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CN116651393A - A composite structure adsorbent for solidifying heavy metals in solid waste heat treatment and preparation method thereof - Google Patents

A composite structure adsorbent for solidifying heavy metals in solid waste heat treatment and preparation method thereof Download PDF

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Publication number
CN116651393A
CN116651393A CN202310740187.8A CN202310740187A CN116651393A CN 116651393 A CN116651393 A CN 116651393A CN 202310740187 A CN202310740187 A CN 202310740187A CN 116651393 A CN116651393 A CN 116651393A
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fly ash
composite structure
solid waste
heat treatment
waste heat
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朱绘美
孙晓
李辉
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Xian University of Architecture and Technology
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Xian University of Architecture and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28064Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28066Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/10Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to the technical field of adsorbents, in particular to a composite structure adsorbent for solidifying heavy metals in solid waste heat treatment and a preparation method thereof. The composite structure adsorbent takes spherical ultrafine fly ash as a core and zeolite as a shell; the zeolite is obtained by the hydrothermal reaction of the shell-broken ultrafine fly ash after alkali melting. The invention successfully prepares the composite structure adsorption material capable of efficiently solidifying heavy metals in a high-temperature environment by combining the high-temperature resistance of the fly ash, the physical adsorption of the shell zeolite material and the chemical solidification of the core high-volcanic ash material, can improve the solidification rate of the heavy metals under the solid waste heat treatment conditions of cement kiln cooperative treatment, incinerator and the like, and ensures the environmental safety of the solid waste heat treatment process.

Description

一种固废热处理中固化重金属的复合结构吸附剂及其制备 方法A composite structure adsorbent for solidifying heavy metals in solid waste heat treatment and its preparation method

技术领域technical field

本发明涉及吸附剂技术领域,特别是涉及一种固废热处理中固化重金属的复合结构吸附剂及其制备方法。The invention relates to the technical field of adsorbents, in particular to an adsorbent with a composite structure solidifying heavy metals in solid waste heat treatment and a preparation method thereof.

背景技术Background technique

将生活垃圾、油泥、工业固体废物、农业固体废物、污水厂污泥和医疗垃圾等可燃性固废利用专用焚烧炉、水泥窑协同处置工艺等进行热处理,可以实现固废的减量化、无害化和资源化。然而,大多数废物中均含有一定量的重金属如铅(Pb)、镉(Cd)、锌(Zn)、砷(As)、钡(Ba)、铜(Cu)等,这些重金属若不能有效固化在灰渣中,将会迁移到大气和土壤中造成直接污染,从而损害生态环境和人体健康。特别是其中的半挥发性重金属(Pb、Cd、Zn)在热处理的高温环境下会部分挥发呈气相,当烟气温度降低时,这些重金属蒸气又会通过均相成核或异相成核冷凝形成细小的颗粒物悬浮在烟气中,固化在灰渣内部的比例非常低。Combustible solid waste such as domestic garbage, oil sludge, industrial solid waste, agricultural solid waste, sewage plant sludge, and medical waste is heat-treated using special incinerators and cement kiln co-processing processes, etc., which can achieve solid waste reduction and zero waste. Harmful and resourceful. However, most wastes contain a certain amount of heavy metals such as lead (Pb), cadmium (Cd), zinc (Zn), arsenic (As), barium (Ba), copper (Cu), etc. If these heavy metals cannot be effectively cured In the ash, it will migrate to the atmosphere and soil to cause direct pollution, thereby damaging the ecological environment and human health. In particular, the semi-volatile heavy metals (Pb, Cd, Zn) will partially volatilize in the gas phase under the high temperature environment of heat treatment. When the temperature of the flue gas decreases, these heavy metal vapors will condense through homogeneous nucleation or heterogeneous nucleation. The formation of fine particles is suspended in the flue gas, and the proportion of solidification inside the ash is very low.

使用吸附剂原位捕集重金属,并利用活性硅铝钙相化学固化重金属是一种很有前景的重金属排放控制技术。然而,当前所用的矿物吸附剂、地聚合物吸附剂与氧化物吸附剂在1100℃以上的高温环境下存在晶相转变及结构坍塌现象,使其在高温度条件下对重金属的吸附率和固化率大幅降低,偏高岭土类的矿物吸附剂甚至会完全失去吸附能力。因此,开发可在高温条件下高效吸附并固化重金属的吸附剂,是提升废物处理工艺环境安全性的重要保障。Using adsorbents to trap heavy metals in situ and chemically immobilize heavy metals using active silica-alumina-calcium phases is a promising technology for heavy metal emission control. However, currently used mineral adsorbents, geopolymer adsorbents, and oxide adsorbents have crystal phase transition and structural collapse at high temperatures above 1100°C, making them difficult to absorb and solidify heavy metals at high temperatures. The rate is greatly reduced, and the metakaolin-based mineral adsorbent will even completely lose its adsorption capacity. Therefore, the development of adsorbents that can efficiently adsorb and solidify heavy metals under high temperature conditions is an important guarantee for improving the environmental safety of waste treatment processes.

