石硅藻土基多孔吸附剂放入盛有100ml浓度为1000mg/L的亚甲基蓝水溶液的锥形瓶中外，其余工艺条件与实施例1相同，当吸附时间为48h，亚甲基蓝去除率为85%，单位吸附量为73.17mg/g。以未负载酵母的托勃莫来石硅藻土基多孔吸附剂的吸附实验比较，负载酵母后吸附量提高了65.4%，请看图10。In the third step, except that the tobermullite diatomite-based porous adsorbent loaded with yeast is put into a conical flask filled with 100ml concentration of methylene blue aqueous solution of 1000mg/L, all the other process conditions are the same as in Example 1, when the adsorption time For 48h, the removal rate of methylene blue was 85%, and the unit adsorption capacity was 73.17mg/g. Compared with the adsorption experiment of tobermullite diatomite-based porous adsorbent without yeast loading, the adsorption capacity increased by 65.4% after loading yeast, please see Figure 10.
实施例3Example 3
第一步，将3g烘干的过80目筛硅藻土、0.9g氢氧化钙、0.4g氢氧化钠1.3ml去离子水均匀混合，将混合物在压片机下以30MPa压制成型；将脱模后的样品放入高压水热釜中，反应釜中加入容积1/7的去离子水，样品与水不直接接触。控制反应温度为200℃，反应时间为24h，水热反应后得到的样品为经检测为方沸石硅藻土基多孔吸附剂，请看图4，图4为水热合成方沸石优化硅藻土基吸附剂与硅藻土的XRD图，其中（1）为硅藻土原料的XRD图，（2）为水热合成后的硅藻土基吸附剂的XRD图，从图中可以看出，硅藻土原料的主要成分为石英和蒙脱石，经过水热合成后，得到的硅藻土基多孔吸附剂，扫描电镜看到的结构如图7所示为圆球状结构。其成分在保留了原硅藻土（石英）的基础上，生成了优化矿物方沸石。其抗折强度为23.2Mpa，比表面积为74.42m2/g。In the first step, 3 g of dried diatomite, 0.9 g of calcium hydroxide, 0.4 g of sodium hydroxide and 1.3 ml of deionized water are uniformly mixed, and the mixture is pressed into shape under a tablet machine at 30 MPa; The molded sample was placed in a high-pressure hydrothermal kettle, and 1/7 of the volume of deionized water was added to the reaction kettle, so that the sample did not directly contact with the water. The reaction temperature was controlled at 200°C, and the reaction time was 24 hours. The sample obtained after the hydrothermal reaction was detected as analcite diatomite-based porous adsorbent, please see Figure 4, Figure 4 is the hydrothermal synthesis of analzeite-optimized diatomite The XRD pattern of diatomite-based adsorbent and diatomite, in which (1) is the XRD pattern of diatomite raw material, and (2) is the XRD pattern of diatomite-based adsorbent after hydrothermal synthesis. It can be seen from the figure that The main components of diatomite raw materials are quartz and montmorillonite. After hydrothermal synthesis, the obtained diatomite-based porous adsorbent has a spherical structure as shown in Figure 7 by scanning electron microscope. Its composition is based on the retention of the original diatomaceous earth (quartz), resulting in the optimized mineral analcime. Its flexural strength is 23.2Mpa, and its specific surface area is 74.42m2 /g.
第二步，取3g上述方法制备得到的方沸石硅藻土基多孔吸附剂，放入盛有液体培养基的150ml锥形瓶。加入0.5g市售用于处理染料废水的酵母粉，调节pH值为7，并在速度为120rpm的往复摇床上，以25℃的恒温条件培养24h，用去离子水冲洗去除酵母的代谢产物、残余培养基，最终得到负载酵母的方沸石硅藻土基多孔吸附剂。In the second step, take 3 g of the analcite diatomite-based porous adsorbent prepared by the above method, and put it into a 150 ml Erlenmeyer flask filled with a liquid medium. Add 0.5 g of commercially available yeast powder used to treat dye wastewater, adjust the pH value to 7, and culture on a reciprocating shaker at a speed of 120 rpm at a constant temperature of 25°C for 24 hours, rinse with deionized water to remove yeast metabolites, The remaining culture medium is finally obtained as an analcite diatomite-based porous adsorbent loaded with yeast.
