CN114942252B - Method for judging key occurrence phases of heavy metals in solid hazardous waste - Google Patents
Method for judging key occurrence phases of heavy metals in solid hazardous waste Download PDFInfo
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- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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Abstract
The invention provides a method for judging a key occurrence phase of heavy metal in solid hazardous waste, which comprises the following steps: s1, performing phase measurement on solid hazardous waste to be measured to obtain phase composition in the solid hazardous waste to be measured; s2, when the obtained phase contains a heavy metal phase, judging a heavy metal key occurrence phase of the solid hazardous waste to be detected according to the heavy metal phase; s3, when the obtained phase does not contain a heavy metal phase, performing step dissociation treatment on the solid hazardous waste to be detected according to the obtained non-heavy metal phase; and S4, determining the non-heavy metal phase corresponding to the step dissociation liquid with the highest heavy metal content as the key occurrence phase of the heavy metal in the solid hazardous waste. The method can reduce the identification difficulty, time and workload on the premise of accurately identifying the key occurrence phases of the heavy metals in the hazardous waste, has a low threshold, and can be suitable for industrial rapid application.
Description
Technical Field
The invention relates to the field of identification of heavy metal occurrence phases, in particular to a method for judging a key occurrence phase of heavy metal in solid hazardous waste.
Background
Heavy metals are widely used in various aspects of human production and life. Especially in the basic chemical raw material manufacturing industry, heavy metals with strong toxicity such as chromium, arsenic and the like are often involved. The industry generally forms hazardous waste containing heavy metals in two ways: 1. by-products formed during synthesis, reaction and processing of heavy metal raw materials; 2. and (3) precipitates formed when the solution is subjected to impurity removal after reaction in a liquid phase environment containing heavy metals. The heavy metal content in the byproducts and the precipitates is high, the toxicity is high, and the extraction of the byproducts and the precipitates can realize resource utilization and harmlessness at the same time.
In the process, the key occurrence phases of the heavy metals need to be identified first, so that a targeted extraction method can be developed. However, the existing identification method for occurrence states of heavy metals mainly aims at chemical forms of the heavy metals; such as: the Chinese patent with publication number CN106290785A discloses a method for separating heavy metals in different forms in soil by adopting a DGT technology, which divides the forms of the heavy metals into an ionic state, an organic easily-dissociated state and a non-easily-dynamic state; for another example, chinese patent publication No. CN106399695A discloses a method for extracting heavy metal elements from petroleum coke step by step, which separates the heavy metal into an ion-exchangeable state, a reducible state, an oxidizable state, and a residue state. However, the classification of the chemical forms cannot guide the selection of a suitable method for recycling the heavy metals in the hazardous wastes.
Chinese patent No. CN113406127B discloses a method for analyzing and determining critical phases of heavy metal occurrence in industrial solid waste, which comprises performing N concentration gradient dissociation measurements on the heavy metal solid waste to be determined under the same dissociation conditions, obtaining dissociation degrees of the heavy metal elements to be determined under N different concentration gradients, performing quantitative phase analysis on dissociated solid residues to obtain the relative content of each phase in M phases of the heavy metal solid waste to be determined, then solving to obtain the occurrence distribution ratio of the heavy metal elements in the phases, accumulating the occurrence ratios of the heavy metal elements in the phases from high to low, and determining the phase whose occurrence ratio exceeds a preset accumulation threshold as the critical phase of the heavy metal elements. Although accurate analysis of occurrence states of heavy metals in the industrial solid waste is realized to a certain extent, a refined technical support is provided for selection of treatment and disposal technologies of the industrial solid waste. However, this patent also has at least the following drawbacks:
1. the patent relates to multiple times of XRD pattern refinement fitting and phase quantitative analysis, and has large workload and long consumed time;
2. the complex mathematical methods, including matrix calculation and correlation analysis, are required in the patent, which not only affects the rapid industrial application, but also has high requirements and thresholds for technicians.
