WO2023019992A1 - 一种工业固体废物中重金属赋存关键矿相的分析判定方法 - Google Patents

一种工业固体废物中重金属赋存关键矿相的分析判定方法 Download PDF

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WO2023019992A1
WO2023019992A1 PCT/CN2022/087877 CN2022087877W WO2023019992A1 WO 2023019992 A1 WO2023019992 A1 WO 2023019992A1 CN 2022087877 W CN2022087877 W CN 2022087877W WO 2023019992 A1 WO2023019992 A1 WO 2023019992A1
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heavy metal
solid waste
dissociation
cleaning
occurrence
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French (fr)
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林璋
林乐
梁彦杰
刘学明
柯勇
颜旭
田晨
刘章斌
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中南大学
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    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
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    • G01N2223/00—Investigating materials by wave or particle radiation
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    • G01N2223/056—Investigating materials by wave or particle radiation by diffraction, scatter or reflection diffraction
    • G01N2223/0566—Investigating materials by wave or particle radiation by diffraction, scatter or reflection diffraction analysing diffraction pattern
    • G—PHYSICS
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    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/637—Specific applications or type of materials liquid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/652—Specific applications or type of materials impurities, foreign matter, trace amounts

Definitions

  • the invention relates to the technical field of detection and analysis of materials, in particular to an analysis and determination method for key mineral phases of heavy metals in industrial solid waste.
  • Industrial solid waste can easily lead to various types of environmental pollution, among which the pollution caused by heavy metal industrial solid waste is the worst. Therefore, the rational treatment and disposal of industrial solid wastes containing heavy metals has become extremely important.
  • the Tessier continuous extraction method divides heavy metals into five binding forms: ion exchange state, carbonate binding state, iron (manganese) oxide binding state, organic matter and sulfide binding state, and residue state, while the BCR continuous extraction method Heavy metals were divided into acid extractable state, reducible state, oxidizable state and residue state.
  • these two methods can only classify the occurrence states of heavy metals into several types with the same or similar chemical properties, and cannot know the quantitative information on the occurrence of heavy metals in specific mineral phases, which cannot meet the requirements of increasingly refined and customized industrial solid waste.
  • Handle disposal scheme design due to the inherent defects of continuous extraction operations, each step of operation can only be started after the previous step is completed, and the experimental cycle is longer.
  • the main purpose of the present invention is to provide a method for analyzing and judging the key mineral phases of heavy metals in industrial solid wastes, aiming to solve the complex and unquantifiable characterization methods for the key mineral phases of heavy metals in industrial solid wastes in the prior art technical problem.
  • the present invention provides a method for analyzing and judging key mineral phases of heavy metals in industrial solid waste, comprising the steps of:
  • step S3 performing quantitative analysis on the mineral phase of the dissociated solid residue after dissociation in step S2, to obtain the relative content Wi ik of each mineral phase in the M mineral phases of the heavy metal solid waste to be measured, and then according to the formula Calculate the degree of dissociation for each of the described mineral phases
  • k 1,2,3,...,M
  • li ik represents the degree of dissociation of mineral phase k in the ith concentration gradient measurement
  • W 0k is the mineral phase under the initial conditions of the heavy metal solid waste to be measured
  • the mass fraction of k, m 0 is the initial sample mass of the heavy metal solid waste to be measured
  • mi is the mass of the dissociated solid residue after the measurement of the i-th concentration gradient
  • Wi ik is the dissociation after the measurement of the i-th concentration gradient
  • the calculation formula of the d ij includes ⁇ 0j is the mass fraction of heavy metal element j under the initial conditions of the heavy metal solid waste to be measured, c ij is the concentration of heavy metal element j in the dissociation solution after the i-th concentration gradient measurement, V ij is the i-th concentration gradient measurement The volume of post-dissociation solution.
  • step S2 it also includes pre-cleaning the heavy metal solid waste to be tested; wherein, the calculation method of ⁇ 0j is Wherein, ⁇ 'j is the mass fraction of heavy metal element j in the heavy metal solid waste to be measured without pre-cleaning, ma is the mass of the heavy metal solid waste to be measured without pre-cleaning, and m b is after pre-cleaning The quality of the heavy metal solid waste to be measured, c'j is the concentration of heavy metal element j in the cleaning solution after the heavy metal solid waste to be measured without pre-cleaning, V is the heavy metal solid waste to be measured after pre-cleaning The volume of cleaning solution.
  • step S1 it also includes the step of pretreating the heavy metal solid waste to be tested: air-drying the sample of the heavy metal solid waste to be tested at 60-105°C and then grinding it to 200 mesh Sample powder below.
  • the step of performing N concentration gradient dissociation assays under the same dissociation conditions includes: performing non-specific dissociation on solid waste in acid solutions with N concentration gradients under the same time and external field action, and The dissociated solution after dissociation is subjected to the determination of the content of heavy metal elements; wherein, the acid solution is a mixed acid with a substance ratio of nitric acid:hydrochloric acid of 1:3; the ratio of dissociated liquid to solid is 8 to 12:1 (L/kg) , the temperature is 15-35°C, the dissociation time is 1-2h; the external field action includes ultrasonic waves, the ultrasonic frequency is 20kHz-40kHz, and the power is 200-500W.
  • the number of N is equal to the number M of ore phases of the heavy metal solid waste to be tested, wherein the hydrogen ion concentration range of the acid solution in the N concentration gradient dissociation assay is 0-12mol/L.
  • the step of quantitative analysis of mineral phases includes: obtaining an X-ray diffraction spectrum through X-ray diffraction analysis, and determining all mineral phases in the dissociated solid residue based on the method of standard-added Rietveld full-spectrum fitting refinement.
  • Relative content wherein the mineral phase not included in the dissociated solid residue is selected as an internal standard substance, and the internal standard substance includes aluminum oxide or zinc oxide.
