CN110683596A - Production method for realizing phosphorus fixation capacity amplification of clay mineral - Google Patents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明属于水污染治理技术领域，涉及一种快速实现粘土矿物固磷容量扩增的干法生产方法。The invention belongs to the technical field of water pollution control, and relates to a dry production method for rapidly realizing the expansion of the solid phosphorus capacity of clay minerals.
背景技术Background technique
大量研究表明，磷是湖泊富营养化的限制因子。因此，控磷被认为是湖泊富营养化水体治理的关键。然而，国内外相关研究表明，即使湖泊外源磷的输入得到有效控制后，湖泊富营养化问题仍可以持续几十年。这主要是因为来自湖泊底泥(或沉积物)磷的持续释放，从而可使上覆水体中磷得到有效的补充，进而为蓝藻的暴发提供磷源基础。这些研究表明，湖泊内源磷的控制是湖泊治理的关键。Numerous studies have shown that phosphorus is the limiting factor for lake eutrophication. Therefore, phosphorus control is considered to be the key to lake eutrophication water treatment. However, relevant studies at home and abroad have shown that even after the input of exogenous phosphorus in lakes is effectively controlled, the problem of lake eutrophication can still persist for decades. This is mainly due to the continuous release of phosphorus from lake sediments (or sediments), which can effectively replenish phosphorus in the overlying water, thereby providing a phosphorus source basis for the outbreak of cyanobacteria. These studies suggest that the control of endogenous phosphorus in lakes is the key to lake governance.
对于湖泊底泥磷的控制目前主要有底泥疏浚、曝气增氧、水生植物恢复以及底泥原位钝化控磷技术。其中，底泥原位钝化控磷技术近年来逐渐被广泛应用。在国际湖泊水环境治理中取得了显著的控制效果，该技术可有效降低水体中磷的含量，并能削减水体叶绿素a的浓度，缓解湖泊富营养化水平。底泥原位钝化技术的核心是控磷材料的研制。国际上已经逐渐经历从最终的铁铝药剂发展到今天的粘土矿物材料为载体的锁磷剂。经过大量的研究，国际上普遍认为铝基改性材料以及镧基改性材料均可以有效控制湖泊底泥内源磷的含量。上述材料主要是利用含铝药剂(结晶氯化铝、聚合氯化铝以及硫酸铝)、含镧药剂(氯化镧)对粘土矿物材料(凹凸棒、膨润土、沸石等)进行改性。其中以澳洲亚联邦科学与工业组织(Commonwealth Scientific and Industrial Research Organisation(CSIRO))发明的
目前，湖泊富营养化问题比较严重，水体中有机质含量以及pH值通常较高。因此，单一的利用含铝药剂或含镧药剂对粘土进行改性获得的产品已无法有效长久控制湖泊中磷的含量。将上述金属进行合理组配，并与粘土进行充分混合反应，所制备的产品必将为富营养化湖泊磷的削减做出贡献。At present, the problem of eutrophication in lakes is relatively serious, and the organic matter content and pH value in the water body are usually high. Therefore, a single product obtained by modifying clay with an aluminum-containing agent or a lanthanum-containing agent cannot effectively control the phosphorus content in the lake for a long time. By rationally combining the above metals and fully mixing them with clay, the prepared products will surely contribute to the reduction of phosphorus in eutrophic lakes.
粘土矿物由于其天然、无毒，储量丰富且比表面积大等特点，被普遍作为固磷材料改性的载体。Clay minerals are widely used as carriers for modification of phosphorus-fixing materials due to their natural, non-toxic, abundant reserves and large specific surface area.