发明内容Contents of the invention

基于上述内容,本发明提供一种固废热处理中固化重金属的复合结构吸附剂(简称:复合结构吸附剂)及其制备方法。Based on the above, the present invention provides a composite structure adsorbent for solidifying heavy metals in solid waste heat treatment (composite structure adsorbent for short) and a preparation method thereof.

为实现上述目的,本发明提供了如下方案:To achieve the above object, the present invention provides the following scheme:

本发明技术方案之一,一种固废热处理中固化重金属的复合结构吸附剂,以球形超细粉煤灰为核心,以沸石为外壳;One of the technical solutions of the present invention is a composite structure adsorbent for solidifying heavy metals in solid waste heat treatment, with spherical ultrafine fly ash as the core and zeolite as the shell;

所述沸石通过破壳超细粉煤灰经碱熔融后水热反应得到。The zeolite is obtained by hydrothermal reaction after shell breaking ultrafine fly ash is melted with alkali.

进一步地,所述固废热处理中固化重金属的复合结构吸附剂的比表面积不小于700m2/kg。Further, the specific surface area of the composite structure adsorbent solidifying heavy metals in the solid waste heat treatment is not less than 700m 2 /kg.

进一步地,所述球形超细粉煤灰为通过对粉煤灰进行分选得到的中位粒径小于5μm、比表面积不小于800m2/kg的粉煤灰。Further, the spherical ultrafine fly ash is a fly ash obtained by classifying fly ash with a median particle size of less than 5 μm and a specific surface area of not less than 800 m 2 /kg.

进一步地,所述破壳超细粉煤灰为通过对粉煤灰进行粉磨得到的中位粒径小于5μm、比表面积不小于900m2/kg的粉煤灰。Further, the broken-shell ultrafine fly ash is a fly ash obtained by pulverizing fly ash with a median particle size of less than 5 μm and a specific surface area of not less than 900 m 2 /kg.

本发明技术方案之二,一种上述固废热处理中固化重金属的复合结构吸附剂的制备方法,包括以下步骤:The second technical solution of the present invention is a method for preparing a composite structure adsorbent that solidifies heavy metals in the above-mentioned solid waste heat treatment, comprising the following steps:

步骤1,将破壳超细粉煤灰和氢氧化钠进行碱熔融处理,之后加水进行水热反应,得到沸石相悬浮液;Step 1, performing alkali melting treatment on shell-broken ultrafine fly ash and sodium hydroxide, and then adding water to perform hydrothermal reaction to obtain a zeolite phase suspension;

步骤2,将球形超细粉煤灰加入到所述沸石相悬浮液中,搅拌,离心所得固体烘干,粉磨,得到所述固废热处理中固化重金属的复合结构吸附剂。Step 2, adding spherical ultrafine fly ash into the zeolite phase suspension, stirring, centrifuging, drying and grinding the obtained solid to obtain a composite structure adsorbent solidified with heavy metals in the solid waste heat treatment.

进一步地,步骤1中,所述碱熔融处理具体为:在500-600℃下保温2h。Further, in step 1, the alkali melting treatment specifically includes: keeping the temperature at 500-600° C. for 2 hours.

碱熔融处理的温度低于上述记载的范围不利于地聚合反应的充分进行,高于上述范围会造成反应产物分解。因此,本发明优选的限定碱熔融处理的温度为500-600℃。The temperature of the alkali melting treatment lower than the above-mentioned range is unfavorable for sufficient progress of the polymerization reaction, and higher than the above-mentioned range may cause decomposition of the reaction product. Therefore, the present invention preferably limits the temperature of the alkali melting treatment to 500-600°C.

进一步地,步骤1中,所述水热反应具体为:在80-100℃、600-1000r/min条件下搅拌加热1-2h。Further, in step 1, the hydrothermal reaction specifically includes: stirring and heating at 80-100° C. and 600-1000 r/min for 1-2 hours.

水热反应的温度和时间超出上述设置时,会造成反应不充分,部分产物以N-A-S-H凝胶形式存在,而不是沸石。When the temperature and time of the hydrothermal reaction exceed the above settings, the reaction will be insufficient, and some products will exist in the form of N-A-S-H gel instead of zeolite.

进一步地,步骤2中,所述搅拌的时间不小于10min。Further, in step 2, the stirring time is not less than 10 minutes.

搅拌的目的是使得球形超细粉煤灰颗粒均匀分散于悬浮液中,保证沸石相完全包裹球形超细粉煤灰,可以通过适当延长搅拌时间来保证。The purpose of stirring is to make the spherical ultrafine fly ash particles evenly disperse in the suspension and ensure that the zeolite phase completely covers the spherical ultrafine fly ash, which can be ensured by appropriately extending the stirring time.