  • the preset accumulation threshold is 80%-95%.
  • the method for determining the content of heavy metal elements is one or any combination of inductively coupled plasma emission spectroscopy, atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, and atomic fluorescence spectroscopy.
  • the heavy metal solid waste to be tested is subjected to N concentration gradient dissociation measurements under the same dissociation conditions, and the N concentration gradients are obtained.
  • N concentration gradients are obtained.
  • quantitatively analyze the mineral phase of the dissociated solid residue after dissociation obtain the relative content of each mineral phase in the M mineral phases of the heavy metal solid waste to be measured, and then solve it to obtain
  • the occurrence and distribution ratio of the heavy metal elements in the mineral phases, the occurrence ratio of the heavy metal elements in the mineral phases is accumulated from high to low, and the mineral phases whose cumulative occurrence ratio exceeds the preset accumulation threshold are determined as The key mineral phases for the occurrence of the heavy metal elements.
  • Fig. 1 is the flow chart of the method for analyzing and judging key mineral phases of heavy metal occurrence in industrial solid waste of the present invention
  • Fig. 2 is an X-ray diffraction analysis spectrum of chromium slag in an embodiment.
  • Fig. 1 for the analysis and judgment method of heavy metal occurrence key mineral phase in industrial solid waste in a specific example of the present invention, comprise steps:
  • the determination of the content of heavy metal elements can be qualitative and then quantitative.
  • the qualitative method can be X-ray fluorescence spectroscopy
  • the quantitative method can be one or more of inductively coupled plasma emission spectroscopy, atomic absorption spectroscopy, and laser-induced breakdown spectroscopy. any combination of .
  • step S1 it also includes the step of pretreating the heavy metal solid waste to be tested: air-drying the sample of the heavy metal solid waste to be tested at 60-105°C and then grinding it to 200 mesh The following sample powders were then dried to constant weight.
  • the step of performing N concentration gradient dissociation assays under the same dissociation conditions includes: performing non-specific dissociation on solid waste in acid solutions with N concentration gradients under the same time and external field action, and The dissociated solution after dissociation is subjected to the determination of the content of heavy metal elements; wherein, the acid solution is a mixed acid with a substance ratio of nitric acid:hydrochloric acid of 1:3; the ratio of dissociated liquid to solid is 8 to 12:1 (L/kg) , the temperature is 15-35°C, the dissociation time is 1-2h; the external field action includes ultrasonic waves, the ultrasonic frequency is 20kHz-40kHz, and the power is 200-500W.
  • the method for determining the content of heavy metal elements can be one or any combination of inductively coupled plasma emission spectroscopy, atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, and atomic fluorescence spectroscopy.
  • the calculation formula of the d ij includes ⁇ 0j is the mass fraction of heavy metal element j under the initial conditions of the heavy metal solid waste to be measured, c ij is the concentration of heavy metal element j in the dissociation solution after the i-th concentration gradient measurement, V ij is the i-th concentration gradient measurement The volume of post-dissociation solution.
  • step S2 it also includes pre-cleaning the heavy metal solid waste to be tested; wherein, the calculation method of ⁇ 0j is Wherein, ⁇ 'j is the mass fraction of heavy metal element j in the heavy metal solid waste to be measured without pre-cleaning, ma is the mass of the heavy metal solid waste to be measured without pre-cleaning, and m b is after pre-cleaning The quality of the heavy metal solid waste to be measured, c'j is the concentration of heavy metal element j in the cleaning solution after the heavy metal solid waste to be measured without pre-cleaning, V is the heavy metal solid waste to be measured after pre-cleaning The volume of cleaning solution.
  • the method for determining the content of heavy metal elements is any combination of one or more of inductively coupled plasma emission spectroscopy, atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, and atomic fluorescence spectroscopy;
  • the steps of the mineral phase quantitative analysis include : Obtain an X-ray diffraction spectrum by X-ray diffraction analysis, determine the relative content of all mineral phases in the dissociated solid residue based on the Rietveld full-spectrum fitting refinement method, wherein, select the dissociated solid residue
  • the mineral phase not included in the residue was used as an internal standard substance, and the internal standard substance included aluminum oxide or zinc oxide.
  • step S3 performing quantitative analysis on the mineral phase of the dissociated solid residue after dissociation in step S2, to obtain the relative content Wi ik of each mineral phase in the M mineral phases of the heavy metal solid waste to be measured, and then according to the formula Calculate the degree of dissociation for each of the described mineral phases
  • k 1,2,3,...,M
  • li ik represents the degree of dissociation of mineral phase k in the ith concentration gradient measurement
  • W 0k is the mineral phase under the initial conditions of the heavy metal solid waste to be measured
  • the mass fraction of k, m 0 is the initial sample mass of the heavy metal solid waste to be measured
  • mi is the mass of the dissociated solid residue after the measurement of the i-th concentration gradient
  • Wi ik is the dissociation after the measurement of the i-th concentration gradient
  • the number of N is equal to the number M of ore phases of the heavy metal solid waste to be tested, wherein the hydrogen ion concentration range of the acid solution in the N concentration gradient dissociation assay is 0-12 mol/L.
  • the step of quantitative analysis of mineral phases includes: obtaining an X-ray diffraction spectrum through X-ray diffraction analysis, and determining the amount of all mineral phases in the dissociated solid residue based on the method of standard-added Rietveld full-spectrum fitting refinement.
  • Relative content wherein the mineral phase not included in the dissociated solid residue is selected as an internal standard substance, and the internal standard substance includes aluminum oxide or zinc oxide.
  • the preset accumulation threshold is 80%-95%.