目前粘土矿物的改性方法主要以粘土湿法活性负载为主，该种方法主要是将粘土矿物置于含镧或者含铝溶液进行过量反应，而后以离心法或挤压脱水法获取制备的锁(固)磷材料。改性过程中产生大量的废液，无法得到合理处理，甚至引起二次污染。CN109574104A公开了一种双金属抗风浪型锁磷材料及其制备方法和应用，该方法先将凹凸棒颗粒在高温活化固结，然后将固结的颗粒置于氯化镧、六水合氯化铝溶液中进行置换反应，将反应后的颗粒材料洗涤干燥后即获取双金属锁磷剂材料，该方法克服了现有锁磷剂负载金属元素单一的问题，获取的锁磷材料可用于浅水湖泊中(浅水湖风浪扰动大，而颗粒态的锁磷材料具有抗风浪的优势)内源磷释放的控制，但仍属于湿法生产，存在废液的问题。At present, the modification method of clay minerals is mainly based on the active loading of clay by wet method. This method mainly involves placing clay minerals in a solution containing lanthanum or aluminum for excessive reaction, and then obtaining the prepared locks by centrifugal method or extrusion dehydration method. (Solid) Phosphorus material. A large amount of waste liquid is generated in the modification process, which cannot be properly treated, and even causes secondary pollution. CN109574104A discloses a bimetallic anti-wind and wave type phosphorus-locking material and its preparation method and application. In the method, attapulgite particles are activated and consolidated at high temperature, and then the consolidated particles are placed in lanthanum chloride, aluminum chloride hexahydrate The replacement reaction is carried out in the solution, and the reacted particulate material is washed and dried to obtain a bimetallic phosphorus-locking agent material. The method overcomes the problem that the existing phosphorus-locking agent supports a single metal element, and the obtained phosphorus-locking material can be used in shallow lakes. (The wind and wave disturbance in shallow lakes is large, and the granular phosphorus-locking material has the advantage of resisting wind and waves) The control of endogenous phosphorus release is still a wet production, and there is a problem of waste liquid.
发明内容SUMMARY OF THE INVENTION
本发明主要是针对目前国际上的粘土型锁(固)磷剂制备程序复杂繁琐(一般为水合负载法，生产过程中产生大量废液)，易引起二次污染的问题，提出一种快速实现粘土矿物，尤其是凹凸棒粘土固磷容量扩增的干法生产方法。该方法具有简单，成本低廉，制备出的锁(固)磷材料固磷容量大、生产工艺简单，且无二次污染，无残留废液产生的特点。所制备的产品可应用于控制生活或工业污水、富营养化水体以及污染底泥中磷的释放，有效控制和缓解水体富营养化程度。The present invention is mainly aimed at the problem that the current international clay-type locking (fixing) phosphorus agent preparation procedure is complicated and tedious (usually a hydration loading method, and a large amount of waste liquid is generated in the production process), which is easy to cause secondary pollution, and proposes a rapid realization method. Dry production method for capacity expansion of clay minerals, especially attapulgite clays, for phosphorus-fixing capacity. The method has the characteristics of simplicity, low cost, large phosphorus-fixing capacity of the prepared (solid) phosphorus material, simple production process, no secondary pollution, and no residual waste liquid. The prepared product can be applied to control the release of phosphorus in domestic or industrial sewage, eutrophic water body and polluted sediment, and effectively control and alleviate the degree of eutrophication of water body.
为实现上述目的，本发明所采用的技术方案如下：For achieving the above object, the technical scheme adopted in the present invention is as follows:
一种实现粘土矿物固磷容量扩增的生产方法，包括如下步骤：A production method for realizing the expansion of clay mineral solid phosphorus capacity, comprising the following steps:
将粘土矿物的粉末与氯化镧和聚合氯化铝的混合溶液混匀后后挤出成颗粒，即得；所述粘土矿物与所述混合溶液的固液质量比大于等于6:1。The powder of the clay mineral is mixed with the mixed solution of lanthanum chloride and polyaluminum chloride, and then extruded into particles; the solid-liquid mass ratio of the clay mineral and the mixed solution is greater than or equal to 6:1.
粘土矿物粉末与氯化镧和聚合氯化铝的混合溶液混匀可实现粘土矿物的孔道扩增与负载。Mixing the clay mineral powder with the mixed solution of lanthanum chloride and polyaluminum chloride can realize the expansion and loading of the pores of the clay mineral.
只有将固液成分的质量比控制在固液质量比大于等于6:1，才能够成功实现挤出造粒。Extrusion granulation can be successfully achieved only if the mass ratio of solid-liquid components is controlled to be greater than or equal to 6:1.
优选的，所述粘土矿物为中品位或高品位的粘土矿物。中高品位的粘土矿物进入水体中可以迅速崩解，溶解于水，而品位比较低的粘土矿物进入水体后不易崩解和溶解，会影响除磷效果。Preferably, the clay minerals are medium-grade or high-grade clay minerals. The clay minerals of medium and high grade can disintegrate quickly and dissolve in water when they enter the water body, while the clay minerals of lower grade are not easy to disintegrate and dissolve after entering the water body, which will affect the phosphorus removal effect.
优选的，所述粘土矿物中矿物组分的质量含量大于等于40％。Preferably, the mass content of mineral components in the clay mineral is greater than or equal to 40%.