进一步地,步骤2中,所述烘干具体为:105±5℃烘干8h。Further, in step 2, the drying is specifically: drying at 105±5° C. for 8 hours.

进一步地,步骤2中,粉磨至比表面积不小于700m2/kg。粉磨工艺可以采用球磨机、雷蒙磨、轮辊磨、盘磨、气流磨等设备。Further, in step 2, grind until the specific surface area is not less than 700m 2 /kg. The grinding process can use equipment such as ball mill, Raymond mill, wheel-roller mill, disc mill, jet mill, etc.

粉磨至比表面积不小于700m2/kg属于超细粉体的范畴;若比表面积低于700m2/kg,会降低吸附剂的吸附效率。Grinding until the specific surface area is not less than 700m 2 /kg belongs to the category of ultrafine powder; if the specific surface area is less than 700m 2 /kg, the adsorption efficiency of the adsorbent will be reduced.

进一步地,所述破壳超细粉煤灰与所述氢氧化钠、球形超细粉煤灰和水的质量比为20~40:5~8:50~80:80。Further, the mass ratio of the broken shell ultrafine fly ash to the sodium hydroxide, spherical ultrafine fly ash and water is 20-40:5-8:50-80:80.

氢氧化钠与破壳超细粉煤灰的比例在上述范围内,利于粉煤灰中活性硅铝地聚合反应的快速进行,进而生成沸石。氢氧化钠与球形超细粉煤灰和水的比例在上述范围内,利于步骤2(包浆步骤)的顺利进行;不然,可能造成球形超细粉煤灰表面沸石包裹不完全、分布不均。The ratio of sodium hydroxide to shell-broken ultrafine fly ash is within the above range, which is beneficial to the rapid progress of the polymerization reaction of active silica and aluminum in the fly ash, and then generates zeolite. The ratio of sodium hydroxide to spherical ultrafine fly ash and water is within the above range, which is conducive to the smooth progress of step 2 (coating step); otherwise, it may cause incomplete and uneven distribution of zeolite on the surface of spherical ultrafine fly ash .

本发明以粉煤灰作为主要原料制备复合结构吸附剂,并通过粉煤灰颗粒形态的变化应对不同功能需求。具体的,采用高活性、高比表面积的破壳超细粉煤灰作为生产沸石的主要原料,以此加速沸石相的生成并提高其纯度;以高球形度的球形超细粉煤灰为内核材料,提高吸附剂的分散性;进而制成以球形超细粉煤灰为内核、沸石相为外壳的复合结构吸附剂。联合发挥外壳多孔沸石相对重金属的强吸附作用,以及内核超细粉煤灰的高火山灰活性对重金属的化学固化作用,在高温条件下起到高效固化重金属的效果。The invention uses fly ash as the main raw material to prepare the composite structure adsorbent, and responds to different functional requirements by changing the shape of the fly ash particles. Specifically, shell-broken ultra-fine fly ash with high activity and high specific surface area is used as the main raw material for the production of zeolite, so as to accelerate the formation of zeolite phase and improve its purity; use spherical ultra-fine fly ash with high sphericity as the core materials to improve the dispersibility of the adsorbent; and then make a composite structure adsorbent with spherical ultra-fine fly ash as the inner core and zeolite phase as the outer shell. Combined with the strong adsorption of porous zeolite on the outer shell relative to heavy metals, and the chemical solidification of heavy metals by the high pozzolanic activity of ultrafine fly ash in the inner core, it can effectively solidify heavy metals under high temperature conditions.

本发明公开了以下技术效果:The invention discloses the following technical effects:

本发明复合结构吸附剂优选具有优异高温稳定性的粉煤灰为原料,在高活性粉煤灰外部构造一层具有强吸附作用的沸石外壳,沸石内部含有的大量架状空穴通道及表面不饱和电荷,对重金属具有高效的物理吸附作用。本发明复合结构吸附剂的核心为高球形度的超细粉煤灰,一方面其可发挥支撑作用,提高吸附剂粉体的分散性,另一方面其高比表面积及高火山灰活性有助于其中硅铝相与重金属的化学结合。以上赋予该复合结构吸附剂物理吸附和化学固化的耦合作用。此外,本发明复合结构吸附剂的核心材料与外壳材料均具有优异的高温稳定性,可消除在高温环境下的结构坍塌和晶型转变产生的吸附失活现象,本发明复合结构吸附剂可高效固化固废热处理中排出的重金属。The composite structure adsorbent of the present invention preferably has fly ash with excellent high temperature stability as a raw material, and a layer of zeolite shell with strong adsorption is constructed outside the high-activity fly ash. Saturated charge, has efficient physical adsorption for heavy metals. The core of the composite structure adsorbent of the present invention is ultra-fine fly ash with high sphericity. On the one hand, it can play a supporting role and improve the dispersibility of the adsorbent powder. On the other hand, its high specific surface area and high pozzolanic activity contribute to Among them, the chemical combination of silicon aluminum phase and heavy metal. The above endows the composite structure adsorbent with the coupling effect of physical adsorption and chemical solidification. In addition, both the core material and the shell material of the composite structure adsorbent of the present invention have excellent high temperature stability, which can eliminate the phenomenon of adsorption deactivation caused by structural collapse and crystal transformation under high temperature environment, and the composite structure adsorbent of the present invention can efficiently Solidification of heavy metals discharged in solid waste heat treatment.