  • the determination of the key mineral phases for the occurrence of heavy metals is for different heavy metals. Specifically, it can be as follows: refer to the Pareto rule, and arrange the occurrence distribution ratio of the heavy metal element j in each mineral phase from high to low , then it can be considered that the key mineral phases for the occurrence of heavy metal element j in the solid waste sample are the first few mineral phases whose cumulative occurrence distribution ratio is equal to or exceeds 80%.
  • the object of this embodiment is taken from the chromium slag produced by a certain chromium salt enterprise in Yunnan, which is a typical industrial solid waste containing heavy metals.
  • chromium is the most concerned heavy metal element in pollution control engineering.
  • the solid waste is preferably quartered to take an appropriate amount of original samples, pulverized with a pulverizer until it completely passes through a 200-mesh sieve, then placed in an open beaker, and dried in a blast oven at 105°C Dry for 6 hours to constant weight.
  • the obtained solution was centrifuged at 8000rpm for 10min, washed three times, the supernatant was fixed to 250ml, diluted to a concentration range suitable for ICP-AES detection, and the content of heavy metal elements was determined by ICP-AES; the residual solid was placed in an open beaker , dried in a blast oven at 105°C for 8 hours to constant weight.
  • use an analytical balance to weigh the solid waste samples before and after pre-cleaning, accurate to four decimal places.
  • Concentration Gradient Dissociation Determination Those skilled in the art know that the analysis of the content of heavy metal elements in the original sample generally adopts the method of strong acid digestion combined with instrumental characterization.
  • the solid waste is preferably digested with aqua regia-HF-HClO4 mixed acid system at 250°C, and the remaining clear solution is constant to volume and diluted to a concentration range suitable for ICP-AES detection, and then used ICP-AES Determine the content of heavy metal elements.
  • a concentrated mixed acid solution with a substance ratio of 1:3 was first prepared, in which the concentration of hydrochloric acid was 9 mol/L, and the concentration of nitric acid was 3 mol/L. Then through the dilution operation, the required concentration gradient is prepared, which are 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 1mol/L, 2mol/L, 4mol/L , 6mol/L, 8mol/L, 10mol/L, 12mol/L.
  • the basic principle of concentration gradient design is to ensure that all kinds of mineral phase particles have the opportunity to completely dissociate or almost completely dissociate, and to make the degree of dissociation of the same mineral phase different under different concentration experimental conditions.
  • the gradient design of "low concentration sparse, high concentration dense” can be adopted; for solid waste with poor stability, such as chemical precipitation sludge and fly ash, " Low concentration dense, high concentration sparse” gradient design; if unsure, adopt the gradient design used in this embodiment.
  • the solid waste sample was dissociated for 1 hour under the condition of 30 kHz ultrasonic wave and temperature of 25° C. according to the liquid-solid ratio of 10:1 (L/kg). After dissociation, the solution was centrifuged at 8000rmp for 10min, the residue was washed three times with 20ml of deionized water, combined with the supernatant to make up to 100ml, and after dilution, ICP-AES was used to determine the content of heavy metal elements. The solid part was dried for 8h to constant weight and weighed.
  • the dissociation degree of heavy metal element Cr in the sample after pre-cleaning can be calculated. details as follows:
  • step S4 the dissociation degree of each concentration gradient experiment (d1-d12) heavy metal element Cr can be obtained by the formula Calculate, as follows:
  • Quantitative analysis of mineral phases was carried out on the dissociated solid residue after dissociation: the quantitative analysis method of mineral phases was X-ray diffraction analysis (XRD), specifically, all mineral phases (including those without The relative content of ⁇ -Al 2 O 3 powder was selected as the internal standard substance, and the mixing ratio was 10%.
  • XRD X-ray diffraction analysis
  • all mineral phases including those without The relative content of ⁇ -Al 2 O 3 powder was selected as the internal standard substance, and the mixing ratio was 10%.
  • XRD X-ray diffraction analysis
  • the refinement of Rietveld full-spectrum fitting needs to be based on the fine scanning of XRD, and different analysis software can realize the refinement function.
  • the X-ray diffractometer of Bruker Company is selected, and the fine scanning is carried out in the range of 5-80° with 0.01° as the step size and 2.5s as the step, and the data result analysis software is TOPAS.
  • the dissociation degree of mineral phase in each concentration gradient dissociation experiment can be calculated. details as follows:
  • the heavy metal element Cr is present in the amorphous phase, hydrogarnet (Ca 3 Al 1.54 Fe 0.46 (OH) 12 ), andandite (Ca 2 Fe 1.28 Al 0.72 O 5 ), calcium carbonate (CaCO 3 ) and the cumulative occurrence distribution ratio of the first four mineral phases are 0.8414 (greater than 0.8), then it can be considered that the amorphous phase, hydrogarnet (Ca 3 Al 1.54 Fe 0.46 (OH) 12 ), andorite (Ca 2 Fe 1.28 Al 0.72 O 5 ), and calcium carbonate (CaCO 3 ) are key mineral phases for the occurrence of heavy metal element Cr in the solid waste.

