CN105236539B - A kind of efficient modification clay for eliminating red tide - Google Patents
A kind of efficient modification clay for eliminating red tide Download PDFInfo
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- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 4
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- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 2
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 claims description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 claims 5
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 9
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
本发明设计属于水生态安全领域防灾减灾策略，进一步的说涉及近海水域赤潮的控制与治理领域，具体是一种高效消除赤潮的改性粘土。改性粘土为无机铝盐、粘土矿物和氧化剂的复配物，其中按重量份数计，无机铝盐：粘土矿物：氧化剂＝1:1‑500:0‑50。使用时将该改性粘土与海水混合成均匀的悬浊液，按照一定浓度喷洒在赤潮水体表面，可以达到快速消除水体中大量赤潮生物的效果。该改性粘土能够克服常见PAC改性粘土在治理赤潮时施用条件苛刻、难于高效大范围施用的问题。The design of the present invention belongs to the disaster prevention and reduction strategy in the field of water ecological security, and further relates to the field of control and management of red tides in offshore waters, specifically a modified clay that can efficiently eliminate red tides. The modified clay is a compound of inorganic aluminum salt, clay mineral and oxidizing agent, wherein, in parts by weight, inorganic aluminum salt: clay mineral: oxidizing agent=1:1-500:0-50. When used, the modified clay is mixed with seawater to form a uniform suspension, which is sprayed on the surface of the red tide water body according to a certain concentration, so as to achieve the effect of quickly eliminating a large number of red tide organisms in the water body. The modified clay can overcome the problems of harsh application conditions and difficulty in efficient and large-scale application of the common PAC modified clay when controlling red tide.
Description
技术领域technical field
本发明设计属于水生态安全领域防灾减灾策略，进一步的说涉及近海水域赤潮的控制与治理领域，具体是一种高效消除赤潮的改性粘土。The design of the present invention belongs to the disaster prevention and reduction strategy in the field of water ecological security, and further relates to the field of control and management of red tides in offshore waters, specifically a modified clay that can efficiently eliminate red tides.
背景技术Background technique
赤潮(Red tide)是指在一定的环境条件下，海水中的浮游微藻、原生动物或细菌等在短时间内突发性增殖和聚集，而引起的水体生态系统严重破坏、水色变化的灾害性生态异常现象。Red tide refers to the sudden proliferation and accumulation of planktonic microalgae, protozoa or bacteria in seawater under certain environmental conditions, which causes serious damage to the water ecosystem and changes in water color. Sexual abnormalities.
近年来我国近海赤潮爆发的频率和强度不断增加，已严重影响到近海生态安全。为有效地减轻赤潮灾害的危害，特别是在一些养殖区、育苗区和一些景观或功能性水域，对可快速有效地消除赤潮的方法具有迫切需求。In recent years, the frequency and intensity of red tide outbreaks in my country's coastal waters have been increasing, which has seriously affected the ecological security of coastal waters. In order to effectively reduce the harm of red tide disasters, especially in some breeding areas, nursery areas and some landscape or functional waters, there is an urgent need for methods that can quickly and effectively eliminate red tides.
目前，赤潮防治的方法主要有化学法、物理法、生物法。尽管从理论上讲能够治理赤潮的方法很多，但是符合无二次污染、成本低等要求的非常少，因此这些方法大多局限于实验室研究中。能够在赤潮爆发现场大规模应用，并取得理想效果的就更少，因此赤潮治理仍是一个国际难题。At present, the methods of red tide prevention and control mainly include chemical method, physical method and biological method. Although there are many methods that can control red tide in theory, there are very few that meet the requirements of no secondary pollution and low cost, so these methods are mostly limited to laboratory research. There are even fewer that can be applied on a large scale at the scene of red tide outbreaks and achieve ideal results. Therefore, red tide control is still an international problem.