本发明联合利用粉煤灰的耐高温性、外壳沸石材料的物理吸附和核心高火山灰材料的化学固化作用,成功制备出可在高温环境下高效固化重金属的复合结构吸附材料,能够提高水泥窑协同处置、焚烧炉等固废热处理条件下重金属的固化率,确保固废热处理工艺的环境安全性。The invention combines the high temperature resistance of fly ash, physical adsorption of shell zeolite material and chemical solidification of core high pozzolanic material to successfully prepare a composite structure adsorption material that can efficiently solidify heavy metals in a high temperature environment, which can improve cement kiln synergy The solidification rate of heavy metals under solid waste heat treatment conditions such as disposal and incinerators ensures the environmental safety of the solid waste heat treatment process.

附图说明Description of drawings

为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required in the embodiments. Obviously, the accompanying drawings in the following description are only some of the present invention. Embodiments, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

图1为本发明复合结构吸附剂的制备流程示意图。Figure 1 is a schematic diagram of the preparation process of the composite structure adsorbent of the present invention.

图2为本发明实施例以及对比例中所使用的破壳超细粉煤灰、球形超细粉煤灰的SEM图;其中,左图为破壳超细粉煤灰,右图为球形超细粉煤灰。Fig. 2 is the SEM figure of broken shell ultrafine fly ash and spherical ultrafine fly ash used in the examples of the present invention and comparative examples; wherein, the left picture is broken shell ultrafine fly ash, and the right picture is spherical ultrafine fly ash fine fly ash.

图3为本发明实施例以及对比例中所使用的破壳超细粉煤灰、球形超细粉煤灰的粒径分布。Fig. 3 is the particle size distribution of shell-cracked ultrafine fly ash and spherical ultrafine fly ash used in the examples of the present invention and comparative examples.

图4为本发明煅烧实验装置;图中,1-气瓶;2-浮子流量计;3-热电偶;4-管式炉;5-刚玉坩埚;6-尾气处理装置。Fig. 4 is the calcination experimental device of the present invention; in the figure, 1-gas cylinder; 2-rotameter; 3-thermocouple; 4-tube furnace; 5-corundum crucible; 6-tail gas treatment device.

图5为本发明实施例1-4中步骤1制备的沸石结构的SEM图。Fig. 5 is an SEM image of the zeolite structure prepared in step 1 in Examples 1-4 of the present invention.

图6为本发明实施例4制备的复合结构吸附剂的SEM图。Fig. 6 is an SEM image of the composite structure adsorbent prepared in Example 4 of the present invention.

具体实施方式Detailed ways

现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the present invention will now be described in detail. The detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features and embodiments of the present invention.

应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值,以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terminology described in the present invention is only used to describe specific embodiments, and is not used to limit the present invention. In addition, regarding the numerical ranges in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Any stated value or intervening value in a stated range, and each smaller range between any other stated value or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded from the range.

除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials in connection with which the documents are described. In case of conflict with any incorporated document, the contents of this specification control.

在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and changes can be made in the specific embodiments of the present invention described herein without departing from the scope or spirit of the present invention. Other embodiments will be apparent to the skilled person from the description of the present invention. The description and examples of the invention are illustrative only.

关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。As used herein, "comprising", "comprising", "having", "comprising" and so on are all open terms, meaning including but not limited to.

本发明实施例以及对比例中所用原材料,如无特殊说明,均可自市售途径获得。The raw materials used in the examples of the present invention and the comparative examples can be obtained from commercially available sources unless otherwise specified.

本发明实施例以及对比例中所用原料及性能如下:Raw material used and performance in the embodiment of the present invention and comparative example are as follows:

破壳超细粉煤灰:燃煤电厂副产品,将I级粉煤灰超细粉磨加工所得,中位粒径(d50)为2~3μm,其化学组分、微观形貌及粒径分布分别如表1、图2中左图和图3所示,比表面积为1042m2/kg。Broken shell ultrafine fly ash: a by-product of coal-fired power plants, obtained by ultrafine grinding of class I fly ash, with a median particle size (d 50 ) of 2-3 μm, its chemical composition, microscopic appearance and particle size The distribution is shown in Table 1, the left figure in Figure 2 and Figure 3 respectively, and the specific surface area is 1042m 2 /kg.