优选是，所述粘土矿物的粉末筛分目数大于等于100目。Preferably, the powder sieving mesh number of the clay mineral is greater than or equal to 100 meshes.
优选的，铝在所述混合溶液和所述粘土矿物的混合物中的质量分数为1％～4％，镧在所述混合溶液和所述粘土矿物的混合物中的质量分数为2％～5％。Preferably, the mass fraction of aluminum in the mixture of the mixed solution and the clay mineral is 1% to 4%, and the mass fraction of lanthanum in the mixture of the mixed solution and the clay mineral is 2% to 5% .
最优选的，铝在所述混合溶液和所述粘土矿物的混合物中的质量分数为3％，镧在所述混合溶液和所述粘土矿物的混合物中的质量分数为5％。Most preferably, the mass fraction of aluminum in the mixture of the mixed solution and the clay minerals is 3%, and the mass fraction of lanthanum in the mixture of the mixed solution and the clay minerals is 5%.
进一步的，所述的粘土矿物与所述混合溶液混合时间大于等于4小时。Further, the mixing time of the clay mineral and the mixed solution is greater than or equal to 4 hours.
进一步的，所述挤出为采用挤压机挤出。Further, the extrusion is to use an extruder.
优选的，所述颗粒为直径4～6mm，长度2～8mm的柱形体。Preferably, the particles are cylindrical bodies with a diameter of 4-6 mm and a length of 2-8 mm.
优选的，所述粘土矿物为凹凸棒粘土、膨润土、海泡石或硅藻土。Preferably, the clay mineral is attapulgite, bentonite, sepiolite or diatomaceous earth.
上述实现粘土矿物固磷容量扩增的生产方法生产的产品可应用于生活污水、工业废水以及富营养化水体底泥内源磷的控制。The products produced by the above-mentioned production method for realizing the expansion of the solid phosphorus capacity of clay minerals can be applied to the control of endogenous phosphorus in domestic sewage, industrial wastewater and eutrophication water body sediment.
本发明所述的实现粘土矿物固磷容量扩增的生产方法适用于多数粘土矿物材料。干法生产方法是直接计算好镧和铝的投加量并进行充分混拌，达到镧铝活性负载的目的，最后经过物理的挤出，增强混合物料的强度并塑形，能够保证每批次物料的中镧和铝的含量比较精确，实现制备产品的质量控制，且镧和铝负载量高，无损耗。最重要的是该方法在整个制备过程不产生废液、废渣，生产过程环保，不需要特殊的污水净化装置，整个生产过程非常简单，且制备的固磷材料具有较显著的固磷效果，普遍高于国际市售产品。且生产过程中将镧和铝双元素纳入制备过程中，制备的锁磷材料具有适用面广，功能强大的特点，适用水体的pH值范围较广。此外，由于粘土矿物材料储备丰富、材料取材广泛、价格便宜、天然无毒且生态安全性较高，故所制备的材料具有广阔的应用前景。The production method for realizing the expansion of the solid phosphorus capacity of clay minerals according to the present invention is applicable to most clay mineral materials. The dry production method is to directly calculate the dosage of lanthanum and aluminum and mix them fully to achieve the purpose of active loading of lanthanum and aluminum. Finally, through physical extrusion, the strength of the mixed material is enhanced and shaped, which can ensure that each batch is The content of lanthanum and aluminum in the material is relatively accurate, and the quality control of the prepared product is realized, and the loading of lanthanum and aluminum is high, and there is no loss. The most important thing is that this method does not produce waste liquid and waste residue in the whole preparation process, the production process is environmentally friendly, no special sewage purification device is required, the whole production process is very simple, and the prepared phosphorus-fixing material has a relatively significant phosphorus-fixing effect. higher than that of internationally marketed products. In addition, the dual elements of lanthanum and aluminum are incorporated into the preparation process in the production process, and the prepared phosphorus-locking material has the characteristics of wide application and powerful functions, and is suitable for a wide range of pH values of water bodies. In addition, the prepared materials have broad application prospects due to the abundant reserves of clay mineral materials, a wide range of materials, low prices, natural non-toxicity and high ecological safety.
附图说明Description of drawings
图1是不同金属负载干法生产的锁磷剂除磷效果对比图。图中的百分数为相应元素在混合溶液和凹凸棒粘土的混合物中的质量分数。Figure 1 is a comparison diagram of the phosphorus removal effect of phosphorus locking agents produced by different metal-loaded dry methods. The percentages in the figure are the mass fractions of the corresponding elements in the mixture of the mixed solution and attapulgite clay.