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Abstract

一种工业固体废物中重金属赋存关键矿相的分析判定方法，通过对待测重金属固体废物在相同解离条件下进行N个浓度梯度解离测定，并获得N个不同浓度梯度下的待判定重金属元素的解离度，对解离后的解离固体残留物进行矿相定量分析，获得待测重金属固体废物的M个矿相中每个矿相的相对含量，然后求解得到重金属元素在矿相中的赋存分布比例，将重金属元素在矿相中赋存比例由高到低进行累计，且累计赋存比例超过预设累计阈值的矿相判定为重金属元素的赋存关键矿相。该方法实现了工业固体废物中重金属赋存状态的准确分析，为工业固废的处理处置技术选择提供了精细化技术支持。

Description

一种工业固体废物中重金属赋存关键矿相的分析判定方法 技术领域
本发明涉及材料的检测分析技术领域，尤其涉及一种工业固体废物中重金属赋存关键矿相的分析判定方法。
背景技术
工业固体废物极易导致多种类型的环境污染，其中以重金属工业固体废物所致污染影响最为恶劣。因此，合理处理处置含重金属的工业固体废物就变得格外重要。
合理的处理处置重金属工业固废，首要的就是要对工业固废中重金属赋存状态进行系统性解析。目前，在环境领域常用的赋存状态判定方法主要是Tessier五步连续提取法和BCR三步连续提取法。这两种方法最早是为探明河流沉积物和土壤中重金属形态而开发，后被应用于固体废物的相关研究，然而实际上由于缺乏固废的标准参考物质，这种研究者自发的迁移应用的合理性并未得到验证。其次，Tessier连续提取法将重金属分为5种结合形态：即离子交换态、碳酸盐结合态、铁(锰)氧化物结合态、有机质及硫化物结合态、残渣态，而BCR连续提取法则将重金属分为酸可提取态、可还原态、可氧化态和残渣态。但这两种方法仅能将重金属的赋存状态归纳为化学性质相同或相近的几类，无法知悉重金属在具体矿相中赋存定量信息，已无法满足日趋精细化、定制化的工业固废处理处置方案设计。另外，由于连续提取操作的固有缺陷，每步操作只能待上一步操作完成后开始，其实验周期较长。
因此，有必要开发一种新的工业固体废物中重金属赋存关键矿相的分析判定方法，以准确可靠地量化重金属在各矿相中的赋存比例，并判定出影响处理处置技术选择的重金属赋存关键矿相。
发明内容
本发明的主要目的是提供一种工业固体废物中重金属赋存关键矿相的分析判定方法，旨在解决现有技术中对工业固体废物中重金属赋存关键矿相的表征方法复杂且无法定量化技术问题。
为实现上述目的，本发明提供一种工业固体废物中重金属赋存关键矿相的分析判定方法，包括步骤：
S1，对待测重金属固体废物进行重金属元素含量测定，获取所述待测重金属固体废物中赋存的P种待判定重金属元素的含量；
S2，对所述待测重金属固体废物在相同解离条件下进行N个浓度梯度解离测定，并获得N个不同浓度梯度下的所述待判定重金属元素的解离度
Figure PCTCN2022087877-appb-000001
所述d ij代表第i个浓度梯度解离测定中待判定重金属元素j的解离度，d ij∈(0,1)，i＝1,2,3,...,N，j＝1,2,...,P；
S3，对步骤S2中解离后的解离固体残留物进行矿相定量分析，获得所述待测重金属固体废物的M个矿相中每个矿相的相对含量W ik，然后根据公式
Figure PCTCN2022087877-appb-000002
计算每个所述矿相的解离度
Figure PCTCN2022087877-appb-000003
其中，k＝1,2,3,...,M，l ik代表第i个浓度梯度测定中矿相k的解离度，W 0k为所述待测重金属固体废物的初始条件下矿相k的质量分数，m 0为所述待测重金属固体废物的初始样品质量，m i为第i个浓度梯度测定后的解离固体残留物质量，W ik为第i个浓度梯度测定后解离固体残留物中矿相k的质量分数；
S4，根据公式L n×m×R m×p＝Exp n×p，求解得到所述重金属元素在所述矿相中的赋存分布比例
Figure PCTCN2022087877-appb-000004
S5，将重金属元素j在所述矿相中赋存比例由高到低进行累计，且累计赋存比例超过预设累计阈值的矿相判定为所述重金属元素j的赋存关键矿相。
进一步的，所述d ij的计算公式包括
Figure PCTCN2022087877-appb-000005
ω 0j为所述待测重金属固体废物的初始条件下重金属元素j的质量分数，c ij为第i个浓度梯度测定后解离溶液中重金属元素j的浓度，V ij为第i个浓度梯度测定后解离溶液的体积。
进一步的，所述步骤S2之前，还包括对所述待测重金属固体废物进行预 清洗处理；其中，所述ω 0j的计算方式为
Figure PCTCN2022087877-appb-000006
其中，ω' j为未经预清洗的所述待测重金属固体废物中重金属元素j的质量分数，m a为未经预清洗的所述待测重金属固体废物的质量，m b为预清洗后的所述待测重金属固体废物的质量，c' j为未经预清洗的所述待测重金属固体废物后清洗液中重金属元素j的浓度，V为预清洗后的所述待测重金属固体废物清洗液的体积。
进一步的，所述预清洗的步骤包括：采用0.1mol/L的pH＝7.0醋酸铵溶液作为预清洗试剂，将所述待测重金属固体废物与0.1mol/L的pH＝7.0醋酸铵溶液以液固比10：1(L/kg)混合后，在15～35℃条件下水平震荡1-2h，所得溶液在6000rpm-10000rpm条件下离心3-10min得到清洗液和预清洗后的所述待测重金属固体废物；对所述清洗液进行重金属元素含量测定，以及对所述预清洗后的所述待测重金属固体废物进行矿相定量分析。
进一步的，所述步骤S1之前，还包括对所述待测重金属固体废物进行预处理的步骤：将所述待测重金属固体废物的样品在60～105℃下进行空气烘干后研磨至200目以下的样品粉末。