利用粘土治理有害藻华被证明是一种有效的方法，也可能是目前唯一得以大规模应用的方法，它因成本低、来源广、效率高、污染小而受到青睐。这种方法作用的主要原理是利用粘土颗粒和有害藻华生物的絮凝作用将有害藻华生物从水体表层沉降到底层。上世纪七十年代，日本开展了粘土法治理海水赤潮的现场研究，该方法成本低、无污染，引起了国际上的重视。上个世纪90年代韩国也利用黄土治理有害藻华，取得了良好的效果。但粘土原土对藻华生物的去除效率很低、用土量大是该方法的重要缺陷。在实际应用时只能靠增加粘土用量来提高去除效率，容易存在淤泥渣量过大的情况。针对该缺陷，上世纪九十年代中国科学院海洋研究所俞志明研究员提出了利用粘土表面改性技术提高去除效率的粘土表面改性理论(Yu et al.1994a,1994b,1995)。在此理论指导下，制备出的PAC改性粘土(俞志明等，1994c)，大大提高了去除藻华生物的效率。但是在研究中发现，使用海水配制的PAC改性粘土悬浮液除藻效率低于去离子水配制的粘土悬浮液。在海水中治理有害藻华时，去除效率仍然具有较大的提升空间。提高改性粘土技术在去除海水有害藻华中的效率一直是研究的重点。The use of clay to control harmful algal blooms has been proven to be an effective method, and it may be the only method that can be applied on a large scale at present. It is favored because of its low cost, wide source, high efficiency and low pollution. The main principle of this method is to use the flocculation of clay particles and harmful algal blooms to settle harmful algal blooms from the surface of the water body to the bottom. In the 1970s, Japan carried out on-site research on the clay method to control seawater red tides. This method is low in cost and pollution-free, and has attracted international attention. In the 1990s, South Korea also used loess to control harmful algal blooms and achieved good results. However, the removal efficiency of clay raw soil on algal blooms is very low, and the large amount of soil is an important defect of this method. In actual application, the removal efficiency can only be improved by increasing the amount of clay, and it is easy to have an excessive amount of sludge. In response to this defect, in the 1990s, researcher Yu Zhiming of the Institute of Oceanology, Chinese Academy of Sciences proposed the theory of clay surface modification using clay surface modification technology to improve removal efficiency (Yu et al.1994a, 1994b, 1995). Under the guidance of this theory, the prepared PAC modified clay (Yu Zhiming et al., 1994c) greatly improved the efficiency of removing algal blooms. However, it was found in the study that the algae removal efficiency of the PAC-modified clay suspension prepared with seawater was lower than that of the clay suspension prepared with deionized water. When controlling harmful algal blooms in seawater, the removal efficiency still has a large room for improvement. Improving the efficiency of modified clay technology in the removal of harmful algal blooms in seawater has been the focus of research.
通过强氧化作用灭杀赤潮生物已经有很多的报道，如有人提出了利用氧自由基专利号CN 1594136A，CN1810672A，CN102107944A和CN103058349A)，硫酸自由基(专利号CN101172692A)，该方法不仅能够灭杀藻细胞，并且具有提高水体中氧含量、进而提高水体中污染物降解速率的作用。但实践中发现，通过灭杀途径消除赤潮生物时需要的氧化剂剂量偏高，而且，灭杀藻细胞常常会造成藻细胞的破碎，细胞中的一些物质，如藻毒素、胞内溶解有机物等等会从细胞中释放出来，可能会造成二次污染。而在絮凝沉降法消除赤潮生物时，藻细胞的运动能力会降低改性粘土去除藻华生物的效率，但若降低藻细胞的运动能力则能够增强改性粘土去除藻华生物的效率。因此现急需一种行之有效的方式方法。There are many reports on killing red tide organisms by strong oxidation, such as the use of oxygen free radicals (patent No. CN 1594136A, CN1810672A, CN102107944A and CN103058349A), sulfuric acid free radicals (patent No. CN101172692A), this method can not only kill algae cells, and has the effect of increasing the oxygen content in the water body, thereby increasing the degradation rate of pollutants in the water body. However, it has been found in practice that the dose of oxidant required to eliminate red tide organisms through killing is relatively high, and killing algal cells often causes the destruction of algal cells, and some substances in the cells, such as algal toxins, intracellular dissolved organic matter, etc. It will be released from the cells and may cause secondary pollution. When the flocculation and sedimentation method is used to eliminate red tide organisms, the motility of algal cells will reduce the efficiency of modified clay to remove algal blooms, but if the motility of algal cells is reduced, the efficiency of modified clay to remove algal blooms can be enhanced. Therefore be badly in need of a kind of effective way now.
发明内容Contents of the invention
本发明的目的是针对海水赤潮治理提供一种高效消除赤潮的改性粘土。The object of the present invention is to provide a modified clay for efficiently eliminating red tides for the control of seawater red tides.
为实现上述目的，本发明所采用的技术方案为：To achieve the above object, the technical solution adopted in the present invention is:
一种高效消除赤潮的改性粘土，改性粘土为无机铝盐、粘土矿物和氧化剂的复配物，其中按重量份数计，无机铝盐：粘土矿物：氧化剂＝1:1-500:0-50。A modified clay for efficiently eliminating red tide, the modified clay is a compound of inorganic aluminum salt, clay mineral and oxidizing agent, wherein in parts by weight, inorganic aluminum salt: clay mineral: oxidizing agent = 1:1-500:0 -50.