球形超细粉煤灰:中位粒径(d50)为1.5~2.5μm,对I级粉煤灰分选所得;其化学组分、微观形貌及粒径分布分别如表1、图2中右图和图3所示,比表面积为768m2/kg。Spherical ultrafine fly ash: the median particle size (d 50 ) is 1.5-2.5 μm, obtained from class I fly ash; its chemical composition, microscopic appearance and particle size distribution are shown in Table 1 and Figure 2 respectively As shown in the figure on the right and Figure 3, the specific surface area is 768m 2 /kg.

表1超细粉煤灰的化学组分,wt%Table 1 Chemical composition of ultrafine fly ash, wt%

氢氧化钠:市售固体质量分数大于96wt.%的工业片碱。Sodium hydroxide: commercial caustic soda with solid mass fraction greater than 96wt.%.

水:自来水。Water: tap water.

本发明复合结构吸附剂的制备流程示意图如图1所示。The schematic diagram of the preparation process of the composite structure adsorbent of the present invention is shown in Fig. 1 .

本发明实施例以及对比例中所使用的破壳超细粉煤灰、球形超细粉煤灰的SEM图如图2所示;其中,左图为破壳超细粉煤灰,右图为球形超细粉煤灰。The SEM figure of the broken shell ultrafine fly ash and spherical ultrafine fly ash used in the embodiment of the present invention and comparative examples is as shown in Figure 2; wherein, the left picture is the broken shell ultrafine fly ash, and the right picture is Spherical ultrafine fly ash.

本发明实施例以及对比例中所使用的破壳超细粉煤灰、球形超细粉煤灰的粒径分布如图3所示。The particle size distributions of the cracked ultrafine fly ash and spherical ultrafine fly ash used in the examples of the present invention and the comparative examples are shown in FIG. 3 .

本发明煅烧实验装置如图4所示;图中,1-气瓶;2-浮子流量计;3-热电偶;4-管式炉;5-刚玉坩埚;6-尾气处理装置。The calcination experimental device of the present invention is shown in Figure 4; in the figure, 1-gas cylinder; 2-rotameter; 3-thermocouple; 4-tube furnace; 5-corundum crucible; 6-tail gas treatment device.

实施例1-4Example 1-4

在实施例1-4中,复合结构吸附剂的原料组成按质量份数计,由破壳超细粉煤灰20~40份、氢氧化钠5~8份、球形超细粉煤灰50~80份和水80份组成(具体原料组成见表2)。In Examples 1-4, the raw material composition of the composite structure adsorbent consists of 20 to 40 parts of broken shell ultrafine fly ash, 5 to 8 parts of sodium hydroxide, and 50 to 50 parts of spherical ultrafine fly ash. 80 parts and 80 parts of water (see Table 2 for the specific raw material composition).

上述固废热处理中固化重金属的复合结构吸附剂的制备方法具体为以下步骤:The preparation method of the composite structure adsorbent that solidifies heavy metals in the above solid waste heat treatment specifically includes the following steps:

步骤1,沸石相悬浮液制备:将氢氧化钠和破壳超细粉煤灰原料混合后,在500℃下保温2h进行碱熔融,待其冷却后加水并利用磁力搅拌器在90℃和800r/min的条件下溶解加热2h,即得到沸石相悬浮液(沸石结构SEM图如图5所示),具体流程如图1所示。Step 1, preparation of zeolite phase suspension: After mixing sodium hydroxide and shell-broken ultrafine fly ash raw materials, heat at 500°C for 2 hours for alkali fusion, add water after cooling and use a magnetic stirrer at 90°C and 800r /min under the condition of dissolving and heating for 2 hours to obtain a zeolite phase suspension (the SEM image of the zeolite structure is shown in Figure 5), and the specific process is shown in Figure 1.

步骤2,复合结构吸附剂制备:将球形超细粉煤灰加入沸石相悬浮液,搅拌10分钟使得球形超细粉煤灰颗粒均匀分散于悬浮液中,保证沸石相完全包裹球形超细粉煤灰,离心,在105±5℃下烘干8h,然后粉磨至比表面积不小于700m2/kg,所得粉末产物即为复合结构吸附剂。Step 2, preparation of composite structure adsorbent: add spherical ultrafine fly ash to zeolite phase suspension, stir for 10 minutes to make spherical ultrafine fly ash particles evenly disperse in the suspension, and ensure that zeolite phase completely wraps spherical ultrafine coal Ash, centrifuged, dried at 105±5°C for 8 hours, and then ground until the specific surface area is not less than 700m 2 /kg, and the obtained powder product is the composite structure adsorbent.