进一步的，所述在相同解离条件下进行N个浓度梯度解离测定的步骤包括：在相同时间和外场作用下，在N个浓度梯度的酸溶液中对固体废物进行非特异性解离，对解离后的解离溶液进行重金属元素含量测定；其中，所述酸溶液为硝酸：盐酸的物质的量比为1：3的混酸；解离液固比8～12：1(L/kg)，温度为15～35℃，解离时间1-2h；外场作用包括超声波，超声频率20kHz-40kHz，功率200-500W。
进一步的，N的个数等于所述待测重金属固体废物的矿相个数M，其中，N个浓度梯度解离测定中酸溶液的氢离子浓度范围为0-12mol/L。
进一步的，所述矿相定量分析的步骤包括：通过X射线衍射分析获得X射线衍射图谱，基于加标Rietveld全谱拟合精修的方式确定所述解离固体残留物中的所有矿相的相对含量，其中，选择与所述解离固体残留物中不包括的矿相作为于内标物质，所述内标物质包括氧化铝或者氧化锌。
进一步的，所述预设累计阈值为80％～95％。
进一步的，所述重金属元素含量测定的方法为电感耦合等离子发射光谱、原子吸收光谱、电感耦合等离子质谱、原子荧光光谱中的一种或几 种的任意组合。
在本发明中，通过耦合实验分析与仪器表征的多维信息，对所述待测重金属固体废物在相同解离条件下进行N个浓度梯度解离测定，并获得N个不同浓度梯度下的所述待判定重金属元素的解离度，对解离后的解离固体残留物进行矿相定量分析，获得所述待测重金属固体废物的M个矿相中每个矿相的相对含量，然后求解得到所述重金属元素在所述矿相中的赋存分布比例，将重金属元素在所述矿相中赋存比例由高到低进行累计，且累计赋存比例超过预设累计阈值的矿相判定为所述重金属元素的赋存关键矿相。提供了一种简便、快速、高效、准确的重金属赋存关键矿相的分析判定方法，实现了工业固体废物中重金属赋存状态的准确分析，综合判定了重金属赋存关键矿相，为工业固废的处理处置技术选择提供了精细化技术支持。
附图说明
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，下面将对实施例或现有技术描述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示出的结构获得其他的附图。
图1为本发明的工业固体废物中重金属赋存关键矿相的分析判定方法的流程图；
图2为一实施例中的铬渣的X射线衍射分析图谱。
本发明目的的实现、功能特点及优点将结合实施方式，参照附图做进一步说明。
具体实施方式
下面将结合本发明实施方式中的附图，对本发明实施方式中的技术方案进行清楚、完整地描述，显然，所描述的实施方式仅仅是本发明的一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技 术人员在没有作出创造性劳动前提下所获得的所有其他实施方式，都属于本发明保护的范围。
需要说明，本发明实施方式中所有方向性指示(诸如上、下……)仅用于解释在某一特定姿态(如附图所示)下各部件之间的相对位置关系、运动情况等，如果该特定姿态发生改变时，则该方向性指示也相应地随之改变。
另外，在本发明中如涉及“第一”、“第二”等的描述仅用于描述目的，而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。
并且，本发明各个实施方式之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
请参考图1，为本发明一具体示例中的工业固体废物中重金属赋存关键矿相的分析判定方法，包括步骤：
S1，对待测重金属固体废物进行重金属元素含量测定，获取所述待测重金属固体废物中赋存的P种待判定重金属元素的含量。
具体的，所述重金属元素含量测定可以采用先定性后定量，定性方法可以为X射线荧光光谱，定量方法为电感耦合等离子发射光谱、原子吸收光谱、激光诱导击穿光谱中的一种或几种的任意组合。
进一步的，所述步骤S1之前，还包括对所述待测重金属固体废物进行预处理的步骤：将所述待测重金属固体废物的样品在60～105℃下进行空气烘干后研磨至200目以下的样品粉末，然后烘干至恒重。
S2，对所述待测重金属固体废物在相同解离条件下进行N个浓度梯度解离测定，并获得N个不同浓度梯度下的所述待判定重金属元素的解离度
Figure PCTCN2022087877-appb-000007
所述d ij代表第i个浓度梯度解离测定中待判定重金属元素j的解离度，d ij∈(0,1)，i＝1,2,3,...,N，j＝1,2,...,P。
具体的，所述在相同解离条件下进行N个浓度梯度解离测定的步骤包括：在相同时间和外场作用下，在N个浓度梯度的酸溶液中对固体废物进行非特 异性解离，对解离后的解离溶液进行重金属元素含量测定；其中，所述酸溶液为硝酸：盐酸的物质的量比为1：3的混酸；解离液固比8～12：1(L/kg)，温度为15～35℃，解离时间1-2h；外场作用包括超声波，超声频率20kHz-40kHz，功率200-500W。其中，所采用的重金属元素含量测定的方法可以为电感耦合等离子发射光谱、原子吸收光谱、电感耦合等离子质谱、原子荧光光谱中的一种或几种的任意组合。
进一步的，所述d ij的计算公式包括
Figure PCTCN2022087877-appb-000008
ω 0j为所述待测重金属固体废物的初始条件下重金属元素j的质量分数，c ij为第i个浓度梯度测定后解离溶液中重金属元素j的浓度，V ij为第i个浓度梯度测定后解离溶液的体积。
进一步的，所述步骤S2之前，还包括对所述待测重金属固体废物进行预清洗处理；其中，所述ω 0j的计算方式为
Figure PCTCN2022087877-appb-000009
其中，ω' j为未经预清洗的所述待测重金属固体废物中重金属元素j的质量分数，m a为未经预清洗的所述待测重金属固体废物的质量，m b为预清洗后的所述待测重金属固体废物的质量，c' j为未经预清洗的所述待测重金属固体废物后清洗液中重金属元素j的浓度，V为预清洗后的所述待测重金属固体废物清洗液的体积。