所述的高效消除赤潮改性粘土，其中无机铝盐为硫酸铝、硫酸铝水合物、氯化铝、氯化铝水合物中的一种或几种的混合。In the modified clay with high efficiency for eliminating red tide, the inorganic aluminum salt is one or a mixture of aluminum sulfate, aluminum sulfate hydrate, aluminum chloride, and aluminum chloride hydrate.
所述的高效消除赤潮改性粘土，其中氧化剂为单过硫酸氢钾复合盐或单过硫酸氢钾。In the modified clay for eliminating red tide efficiently, the oxidizing agent is potassium monopersulfate compound salt or potassium monopersulfate.
所述的高效消除赤潮改性粘土，是按比例将无机铝盐与氧化剂均匀混合，混合后加入粉体粘土矿物再次混匀、堆场，熟化1-3h后、研磨至粒度小于200目的粉体。The high-efficiency red tide elimination modified clay is to uniformly mix the inorganic aluminum salt and the oxidizing agent in proportion, after mixing, add powder clay minerals to mix again, stockpile, mature for 1-3 hours, and grind until the particle size is less than 200 mesh powder .
所述的高效消除赤潮改性粘土，使用时将改性粘土与海水混合成均匀的悬浊液，喷洒到暴发赤潮的水体表面至浓度为0.01-20g/L，经过1-4小时的自然沉降后，可以有效去除赤潮生物。The described highly efficient red tide elimination modified clay is used by mixing the modified clay with seawater to form a uniform suspension, spraying it on the surface of the water body where the red tide breaks out to a concentration of 0.01-20g/L, and after 1-4 hours of natural settlement Finally, red tide organisms can be effectively removed.
本发明所具有优点：The present invention has advantages:
本发明基于游离铝离子在偏碱性海水中可以快速水解，在粘土颗粒表面形成具有吸附-絮凝能力的羟铝化合物，从而提高粘土颗粒与藻细胞的结合能力，实现提高粘土絮凝-去除赤潮藻细胞的能力；另外，当在游离铝盐改性粘土中添加适量强氧化剂时，该添加剂溶于水后通过强氧化作用可以有效降低赤潮藻细胞的运动能力，进一步增效改性粘土絮凝去除赤潮生物的能力。The present invention is based on the fact that free aluminum ions can be rapidly hydrolyzed in alkaline seawater, and an aluminum hydroxy compound with adsorption-flocculation ability is formed on the surface of clay particles, thereby improving the binding ability between clay particles and algae cells, and realizing the improvement of clay flocculation-removal of red tide algae In addition, when an appropriate amount of strong oxidant is added to the free aluminum salt modified clay, the additive can effectively reduce the motility of red tide algae cells through strong oxidation after the additive is dissolved in water, and further synergize the flocculation of modified clay to remove red tide biological abilities.
与传统聚合氯化铝(PAC)改性粘土相比较，本发明采用铝离子改性粘土在赤潮水体中发生原位水解作用可以更有效地增进粘土与藻细胞的结合，降低了铝类改性剂的用量。本发明的新型改性粘土各组分之间表现出了显著的互补增效效果，克服了传统改性粘土施用前预分散时需要无盐水(如去离子水等)的限制，特别适用于海水中赤潮的消除。Compared with the traditional polyaluminum chloride (PAC) modified clay, the present invention adopts the aluminum ion modified clay to undergo in-situ hydrolysis in the red tide water body, which can more effectively promote the combination of clay and algae cells, and reduce the aluminum modification. dosage of the agent. The components of the new modified clay of the present invention show significant complementary and synergistic effects, overcome the limitation that no salt water (such as deionized water, etc.) is required for pre-dispersion of the traditional modified clay before application, and are especially suitable for seawater Elimination of red tides.
附图说明Description of drawings
图1为本发明实施例提供的三种铝化合物改性土悬浮液对抑食金球藻除藻效率图。Fig. 1 is a diagram of the algae removal efficiency of three kinds of aluminum compound modified soil suspensions provided by the examples of the present invention on Chrysococcus inhibiting feeding.
图2为本发明实施例提供的三种铝化合物改性土悬浮液对小球藻的除藻效率图，其中，粘土浓度为0.4g/L。Fig. 2 is a diagram of the algae removal efficiency of three kinds of aluminum compound modified soil suspensions against chlorella provided by the embodiment of the present invention, wherein the clay concentration is 0.4 g/L.
图3为本发明实施例提供的三种铝化合物改性土悬浮液对赤潮异弯藻除藻效率图。Fig. 3 is a diagram of the algae-removing efficiency of three kinds of aluminum compound-modified soil suspensions against Heterocurvium akashiwo provided by the examples of the present invention.