图2是不同纯度凹凸棒干法生产锁磷剂性能比较。Figure 2 is a comparison of the performance of attapulgite with different purities for dry production of phosphorus-locking agents.
图3是不同镧与铝含量制备材料的除磷效果。Figure 3 shows the phosphorus removal effect of materials prepared with different lanthanum and aluminum contents.
图4是本发明所制备的除磷材料与其他产品控磷效果对比图。FIG. 4 is a comparison diagram of the phosphorus control effect of the phosphorus removal material prepared by the present invention and other products.
具体实施方式Detailed ways
下面通过具体实施例对本发明所述的技术方案给予进一步详细的说明，但有必要指出以下实施例只用于对发明内容的描述，并不构成对本发明保护范围的限制。实施例中所采用的凹凸棒取自我国凹凸棒主要产地江苏盱眙，但对于原矿产地并无要求，适当的凹凸棒原矿为中等或以上品位。The technical solutions of the present invention will be further described in detail below through specific examples, but it is necessary to point out that the following examples are only used to describe the content of the invention and do not constitute a limitation on the protection scope of the present invention. The attapulgite used in the examples is taken from Xuyi, Jiangsu Province, the main producing area of attapulgite in my country, but there is no requirement for the original ore field, and the appropriate attapulgite raw ore is of medium or above grade.
实施例1Example 1
将矿物组分的质量含量大于等于40％的凹凸棒粘土原矿进行筛选，机械粉碎成筛分目数大于等于100目的粉末。将凹凸棒粘土的粉末与聚合氯化铝和氯化镧的混合溶液按照固液比6～9:1混合，进行充分物理混拌4小时后经市售挤压设备制备成直径为4～6mm，长度为2～8mm的柱形体锁磷剂。称取上述锁磷剂0.5g于不同溶度的磷溶液中，反应24小时后，测定磷的去除效率。结果如图1所示。The attapulgite clay ore with a mass content of mineral components greater than or equal to 40% is screened, and mechanically pulverized into powder with a sieving mesh number greater than or equal to 100 meshes. The powder of attapulgite is mixed with the mixed solution of polyaluminum chloride and lanthanum chloride according to the solid-liquid ratio of 6-9:1, and after thorough physical mixing for 4 hours, it is prepared into a diameter of 4-6mm by commercially available extrusion equipment. , a cylindrical phosphor lock agent with a length of 2-8mm. 0.5 g of the above-mentioned phosphorus-locking agent was weighed into phosphorus solutions of different solubility, and the phosphorus removal efficiency was measured after reacting for 24 hours. The results are shown in Figure 1.
实施例2Example 2
将矿物组分的质量含量大于等于40％的膨润土、海泡石或硅藻土原矿进行筛选，机械粉碎成筛分目数大于等于100目的粉末。将凹凸棒粘土的粉末与聚合氯化铝和氯化镧的混合溶液按照固液比9～15:1混合，铝在所述混合溶液和所述凹凸棒粘土的混合物中的质量分数为1％，镧在所述混合溶液和所述凹凸棒粘土的混合物中的质量分数为2％。进行充分物理混拌8小时后经市售挤压设备制备成直径为4～6mm，长度为2～8mm的柱形体锁磷剂。The bentonite, sepiolite or diatomite ore with a mass content of mineral components greater than or equal to 40% is screened, and mechanically pulverized into powder with a sieving mesh number greater than or equal to 100 meshes. Mix the powder of attapulgite with the mixed solution of polyaluminum chloride and lanthanum chloride according to a solid-liquid ratio of 9 to 15:1, and the mass fraction of aluminum in the mixture of the mixed solution and the attapulgite is 1% , the mass fraction of lanthanum in the mixture of the mixed solution and the attapulgite clay is 2%. After fully physical mixing for 8 hours, a commercially available extrusion equipment is used to prepare a cylindrical phosphor-locking agent with a diameter of 4-6 mm and a length of 2-8 mm.
实施例3Example 3
选择不同品位(低、中、高)的凹凸棒粘土作为载体，按照实施例1所述的方法，进行混合、挤出物理塑形。为模拟实际使用投加效果，将10.0g的不同材料投入500mL的去离子水中，观察分析材料在水中的溶解速率以及溶解程度。物料在水体中的分散程度决定其对水体磷的去除效果。不同材料的除磷效果如图2所示。The attapulgite clay of different grades (low, medium and high) was selected as the carrier, and mixed and extruded for physical shaping according to the method described in Example 1. In order to simulate the actual dosing effect, 10.0 g of different materials were put into 500 mL of deionized water, and the dissolution rate and degree of dissolution of the analyzed materials in water were observed. The degree of dispersion of the material in the water body determines its phosphorus removal effect in the water body. The phosphorus removal effect of different materials is shown in Figure 2.