进一步的，所述预清洗的步骤包括：采用0.1mol/L的pH＝7.0醋酸铵溶液作为预清洗试剂，将所述待测重金属固体废物与0.1mol/L的pH＝7.0醋酸铵溶液以液固比10：1(L/kg)混合后，在15～35℃条件下水平震荡1-2h，所得溶液在6000rpm-10000rpm条件下离心3-10min得到清洗液和预清洗后的所述待测重金属固体废物；对所述清洗液进行重金属元素含量测定，以及对所述预清洗后的所述待测重金属固体废物进行矿相定量分析。其中，所采用的重金属元素含量测定的方法为电感耦合等离子发射光谱、原子吸收光谱、电感耦合等离子质谱、原子荧光光谱中的一种或几种的任意组合；所述矿相定量分析的步骤包括：通过X射线衍射分析获得X射线衍射图谱，基于加标Rietveld全谱拟合精修的方式确定所述解离固体残留物中的所有矿相的相对含量，其中，选择与所述解离固体残留物中不包括的矿相作为于内标物质，所述内标物质包括氧化铝或者氧化锌。
S3，对步骤S2中解离后的解离固体残留物进行矿相定量分析，获得所述待测重金属固体废物的M个矿相中每个矿相的相对含量W ik，然后根据公式
Figure PCTCN2022087877-appb-000010
计算每个所述矿相的解离度
Figure PCTCN2022087877-appb-000011
其中，k＝1,2,3,...,M，l ik代表第i个浓度梯度测定中矿相k的解离度，W 0k为所述待测重金属固体废物的初始条件下矿相k的质量分数，m 0为所述待测重金属固体废物的初始样品质量，m i为第i个浓度梯度测定后的解离固体残留物质量，W ik为第i个浓度梯度测定后解离固体残留物中矿相k的质量分数。
具体的，N的个数等于所述待测重金属固体废物的矿相个数M，其中，N个浓度梯度解离测定中酸溶液的氢离子浓度范围为0-12mol/L。
具体的，所述矿相定量分析的步骤包括：通过X射线衍射分析获得X射线衍射图谱，基于加标Rietveld全谱拟合精修的方式确定所述解离固体残留物中的所有矿相的相对含量，其中，选择与所述解离固体残留物中不包括的矿相作为于内标物质，所述内标物质包括氧化铝或者氧化锌。
S4，根据公式L n×m×R m×p＝Exp n×p，求解得到所述重金属元素在所述矿相中的赋存分布比例
Figure PCTCN2022087877-appb-000012
具体的，所述重金属元素在所述矿相中的赋存分布比例可以表示为：
Figure PCTCN2022087877-appb-000013
其中，R中每列向量r j代表重金属元素j在M个矿相上的赋存分布情况，反映重金属元素j分配至矿相k的比例。因此，有如下关系：L n×m×R m×p＝Exp n×p,R可由以下公式求解：R m×p＝L + n×m×Exp n×p,其中，L +为L矩阵的广义逆矩阵。
S5，将重金属元素j在所述矿相中赋存比例由高到低进行累计，且累计赋存比例超过预设累计阈值的矿相判定为所述重金属元素j的赋存关键矿相。
可选的，在一具体实例中，所述预设累计阈值为80％～95％。具体的，重金属赋存关键矿相的判定是分别针对不同重金属而言的，具体可以为：参考帕累托法则，将重金属元素j在各矿相中的赋存分布比例由高到低排列后，则可认为该固废样品中的重金属元素j的赋存关键矿相为累积赋存分布比例等于或超过80％的前几个矿相。
【实施例】
本实施例对象取自云南某铬盐企业产生的铬渣，是一种典型的含重金属 工业固体废物。其中的铬元素是污染控制工程最为关注的重金属元素。
预处理步骤：根据本发明方法，所述固废优选地采用四分法取适量原始样品，用粉碎机粉碎至完全通过200目筛，然后置于敞口烧杯中，在105℃鼓风烘箱烘干6小时至恒重。
预清洗步骤：取15.0000±0.005g所述固废，采用0.1mol/L的pH＝7.0醋酸铵溶液进行预清洗，液固比10：1(L/kg)，在25℃条件下摇床水平震荡1h。所得溶液在8000rpm条件下离心10min，洗涤三次，上清液定容至250ml、稀释至适宜于ICP-AES检测的浓度范围后，用ICP-AES确定重金属元素含量；残留固体置于敞口烧杯中，在105℃鼓风烘箱烘干8小时至恒重。其中，使用分析天平对预清洗前后所述固废样品进行称重，精确至小数点后四位。
浓度梯度解离测定：本领域技术人员知晓，原始样品重金属元素含量分析一般采用强酸消解结合仪器表征的方式。在本实施中，所述固废优选地使用王水-HF-HClO4混合酸体系在250℃消解，残余澄清溶液定容，并稀释至适宜于ICP-AES检测的浓度范围后，用ICP-AES确定重金属元素含量。
取1.0000±0.005g所述预清洗后样品，同步做一系列浓度梯度解离实验。具体地，为方便操作先配置物质的量比例1：3的混酸浓溶液，其中盐酸浓度9mol/L，硝酸浓度3mol/L。再通过稀释操作，配制出所需浓度梯度，分别为0.01mol/L、0.05mol/L、0.1mol/L、0.2mol/L、0.5mol/L、1mol/L、2mol/L、4mol/L、6mol/L、8mol/L、10mol/L、12mol/L。
浓度梯度设计的基本原则是尽量保证各类矿相颗粒有彻底解离或几乎彻底解离的机会，且使同一矿相的解离度在不同浓度实验条件下具有差异性，梯度实验数应等于矿相数目，即N＝M＝12。对于稳定性较强的固废，如熔渣、尾矿可采用“低浓度稀疏、高浓度密集”的梯度设计；对于稳定性较差的固废，如化学沉淀污泥、飞灰可采用“低浓度密集、高浓度稀疏”的梯度设计；如无法确定则采取本实施例所用梯度设计。
所述固废样品按照液固比10：1(L/kg)，在30kHz超声波、温度25℃条件下，解离1h。解离后溶液在8000rmp条件下离心10min，用20ml去离子水洗涤残渣三次，与上清液合并定容至100ml，稀释后使用ICP-AES测定其中重金属元素的含量。固体部分干燥8h至恒重，称重。
根据公式
Figure PCTCN2022087877-appb-000014
可计算预清洗后样品中重金属元素Cr的解离度。具体如下：
表1 预清洗后样品中重金属元素Cr的解离度