图4为本发明实施例提供的三种铝化合物改性土悬浮液对球形棕囊藻的除藻效率图。Fig. 4 is a diagram of the algae removal efficiency of Phaeocystis globosa by three kinds of aluminum compound modified soil suspensions provided in the examples of the present invention.
具体实施方式Detailed ways
本发明改性粘土由单过硫酸氢钾复合盐、无机铝化合物和粘土组成。在其制备过程中，首先使用无机铝化合物和单过硫酸氢钾复合盐对粘土进行表面改性处理，研磨，混合均匀。改性粘土中各组分的比例，可以按照要去除的赤潮生物种类、丰度，水体的环境条件以及各组分的价格调整。如若爆发海域赤潮细胞密度较大可以适当提高无机铝化合物和单过硫酸氢钾复合盐的比例；若海域具有恶臭等异味，可以适当提高单过硫酸氢钾复合盐的比例。使用时，将改性粘土与淡水或海水混合形成悬浮液，按照一定的浓度喷洒在赤潮爆发区域，经过一段时间的自然沉降后可以有效的去处赤潮生物。The modified clay of the invention is composed of potassium monopersulfate compound salt, inorganic aluminum compound and clay. In the preparation process, the clay is first surface-modified by using inorganic aluminum compound and potassium monopersulfate compound salt, ground and mixed evenly. The proportion of each component in the modified clay can be adjusted according to the species and abundance of red tide organisms to be removed, the environmental conditions of the water body and the price of each component. If the red tide cell density in the outbreak sea area is high, the ratio of inorganic aluminum compound and potassium monopersulfate compound salt can be appropriately increased; if the sea area has odors such as stench, the proportion of potassium monopersulfate compound salt can be appropriately increased. When in use, the modified clay is mixed with fresh water or seawater to form a suspension, which is sprayed on the red tide outbreak area according to a certain concentration. After a period of natural settlement, it can effectively remove red tide organisms.
实施例1Example 1
以无机铝盐为改性剂(无机铝盐为氯化铝、硫酸铝或聚合氯化铝)，将其配成一定浓度的水溶液，再按比例加入粉体粘土矿物，利用碱化物(如苛性钾、苛性钠、纯碱、生石灰、熟石灰等)调整混合物pH值至4～6，熟化稳定后得到不同种类的改性粘土悬浊液。其中以改性粘土悬浊液中铝浓度为2.85×10-2mol/L所得到氯化铝改性土、硫酸铝改性土、聚合氯化铝改性土的去除抑食金球藻(细胞密度1.2×107cells/ml)为例，在藻液中分别用海水混合添加上述不同类型改性粘土达到0.10，0.20，0.25，0.30，0.40，0.50，0.75，1.0g/L，摇匀、静止2.5小时后观测藻液中抑食金球藻细胞密度的变化。各种改性粘土组合物在不同使用浓度时的除藻效率如图1所示，结果表明，氯化铝改性土或硫酸铝改性土的除藻效率较高(参见图1)。Use inorganic aluminum salts as modifiers (inorganic aluminum salts are aluminum chloride, aluminum sulfate or polyaluminum chloride), make it into a certain concentration of aqueous solution, and then add powder clay minerals in proportion, use alkalization (such as caustic Potassium, caustic soda, soda ash, quicklime, slaked lime, etc.) to adjust the pH value of the mixture to 4-6, and obtain different types of modified clay suspensions after aging and stabilization. Wherein the removal of Chrysococcus ( Cell density 1.2×10 7 cells/ml) as an example, add the above-mentioned different types of modified clay to the algae liquid to reach 0.10, 0.20, 0.25, 0.30, 0.40, 0.50, 0.75, 1.0g/L, shake well 1. Observing the change of the cell density of Chryseococcus in the algae liquid after resting for 2.5 hours. The algae removal efficiencies of various modified clay compositions at different concentrations are shown in Figure 1, and the results show that the algae removal efficiency of aluminum chloride modified soil or aluminum sulfate modified soil is higher (see Figure 1).