In view of the above, it is necessary to provide a method for determining a critical occurrence phase of heavy metals in solid hazardous waste to solve the above technical drawbacks.
Disclosure of Invention
The invention mainly aims to provide a method for judging a key occurrence phase of heavy metal in solid hazardous waste, and aims to solve the technical problem.
In order to achieve the aim, the invention provides a method for judging a key occurrence phase of heavy metals in solid hazardous waste, which comprises the following steps:
s1, performing phase measurement on solid hazardous waste to be measured to obtain phase composition in the solid hazardous waste to be measured;
s2, when the obtained phase contains a heavy metal phase, judging a heavy metal key occurrence phase in the solid hazardous waste to be detected according to the heavy metal phase;
s3, when the phase does not contain a heavy metal phase, performing step dissociation treatment on the solid hazardous waste to be detected according to the obtained non-heavy metal phase to obtain a step dissociation liquid corresponding to the dissociated non-heavy metal phase; wherein the step dissociation process comprises:
s31, mixing the solid dangerous waste to be detected with a saturated calcium sulfate dihydrate solution, and then carrying out solid-liquid separation operation to obtain a washing liquid and washing residues;
s32, when the non-heavy metal phase contains a calcium sulfate phase, mixing the washing residue with water, then carrying out solid-liquid separation operation to obtain a first dissociation liquid and a first residue, and then executing the step S33;
when the non-heavy metal phase does not contain a calcium sulfate phase, directly executing a step S33;
s33, when the non-heavy metal phase contains a magnesium hydroxide phase, mixing the washing residue or the first residue with an ammonium salt solution with the concentration of 0.1-1mol/L, then carrying out solid-liquid separation operation to obtain a second dissociation solution and a second residue, and then executing a step S34;
when the non-heavy metal phase does not contain the magnesium hydroxide phase, directly executing the step S34;
s34, when the non-heavy metal phase contains a calcium carbonate phase, mixing the washing residue or the first residue or the second residue with a first acid solution with the concentration of 0.01-0.1mol/L, then carrying out solid-liquid separation operation to obtain a third dissociation solution and a third residue, and then executing the step S35;
when the non-heavy metal phase does not contain a calcium carbonate phase, directly executing a step S35;
s35, when the non-heavy metal phase contains an iron oxide phase, mixing the washing residues or the first residues or the second residues or the third residues with a second acid solution with the concentration of 0.5-2mol/L, then carrying out solid-liquid separation operation to obtain a fourth dissociation solution and fourth residues, and finishing the step dissociation treatment;
when the non-heavy metal phase does not contain an iron oxide phase, directly finishing the step dissociation treatment;
and S4, determining the non-heavy metal phase corresponding to the step dissociation liquid with the highest heavy metal content as the key occurrence phase of the heavy metal in the solid hazardous waste.
Further, the solid hazardous waste to be detected is the solid hazardous waste containing heavy metals generated in the basic chemical raw material manufacturing industry.
Further, the heavy metal content W in the step dissociation liquid i The calculation formula of (2) is as follows:
W i =C i *V i
in the formula:
C i is the cascade solutionThe concentration of heavy metal in the chaotropic agent is mg/L;
V i the volume of the gradient dissociation liquid is shown as L.
Further, the step S4 further includes: calculating the mass ratio H of the heavy metals contained in the heavy metal key occurrence phases in the solid hazardous waste to be detected, and determining the treatment mode of the solid hazardous waste to be detected according to the ratio H;
the formula for calculating the mass ratio H is:
H=（W i /m o ）*100%
in the formula:
W i the unit of the heavy metal content in the step dissociation liquid corresponding to the non-heavy metal phase is mg;
m 0 and the unit of the mass of the solid hazardous waste to be detected is mg.