w` j(mg/g) m a(g) m b(g) c` j(mg/L) V(L) w 0j(mg/g)
47.55 15.0020 14.8320 593.0 0.250 38.10
在步骤S4中，每个浓度梯度实验(d1-d12)重金属元素Cr的解离度可由公式
Figure PCTCN2022087877-appb-000015
计算，具体如下：
表2 浓度梯度实验(d1-d12)重金属元素Cr的解离度
d 1 d 2 d 3 d 4 d 5 d 6
0.031 0.037 0.094 0.210 0.339 0.522
d 7 d 8 d 9 d 10 d 11 d 12
0.539 0.771 0.790 0.883 0.942 0.955
解离后的解离固体残留物进行矿相定量分析：矿相定量分析方法为X射线衍射分析(XRD)，具体为采用加标Rietveld全谱拟合精修的方式确定所有矿相(包括无定形)的相对含量，内标物质选择优级纯α-Al 2O 3粉末，掺入比例10％。本领域技术人员知晓，Rietveld全谱拟合精修需建立在XRD精扫基础上，且不同分析软件均可实现精修功能。本实施例中选用Bruker公司X射线衍射仪，在5-80°范围内以0.01°为步长，2.5s为步时进行精扫，数据结果分析软件为TOPAS。
根据公式
Figure PCTCN2022087877-appb-000016
可计算得每个浓度梯度解离实验矿相解离度。具体如下：
表3 每个浓度梯度解离实验矿相解离度
矿相 浓度1 浓度2 浓度3 浓度4 浓度5 浓度6
无定形 0.0097 0.0181 0.1139 0.3088 0.5255 0.833
MgO 0.0817 0.082 0.0839 0.0876 0.0918 0.0977
Ca 2Fe 1.28Al 0.72O 5 0.0648 0.0687 0.0901 0.1338 0.1823 0.2512
Ca 3Al 1.54Fe 0.46(OH) 12 0.05 0.057 0.0956 0.1741 0.2614 0.3853
Ca 0.5Mg 0.5CO 3 0.0793 0.0802 0.0848 0.0941 0.1046 0.1193
Ca 4Fe 2(CrO 4)(OH) 12·8H 2O 0.0825 0.0826 0.0836 0.0856 0.0878 0.0909
Mg 6Cr 2(CO 3)(OH) 16·4H 2O 0.0818 0.0821 0.0838 0.0873 0.0911 0.0966
MgAl 0.8Fe 1.2O4 0.0832 0.0832 0.0833 0.0836 0.0839 0.0844
Ca 3Al 2.849H 9.6O 12 0.0826 0.0827 0.0836 0.0852 0.087 0.0896
CaCO 3 0.0742 0.0762 0.0867 0.108 0.1318 0.1655
Mg(OH) 2 0.082 0.0823 0.0838 0.0869 0.0904 0.0954
Ca(OH) 2 0.0816 0.082 0.0839 0.0879 0.0923 0.0986
矿相 浓度7 浓度8 浓度9 浓度10 浓度11 浓度12
无定形 0.8616 0.9852 0.947 0.9996 1 1
MgO 0.0982 0.1418 0.1594 0.5291 1 1
Ca 2Fe 1.28Al 0.72O 5 0.2576 0.7663 0.9716 0.9949 1 1
Ca 3Al 1.54Fe 0.46(OH) 12 0.3968 0.9051 0.9501 1 1 1
Ca 0.5Mg 0.5CO 3 0.1207 0.23 0.2741 0.9298 1 1
Ca 4Fe 2(CrO 4)(OH) 12·8H 2O 0.0912 0.1141 0.1234 0.3182 0.6629 0.8487
Mg 6Cr 2(CO 3)(OH) 16·4H 2O 0.0971 0.1374 0.1537 0.4955 1 1
MgAl 0.8Fe 1.2O4 0.0844 0.0877 0.089 0.1169 0.1661 0.1926
Ca 3Al 2.849H 9.6O 12 0.0899 0.1091 0.1169 0.2798 0.5682 0.7237
CaCO 3 0.1686 0.4175 0.518 0.9891 1 1
Mg(OH) 2 0.0958 0.1324 0.1472 0.4572 1 1
Ca(OH) 2 0.0992 0.1456 0.1644 0.5578 1 1
重金属元素在所述矿相中的赋存分布比例计算：根据公式L n×m×R m×p＝Exp n×p求解：R m×p＝L + n×m×Exp n×p,其中，L+为L矩阵的广义逆矩阵。
具体地，在matlab中将矿相解离度数据以矩阵形式写入变量L，将重金属元素解离度数据以矩阵形式写入变量E，令R＝pinv(L)*E，则可求解R矩阵。结果如表4。
表4 重金属元素在所述矿相中的赋存分布比例
  r
无定形 0.4846
MgO 0.0093
Ca 2Fe 1.28Al 0.72O 5 0.1085
Ca 3Al 1.54Fe 0.46(OH) 12 0.1952
Ca 0.5Mg 0.5CO 3 0.0233
Ca 4Fe 2(CrO 4)(OH) 12·8H 2O 0.0049
Mg 6Cr 2(CO 3)(OH) 16·4H 2O 0.0086
MgAl 0.8Fe 1.2O4 0.0007
Ca 3Al 2.849H 9.6O 12 0.0041
CaCO 3 0.0531
Mg(OH) 2 0.0078
Ca(OH) 2 0.0099