表2复合结构吸附剂配合比(质量份数计)Table 2 Composite structure adsorbent mix ratio (in terms of mass parts)

对上述实施例1-4制得的复合结构吸附剂对重金属的固化率进行检测,测试方法如下:The solidification rate of heavy metals is detected by the composite structure adsorbent prepared in the above-mentioned examples 1-4, and the test method is as follows:

采用图4所示的煅烧实验装置,设置800℃-1200℃-1450℃的升温程序,升温速率为20℃/min。将盛有吸附剂和占吸附剂质量0.5%的重金属(PbO/CdO/ZnO三种物质分别进行了固化率检测试验)的刚玉坩埚从管式炉管一端缓缓推到炉管中煅烧。密闭炉门同时打开气瓶气阀以实现炉管内空气流动,用浮子流量计控制气流流量为1L/min。炉管尾部末端通过耐高温硅胶软管连接三个尾气吸收瓶。其中两个尾气吸收瓶内装有250mL的5%HNO3和20%H2O2混合吸收液,一个尾气吸收瓶内装硅胶干燥剂,用于尾气中重金属的吸收。待煅烧实验结束后,将装有样品的坩埚取出用风扇急冷至室温。用HNO3-HCl-HF-H2O2法对煅烧后物料进行消解后采用ICP-MS测定重金属含量。结果如表3所示。The calcination experimental device shown in Figure 4 was used, and the heating program was set at 800°C-1200°C-1450°C, and the heating rate was 20°C/min. The corundum crucible filled with adsorbent and 0.5% of the mass of the adsorbent (PbO/CdO/ZnO three substances were tested for solidification rate respectively) was slowly pushed from one end of the tube furnace tube into the furnace tube for calcination. Close the furnace door and open the gas cylinder valve at the same time to realize the air flow in the furnace tube, and use a float flowmeter to control the air flow to 1L/min. The tail end of the furnace tube is connected to three exhaust gas absorption bottles through a high-temperature resistant silicone hose. Two of the tail gas absorption bottles are filled with 250mL of 5% HNO 3 and 20% H 2 O 2 mixed absorption liquid, and one tail gas absorption bottle is filled with silica gel desiccant for the absorption of heavy metals in the tail gas. After the calcination experiment was over, the crucible containing the samples was taken out and cooled to room temperature with a fan. The calcined material was digested by HNO 3 -HCl-HF-H 2 O 2 method, and the heavy metal content was determined by ICP-MS. The results are shown in Table 3.

复合结构吸附剂对重金属的固化率计算公式如下:The calculation formula for the solidification rate of heavy metals by the composite structure adsorbent is as follows:

式中:R:重金属在吸附剂中的固化率(100%);In the formula: R: solidification rate (100%) of heavy metal in adsorbent;

K:重金属在煅烧后样品中的含量(mg/kg);K: content of heavy metals in the sample after calcination (mg/kg);

S:重金属在煅烧前样品中的含量(mg/kg);S: content of heavy metals in the sample before calcination (mg/kg);

LOI:样品的烧失量(%)。LOI: loss on ignition (%) of a sample.

表3复合结构吸附剂对重金属的固化率(%)The solidification rate (%) of table 3 composite structure adsorbent to heavy metal

项目project PbOPbO CdOCdO ZnOZnO 实施例1Example 1 8686 9292 9595 实施例2Example 2 9090 9393 9292 实施例3Example 3 8585 9090 8989 实施例4Example 4 9292 9494 9696

结果显示,本发明实施例1-4制备的复合结构吸附剂可高效固化固废热处理工艺中排放的重金属;以水泥窑协同处置固废为例,不使用吸附剂时,水泥熟料对PbO、CdO、ZnO的固化率分别为15%、17%和21%。The results show that the composite structure adsorbent prepared in Examples 1-4 of the present invention can efficiently solidify the heavy metals discharged in the solid waste heat treatment process; taking the co-processing of solid waste in cement kiln as an example, when no adsorbent is used, the cement clinker has no effect on PbO, The curing rates of CdO and ZnO are 15%, 17% and 21%, respectively.

实施例4制备的复合结构吸附剂的SEM图如图6所示,图中,球形的是粉煤灰颗粒,外部包裹的即为沸石层,由图6能够看出,实施例4制备的复合结构吸附剂为核壳结构。The SEM image of the composite structure adsorbent prepared in Example 4 is shown in Figure 6. In the figure, the spherical ones are fly ash particles, and the outer wrapping is the zeolite layer. It can be seen from Figure 6 that the composite structure prepared in Example 4 The structured adsorbent has a core-shell structure.

对比例1Comparative example 1

与实施例4不同之处仅在于,省略沸石相悬浮液的制备过程,仅以球形超细粉煤灰作为吸附剂。具体制备步骤如下:The only difference from Example 4 is that the preparation process of the zeolite phase suspension is omitted, and only spherical ultrafine fly ash is used as the adsorbent. Concrete preparation steps are as follows:

将球形超细粉煤灰在在105±5℃下烘干8h,然后粉磨至比表面积不小于700m2/kg,所得粉末产物即为吸附剂。Spherical ultrafine fly ash is dried at 105±5°C for 8 hours, and then ground until the specific surface area is not less than 700m 2 /kg, and the obtained powder product is the adsorbent.