实施例4Example 4
以国际上市售的镧改性膨润土(英文商标名Phoslock)为参照对象。将实施例1制备的锁磷剂与Phoslock在水体中以及底泥中的效果进行比较。具体地分别称取本案研发的锁磷材料以及Phoslock 0.5g置于不同浓度的磷溶液中(1-1000mg P/L)，上述材料置于恒温(25℃)摇床中反应24小时。测定反应后剩余磷浓度，计算去除效果，利用朗格缪尔方程计算不同材料的最大除磷量。将本案研发的材料以及Phoslock按照一定比例与磷污染底泥进行混合反应，7天后测定底泥中活性磷的削减量，以对材料底泥磷的控制效果进行比较，结果如表1和图4所示。The internationally marketed lanthanum-modified bentonite (English brand name Phoslock) was used as a reference. The phosphorus-locking agent prepared in Example 1 was compared with Phoslock's effects in water and sediment. Specifically, the phosphorus-locking materials developed in this case and 0.5 g of Phoslock were respectively weighed and placed in phosphorus solutions of different concentrations (1-1000 mg P/L). The residual phosphorus concentration after the reaction was measured, the removal effect was calculated, and the Langmuir equation was used to calculate the maximum phosphorus removal amount of different materials. The materials developed in this case and Phoslock were mixed and reacted with phosphorus-contaminated sediment in a certain proportion. After 7 days, the reduction of active phosphorus in the sediment was determined to compare the control effect of phosphorus in the sediment. The results are shown in Table 1 and Figure 4. shown.
表1：本案干法生产的镧铝复合材料与国际市售锁磷剂最大固磷容量及其他相关参数对比Table 1: Comparison of the maximum solid phosphorus capacity and other related parameters of the lanthanum-aluminum composite material produced by the dry method in this case and the international commercial phosphorus-locking agent
实施例5Example 5
本发明制备的锁磷剂与现有湿法制备锁磷剂(CN109574104A)的效果对比。The effect of the phosphorus-locking agent prepared by the present invention is compared with that of the existing wet-method preparation of the phosphorus-locking agent (CN109574104A).
按照申请人前期申请的专利《一种双金属抗风浪型锁磷材料及其制备方法和应用》中所述方法，先将凹凸棒颗粒在高温活化固结，然后将上述固结的颗粒置于镧铝(LaCl3和AlCl3·6H2O)溶液中进行置换反应。将反应后的颗粒材料洗涤干燥后即为双金属锁磷剂材料，标记为湿法材料。(六水合氯化铝会使粘土体积膨胀，无法进行挤出塑形。此外，六水合氯化铝酸性较强，所制备的产品pH值较低，会引起环境污染)According to the method described in the patent "A bimetallic anti-wind and wave type phosphorus-locking material and its preparation method and application" previously applied for by the applicant, the attapulgite particles are first activated and consolidated at high temperature, and then the above-mentioned consolidated particles are placed in The substitution reaction was carried out in lanthanum aluminum (LaCl3 and AlCl3 ·6H2 O) solution. After washing and drying the reacted particulate material, the bimetallic phosphorus-locking agent material is obtained, which is marked as the wet method material. (Aluminum chloride hexahydrate will cause the clay volume to expand and cannot be extruded and shaped. In addition, aluminum chloride hexahydrate is highly acidic, and the pH value of the prepared product is low, which will cause environmental pollution)
采用实施例1的方法，将未烧结的凹凸棒粉末直接与氯化镧(LaCl3)和聚合氯化铝经过大型混拌装置混合均匀后，置于挤出机进行物理塑形(直径4-6mm)，烘干后(含水率10％)即为本发明所述的干法生产的锁磷材料，标记为干法材料。上述两种方法在生产工艺、产品除磷性能均存在显著差异，如表2所示。Using the method of Example 1, the unsintered attapulgite powder was directly mixed with lanthanum chloride (LaCl3 ) and polyaluminum chloride through a large-scale mixing device, and then placed in an extruder for physical shaping (diameter 4- 6mm), after drying (
表2：不同生产方式获得锁磷剂性能比较Table 2: Performance comparison of phosphorus-locking agents obtained by different production methods
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