根据所述赋存关键矿相判定方法，将赋存分布比例由高到低排列后，可知重金属元素Cr在无定形相、水榴石(Ca 3Al 1.54Fe 0.46(OH) 12)、钙铁石(Ca 2Fe 1.28Al 0.72O 5)、碳酸钙(CaCO 3)前4个矿相上的累积赋存分布比例为0.8414(大于0.8)，则可认为无定形相、水榴石(Ca 3Al 1.54Fe 0.46(OH) 12)、钙铁石(Ca 2Fe 1.28Al 0.72O 5)、碳酸钙(CaCO 3)为所述固废中重金属元素Cr的赋存关键矿相。
本发明的上述技术方案中，以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是在本发明的技术构思下，利用本发明说明书及附图内容所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围。

Claims (10)

  1. 一种工业固体废物中重金属赋存关键矿相的分析判定方法，其特征在于，包括步骤：
    S1，对待测重金属固体废物进行重金属元素含量测定，获取所述待测重金属固体废物中赋存的P种待判定重金属元素的含量；
    S2，对所述待测重金属固体废物在相同解离条件下进行N个浓度梯度解离测定，并获得N个不同浓度梯度下的所述待判定重金属元素的解离度
    Figure PCTCN2022087877-appb-100001
    所述d ij代表第i个浓度梯度解离测定中待判定重金属元素j的解离度，d ij∈(0,1)，i＝1,2,3,...,N，j＝1,2,...,P；
    S3，对步骤S2中解离后的解离固体残留物进行矿相定量分析，获得所述待测重金属固体废物的M个矿相中每个矿相的相对含量W ik，然后根据公式
    Figure PCTCN2022087877-appb-100002
    计算每个所述矿相的解离度
    Figure PCTCN2022087877-appb-100003
    其中，k＝1,2,3,...,M，l ik代表第i个浓度梯度测定中矿相k的解离度，W 0k为所述待测重金属固体废物的初始条件下矿相k的质量分数，m 0为所述待测重金属固体废物的初始样品质量，m i为第i个浓度梯度测定后的解离固体残留物质量，W ik为第i个浓度梯度测定后解离固体残留物中矿相k的质量分数；
    S4，根据公式L n×m×R m×p＝Exp n×p，求解得到所述重金属元素在所述矿相中的赋存分布比例
    Figure PCTCN2022087877-appb-100004
    S5，将重金属元素j在所述矿相中赋存比例由高到低进行累计，且累计赋存比例超过预设累计阈值的矿相判定为所述重金属元素j的赋存关键矿相。
  2. 根据权利要求1所述的方法，其特征在于，所述d ij的计算公式包括
    Figure PCTCN2022087877-appb-100005
    ω 0j为所述待测重金属固体废物的初始条件下重金属元素j的质量分数，c ij为第i个浓度梯度测定后解离溶液中重金属元素j的浓度，V ij为第i个浓度梯度测定后解离溶液的体积。
  3. 根据权利要求2所述的方法，其特征在于，所述步骤S2之前，还包 括对所述待测重金属固体废物进行预清洗处理；其中，所述ω 0j的计算方式为
    Figure PCTCN2022087877-appb-100006
    其中，ω′ j为未经预清洗的所述待测重金属固体废物中重金属元素j的质量分数，m a为未经预清洗的所述待测重金属固体废物的质量，m b为预清洗后的所述待测重金属固体废物的质量，c′ j为未经预清洗的所述待测重金属固体废物后清洗液中重金属元素j的浓度，V为预清洗后的所述待测重金属固体废物清洗液的体积。
  4. 根据权利要求1所述的方法，其特征在于，所述预清洗的步骤包括：采用0.1mol/L的pH＝7.0醋酸铵溶液作为预清洗试剂，将所述待测重金属固体废物与0.1mol/L的pH＝7.0醋酸铵溶液以液固比10：1(L/kg)混合后，在15～35℃条件下水平震荡1-2h，所得溶液在6000rpm-10000rpm条件下离心3-10min得到清洗液和预清洗后的所述待测重金属固体废物；对所述清洗液进行重金属元素含量测定，以及对所述预清洗后的所述待测重金属固体废物进行矿相定量分析。
  5. 根据权利要求1所述的方法，其特征在于，所述步骤S1之前，还包括对所述待测重金属固体废物进行预处理的步骤：将所述待测重金属固体废物的样品在60～105℃下进行空气烘干后研磨至200目以下的样品粉末。
  6. 根据权利要求1所述的方法，其特征在于，所述在相同解离条件下进行N个浓度梯度解离测定的步骤包括：在相同时间和外场作用下，在N个浓度梯度的酸溶液中对固体废物进行非特异性解离，对解离后的解离溶液进行重金属元素含量测定；其中，所述酸溶液为硝酸：盐酸的物质的量比为1：3的混酸；解离液固比8～12：1(L/kg)，温度为15～35℃，解离时间1-2h；外场作用包括超声波，超声频率20kHz-40kHz，功率200-500W。
  7. 根据权利要求6所述的方法，其特征在于，N的个数等于所述待测重金属固体废物的矿相个数M，其中，N个浓度梯度解离测定中酸溶液的氢离子浓度范围为0-12mol/L。
  8. 根据权利要求1所述的方法，其特征在于，所述矿相定量分析的步骤包括：通过X射线衍射分析获得X射线衍射图谱，基于加标Rietveld全谱拟合精修的方式确定所述解离固体残留物中的所有矿相的相对含量，其中，选择与所述解离固体残留物中不包括的矿相作为于内标物质，所述内标物质包括氧化铝或者氧化锌。
  9. 根据权利要求1所述的方法，其特征在于，所述预设累计阈值为80％～95％。
  10. 根据权利要求1～9中任一项所述的方法，其特征在于，所述重金属元素含量测定的方法为电感耦合等离子发射光谱、原子吸收光谱、电感耦合等离子质谱、原子荧光光谱中的一种或几种的任意组合。
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