实施例2Example 2
如实施例1所述，测定上述不同类型改性粘土去除水体中高密度小球藻的效率，并与相同浓度的未改性粘土相比较。所用小球藻细胞密度1.12×108cells/ml，添加改性粘土至浓度为0.40g/L，摇匀，静止2.5小时后，观测除藻效率。不同粘土的除藻效率如图2所示，结果表明氯化铝改性土或硫酸铝改性土的除藻效率较高(参见图2)。As described in Example 1, the efficiency of the above-mentioned different types of modified clays for removing high-density chlorella in water bodies was determined, and compared with unmodified clays of the same concentration. The cell density of the chlorella used was 1.12×10 8 cells/ml, the modified clay was added to a concentration of 0.40 g/L, shaken well, and the algae removal efficiency was observed after standing still for 2.5 hours. The algae removal efficiency of different clays is shown in Figure 2, and the results show that the algae removal efficiency of aluminum chloride modified soil or aluminum sulfate modified soil is higher (see Figure 2).
实施例3Example 3
如实施例1所述，测定上述不同类型改性粘土去除水体中高密度赤潮异弯藻的效率，并与相同浓度的未改性粘土相比较。所用赤潮异弯藻细胞密度7.2×104cells/ml，添加改性粘土至浓度为0.10，0.20，0.35，0.50，0.75，1.0，1.5，2.0，2.5g/L，摇匀，静止2.5小时后，观测除藻效率。除藻效率如图3所示，结果表明氯化铝改性土或硫酸铝改性土的除藻效率较高(参见图3)。As described in Example 1, the efficiency of the above-mentioned different types of modified clays in removing high-density Heterocurvium akashiwo in water bodies was determined, and compared with the same concentration of unmodified clays. The cell density of Heterocurvium akashiwo used is 7.2×10 4 cells/ml, add modified clay to a concentration of 0.10, 0.20, 0.35, 0.50, 0.75, 1.0, 1.5, 2.0, 2.5 g/L, shake well, and stand still for 2.5 hours , to observe the algae removal efficiency. The algae removal efficiency is shown in Figure 3, and the results show that the algae removal efficiency of the aluminum chloride modified soil or the aluminum sulfate modified soil is higher (see Figure 3).
实施例4Example 4
如实施例1所述，测定上述不同类型改性粘土去除水体中高密度球形棕囊藻的效率，并与相同浓度的未改性粘土相比较。所用球形棕囊藻细胞密度2.3×106cells/ml，添加改性粘土至浓度为0.10，0.20，0.35，0.50，0.75，1.0，1.5，2.0，2.5g/L，摇匀，静止2.5小时后，观测除藻效率。除藻效率如图4所示，结果表明氯化铝改性土或硫酸铝改性土的除藻效率较高(参见图4)。As described in Example 1, the efficiencies of the above-mentioned different types of modified clays for removing Phaeocystis globosa in water bodies with high density were determined, and compared with unmodified clays of the same concentration. The cell density of Phaeocystis globosa used is 2.3×10 6 cells/ml, add modified clay to a concentration of 0.10, 0.20, 0.35, 0.50, 0.75, 1.0, 1.5, 2.0, 2.5g/L, shake well, and stand still for 2.5 hours , to observe the algae removal efficiency. The algae removal efficiency is shown in Figure 4, and the results show that the algae removal efficiency of the aluminum chloride modified soil or the aluminum sulfate modified soil is higher (see Figure 4).
实施例5Example 5
研究该改性粘土技术中三组分之间的交互作用，仅考虑两者之间的交互作用。设计三因素三水平带交互作用的正交实验。设计改性粘土中粘土的用量为0.20,0.50,0.80g，硫酸铝用量为0.05,0.10,0.30g，氧化剂(单过硫酸氢钾复合盐或单过硫酸氢钾)用量为0,0.025,0.075g。制备复合改性粘土。研究其对球形棕囊藻(细胞密度2×106cells/ml)的除藻效率。结果发现，(1)粘土、硫酸铝和单过硫酸氢钾对除藻效率的影响都极显著(p＜0.01)，(2)硫酸铝和单过硫酸氢钾复合盐之间存在显著的交互作用(p＜0.01)，两者的复合应用能明显提高除藻效率。To study the interaction between the three components in this modified clay technology, only the interaction between the two is considered. An orthogonal experiment with three factors and three levels with interaction was designed. The amount of clay in the design modified clay is 0.20, 0.50, 0.80g, the amount of aluminum sulfate is 0.05, 0.10, 0.30g, and the amount of oxidant (potassium monopersulfate compound salt or potassium monopersulfate) is 0, 0.025, 0.075 g. Preparation of composite modified clay. Study its algae removal efficiency on Phaeocystis globosa (cell density 2×10 6 cells/ml). As a result, it was found that (1) clay, aluminum sulfate and potassium monopersulfate had very significant effects on algae removal efficiency (p<0.01), (2) there was a significant interaction between aluminum sulfate and potassium monopersulfate compound salt effect (p<0.01), the combined application of the two can significantly improve the efficiency of algae removal.
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