对本对比例制备的吸附剂进行与实施例4相同的重金属固化率测试实验,结果显示,本对比例制备的吸附剂对PbO的固化率为23%、对CdO的固化率为30%、对ZnO的固化率为32%。The sorbent prepared in this comparative example was subjected to the same heavy metal solidification rate test experiment as in Example 4. The results showed that the sorbent prepared in this comparative example had a solidification rate of 23% for PbO, 30% for CdO, and 30% for ZnO. The curing rate is 32%.

对比例2Comparative example 2

与实施例4不同之处仅在于,步骤1中,将破壳超细粉煤灰替换为比表面积420m2/kg的I级粉煤灰(化学组成与破壳超细粉煤灰同质)。The only difference from Example 4 is that in step 1, the broken-shell ultrafine fly ash is replaced by Class I fly ash with a specific surface area of 420m 2 /kg (the chemical composition is homogeneous with the broken shell ultra-fine fly ash) .

对本对比例制备的吸附剂进行与实施例4相同的重金属固化率测试实验,结果显示,本对比例制备的吸附剂对PbO的固化率为38%、对CdO的固化率为43%、对ZnO的固化率为49%。The sorbent prepared in this comparative example was subjected to the same heavy metal solidification rate test experiment as in Example 4. The results showed that the sorbent prepared in this comparative example had a solidification rate of 38% for PbO, 43% for CdO, and 43% for ZnO. The curing rate is 49%.

对比例3Comparative example 3

与实施例4不同之处仅在于,步骤1中,将破壳超细粉煤灰替换为球形超细粉煤灰。The only difference from Example 4 is that in step 1, the broken shell ultrafine fly ash is replaced by spherical ultrafine fly ash.

对本对比例制备的吸附剂进行与实施例4相同的重金属固化率测试实验,结果显示,本对比例制备的吸附剂对PbO的固化率为41%、对CdO的固化率为47%、对ZnO的固化率为51%。The sorbent prepared in this comparative example was subjected to the same heavy metal solidification rate test experiment as in Example 4. The results showed that the sorbent prepared in this comparative example had a solidification rate of 41% for PbO, 47% for CdO, and 47% for ZnO. The curing rate is 51%.

对比例4Comparative example 4

与实施例4不同之处仅在于,步骤2中,将球形超细粉煤灰替换为比表面积420m2/kg的I级粉煤灰(化学组成与球形超细粉煤灰同质)。The only difference from Example 4 is that in step 2, the spherical ultrafine fly ash is replaced by Class I fly ash with a specific surface area of 420 m 2 /kg (the chemical composition is homogeneous to that of the spherical ultrafine fly ash).

对本对比例制备的吸附剂进行与实施例4相同的重金属固化率测试实验,结果显示,本对比例制备的吸附剂对PbO的固化率为40%、对CdO的固化率为46%、对ZnO的固化率为50%。The sorbent prepared in this comparative example was subjected to the same heavy metal solidification rate test experiment as in Example 4, and the results showed that the sorbent prepared in this comparative example had a solidification rate of 40% for PbO, 46% for CdO, and 46% for ZnO. The curing rate is 50%.

对比例5Comparative example 5

与实施例4不同之处仅在于,步骤2中,将球形超细粉煤灰替换为破壳超细粉煤灰。The only difference from Example 4 is that in step 2, the spherical ultrafine fly ash is replaced by the broken shell ultrafine fly ash.

对本对比例制备的吸附剂进行与实施例4相同的重金属固化率测试实验,结果显示,本对比例制备的吸附剂对PbO的固化率为43%、对CdO的固化率为49%、对ZnO的固化率为52%。The sorbent prepared in this comparative example was subjected to the same heavy metal solidification rate test experiment as in Example 4. The results showed that the sorbent prepared in this comparative example had a solidification rate of 43% for PbO, 49% for CdO, and 49% for ZnO. The curing rate is 52%.

本发明提出一种固废热处理中固化重金属的(粉煤灰基)复合结构吸附剂及其制备方法,通过联用外壳物理吸附和核心化学固化,可高效固化固废热处理工艺中排放的重金属。The invention proposes a (fly ash-based) composite structure adsorbent for solidifying heavy metals in solid waste heat treatment and a preparation method thereof, which can efficiently solidify heavy metals discharged in solid waste heat treatment processes by combining physical adsorption of the shell and chemical curing of the core.

以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。The above-mentioned embodiments are only to describe the preferred mode of the present invention, and are not intended to limit the scope of the present invention. Variations and improvements should fall within the scope of protection defined by the claims of the present invention.