第三步，将负载酵母的方沸石硅藻土基多孔吸附剂放入盛有100ml浓度为1000mg/L的亚甲基蓝水溶液的锥形瓶中，在速度为120rpm的往复摇床上，以25℃的室温条件处理，间隔固定时间取样，在离心机以15000r/min下离心10分钟取上清液，采用分光光度计，在亚甲基蓝最大吸收波长处（665nm）测量吸光度。按吸光度-浓度工作曲线换算成亚甲基蓝水溶液浓度。当吸附时间为48h，亚甲基蓝去除率为94%，单位吸附量为93.28mg/g。以未负载酵母的方沸石优化吸附剂的吸附实验比较，负载酵母后吸附量提高了34.0%，请看图11。In the third step, put the analzem diatomite-based porous adsorbent loaded with yeast into an Erlenmeyer flask filled with 100ml of methylene blue aqueous solution with a concentration of 1000mg/L. On a reciprocating shaker at a speed of 120rpm, the For conditional treatment, samples were taken at regular intervals, centrifuged in a centrifuge at 15,000r/min for 10 minutes to take the supernatant, and the absorbance was measured at the maximum absorption wavelength of methylene blue (665nm) with a spectrophotometer. Convert the concentration of methylene blue aqueous solution according to the absorbance-concentration working curve. When the adsorption time is 48h, the removal rate of methylene blue is 94%, and the unit adsorption capacity is 93.28mg/g. Compared with the adsorption experiment of analzem optimized adsorbent without yeast loading, the adsorption capacity increased by 34.0% after loading yeast, please see Figure 11.
本发明实施例所用的相关原料硅藻土原土产地为浙江省嵊州市，其扫描电镜图请看图1，从图1中可以看出，硅藻土原土的硅藻壁壳中有多级、大量、有序排列的微孔，这是硅藻土具有良好吸附性的原因。硅藻土是一种具有良好自净化能力的无机矿物材料，但在工程应用中存在的最主要问题是在吸附污染物后难以与净化水分离，产生污泥等二次污染。The original place of origin of the relevant raw material diatomite used in the embodiment of the present invention is Shengzhou City, Zhejiang Province. Please see Fig. 1 for its scanning electron micrograph. As can be seen from Fig. 1, there are many Level, a large number of micropores arranged in an orderly manner, this is the reason why diatomite has good adsorption. Diatomite is an inorganic mineral material with good self-purification ability, but the main problem in engineering applications is that it is difficult to separate from purified water after adsorbing pollutants, resulting in secondary pollution such as sludge.
本发明所述的液体培养基主要成分为不含琼脂的察氏培养基，其中包括：1000ml去离子水、30g蔗糖、3g硝酸钠、1g磷酸二氢钾、0.5g氯化钾、0.5七水硫酸镁、0.01g硫酸铁。The main component of the liquid culture medium of the present invention is the Chapei culture medium without agar, which includes: 1000ml deionized water, 30g sucrose, 3g sodium nitrate, 1g potassium dihydrogen phosphate, 0.5g potassium chloride, 0.5 heptahydrate Magnesium sulfate, 0.01g iron sulfate.
本发明水热合成技术能够在保留原硅藻土的基础上，合成得到如水化硅酸钙凝胶（C-S-H）、托勃莫来石、方沸石，经检测这些矿物不仅提高了吸附剂的强度，保证了不生成污泥，同时也提高了多孔性能，请看表1和图8，从图8中可以看出，水热合成后，样品中的孔径分布在介孔范围变得更为广泛，有利于引入负载大量的微生物，有利于染料污水的吸附，提高污水处理效率。另外，经过检测水热合成后，C-S-H，托勃莫来石以及方沸石硅藻土基多孔吸附剂，阳离子交换量都得到了明显提升（请看表2），而亚甲基蓝染料分子为阳离子型染料，因此，水热合成的吸附剂对亚甲基蓝吸附有着天然的优势。The hydrothermal synthesis technology of the present invention can synthesize calcium silicate hydrate gel (C-S-H), tobermullite, and analcite on the basis of retaining the original diatomite. After testing, these minerals not only improve the strength of the adsorbent , to ensure that no sludge is generated, and at the same time improve the porosity, please see Table 1 and Figure 8. It can be seen from Figure 8 that after hydrothermal synthesis, the pore size distribution in the sample becomes more extensive in the mesoporous range , which is conducive to the introduction of a large number of microorganisms, the adsorption of dye sewage, and the improvement of sewage treatment efficiency. In addition, after testing hydrothermal synthesis, the cation exchange capacity of C-S-H, tobermullite and analcite diatomite-based porous adsorbents has been significantly improved (see Table 2), and the methylene blue dye molecule is a cationic dye , therefore, the hydrothermally synthesized adsorbent has a natural advantage for methylene blue adsorption.
从图9、图10、图11吸附曲线可以看出，C-S-H、托勃莫来石及方沸石硅藻土基多孔吸附剂负载与未负载酵母对亚甲基蓝的吸附效果对比，所有的硅藻土基多孔吸附剂对亚甲基蓝溶液本身都有很好的吸附性，而负载了酵母的硅藻土基多孔吸附剂，其吸附亚甲基蓝的效率都得到了大大的提高。From the adsorption curves in Figure 9, Figure 10, and Figure 11, it can be seen that the adsorption effects of C-S-H, tobermullite and analcite diatomite-based porous adsorbents on methylene blue were compared with those of unloaded yeast. Porous adsorbents have good adsorption properties for methylene blue solution itself, and the diatomaceous earth-based porous adsorbent loaded with yeast has greatly improved the adsorption efficiency of methylene blue.
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