Claims (10)

1.一种固废热处理中固化重金属的复合结构吸附剂,其特征在于,以球形超细粉煤灰为核心,以沸石为外壳;1. A composite structure adsorbent for solidifying heavy metals in solid waste heat treatment, characterized in that it takes spherical ultrafine fly ash as the core and takes zeolite as the shell; 所述沸石通过破壳超细粉煤灰经碱熔融后水热反应得到。The zeolite is obtained by hydrothermal reaction after shell breaking ultrafine fly ash is melted with alkali. 2.根据权利要求1所述的固废热处理中固化重金属的复合结构吸附剂,其特征在于,所述固废热处理中固化重金属的复合结构吸附剂的比表面积不小于700m2/kg。2 . The composite structure adsorbent for solidifying heavy metals in solid waste heat treatment according to claim 1 , wherein the specific surface area of the solid waste heat treatment composite structure adsorbent for solidifying heavy metals is not less than 700 m 2 /kg. 3.根据权利要求1或2所述的固废热处理中固化重金属的复合结构吸附剂,其特征在于,所述球形超细粉煤灰为通过对粉煤灰进行分选得到的中位粒径小于5μm、比表面积不小于800m2/kg的粉煤灰。3. the solid waste heat treatment according to claim 1 or 2 is characterized in that, described spherical superfine fly ash is the median particle size obtained by sorting fly ash Fly ash smaller than 5μm and specific surface area not less than 800m 2 /kg. 4.根据权利要求1或2所述的固废热处理中固化重金属的复合结构吸附剂,其特征在于,所述破壳超细粉煤灰为通过对粉煤灰进行粉磨得到的中位粒径小于5μm、比表面积不小于900m2/kg的粉煤灰。4. The solid waste heat treatment according to claim 1 or 2, wherein the solidified heavy metal composite structure adsorbent is characterized in that the broken shell ultra-fine fly ash is the median particle obtained by grinding the fly ash Fly ash with diameter less than 5μm and specific surface area not less than 900m 2 /kg. 5.一种权利要求1~4任一项所述的固废热处理中固化重金属的复合结构吸附剂的制备方法,其特征在于,包括以下步骤:5. A method for preparing a composite structure adsorbent for solidifying heavy metals in the solid waste heat treatment according to any one of claims 1 to 4, characterized in that it comprises the following steps: 步骤1,将破壳超细粉煤灰和氢氧化钠进行碱熔融处理,之后加水进行水热反应,得到沸石相悬浮液;Step 1, performing alkali melting treatment on shell-broken ultrafine fly ash and sodium hydroxide, and then adding water to perform hydrothermal reaction to obtain a zeolite phase suspension; 步骤2,将球形超细粉煤灰加入到所述沸石相悬浮液中,搅拌,离心所得固体烘干,粉磨,得到所述固废热处理中固化重金属的复合结构吸附剂。Step 2, adding spherical ultrafine fly ash into the zeolite phase suspension, stirring, centrifuging, drying and grinding the obtained solid to obtain a composite structure adsorbent solidified with heavy metals in the solid waste heat treatment. 6.根据权利要求5所述的制备方法,其特征在于,步骤1中,所述碱熔融处理具体为:在500-600℃下保温2h。6 . The preparation method according to claim 5 , characterized in that, in step 1, the alkali melting treatment specifically includes: keeping warm at 500-600° C. for 2 hours. 7 . 7.根据权利要求5所述的制备方法,其特征在于,步骤1中,所述水热反应具体为:在80-100℃、600-1000r/min条件下搅拌加热1-2h。7. The preparation method according to claim 5, characterized in that, in step 1, the hydrothermal reaction specifically comprises: stirring and heating at 80-100°C and 600-1000r/min for 1-2h. 8.根据权利要求5所述的制备方法,其特征在于,步骤2中,所述烘干具体为:105±5℃烘干8h。8 . The preparation method according to claim 5 , wherein in step 2, the drying is specifically: drying at 105±5° C. for 8 hours. 9.根据权利要求5所述的制备方法,其特征在于,步骤2中,粉磨至比表面积不小于700m2/kg。9. The preparation method according to claim 5, characterized in that, in step 2, the powder is ground until the specific surface area is not less than 700m 2 /kg. 10.根据权利要求5所述的制备方法,其特征在于,所述破壳超细粉煤灰与所述氢氧化钠、球形超细粉煤灰和水的质量比为20~40:5~8:50~80:80。10. The preparation method according to claim 5, characterized in that, the mass ratio of the broken shell ultrafine fly ash to the sodium hydroxide, spherical ultrafine fly ash and water is 20~40:5~ 8:50~80:80.
CN202310740187.8A 2023-06-21 2023-06-21 A composite structure adsorbent for solidifying heavy metals in solid waste heat treatment and preparation method thereof Pending CN116651393A (en)

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