Further, the solid-liquid ratio of the solid dangerous waste to be detected to the saturated calcium sulfate dihydrate solution is 1g:20 to 100mL;
the solid-liquid ratio of the solid hazardous waste to be detected to the water is 1g:200 to 500mL;
the solid-liquid ratio of the solid hazardous waste to be detected to the ammonium salt solution is 1g:20 to 100mL;
the solid-liquid ratio of the solid dangerous waste to be detected to the first acid solution is 1g:10 to 50mL;
the solid-liquid ratio of the solid hazardous waste to be detected to the second acid solution is 1g:20 to 200mL.
Further, the mixing time in the step S31 is 10 to 30min; the mixing time in the step S32 is 20 to 60min; the mixing time in the step S33 is 10 to 60min; the mixing time in the step S34 is 5 to 20min; the mixing time in the step S35 is 10 to 30min.
Further, the mixing process in the step S35 is performed at a temperature of 50 to 70 ℃.
Further, the preparation process of the saturated calcium sulfate dihydrate solution comprises the following steps: adding calcium sulfate dihydrate into distilled water according to a preset proportion, and continuously stirring for 1 to 4 hours after the calcium sulfate dihydrate is added; standing for 1 to 4 hours after the stirring operation is carried out; and then filtering to obtain filtrate, namely the saturated calcium sulfate solution.
Further, the ammonium salt solution comprises one or more of an ammonium chloride solution and an ammonium acetate solution;
the first acid solution and the second acid solution each comprise one or more of an acetic acid solution, a hydrochloric acid solution, and a nitric acid solution.
Further, in the step S1, before the phase measurement is performed on the solid hazardous waste to be measured, the solid hazardous waste is dried and ground.
Compared with the prior art, the invention has at least the following advantages:
the invention provides a method for rapidly identifying key occurrence phases of heavy metals in hazardous waste through step dissociation, which reduces the identification difficulty and workload and reduces the identification time on the premise of accurately identifying the key occurrence phases of the heavy metals in the hazardous waste; moreover, the threshold of the invention is low, and the invention can be applied to rapid industrial application. Specifically, the method can judge whether the heavy metal phase exists in the hazardous waste or not through phase measurement; under the condition that no heavy metal phase exists, non-heavy metal phases in the hazardous waste can be further analyzed so as to provide basis for dissociation of the phases; through the step dissociation treatment, the heavy metal content corresponding to each non-heavy metal phase after dissociation is obtained, so that the phase corresponding to the dissociation liquid with the highest heavy metal content can be obtained, and the phase is judged as the key occurrence phase of the heavy metal in the hazardous waste.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for determining a key occurrence phase of heavy metals in solid hazardous waste according to the invention;
FIG. 2 is an XRD pattern of a slag obtained in example 1 of the present invention;
FIG. 3 is an XRD pattern of a sample S1, a solid residue S2 and a solid residue S3 in example 2 of the present invention;
figure 4 is an XRD pattern of sample S1 in example 3 of the present invention.
The purpose, function, features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. 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 and are intended to be open ended, i.e., to include any methods, devices, and materials similar or equivalent to those described in the examples.
The skilled person needs to understand that when the element content of the heavy metal is analyzed, the heavy metal content in the sample can be obtained only by one measurement, so that the error is small; when the content of the heavy metal in the supernatant is analyzed every time, one error is generated, and a plurality of errors are generated by a plurality of times of test analysis, so that the recovery rate of the heavy metal is possibly more than 100% under the condition of more sufficient recovery. In addition, the stirring of the shaking table, magnetic stirring and other conditions can adopt a rotating speed of 200rmp, the ultrasonic power of the ultrasonic dissociation device can adopt 1000W, and the rotating speed and the ultrasonic power can be adaptively adjusted according to the actual dissociation condition so as to improve the dissociation efficiency.
It is also clear to those skilled in the art that the invention mainly aims at the solid hazardous waste containing heavy metals generated in the basic chemical raw material manufacturing industry, and the main phases of the solid hazardous waste comprise: naCl, KCl, and Na 2 SO 4 And water-soluble salt; caSO 4 ·2H 2 O、CaSO 4 ·0.5H 2 O and CaSO 4 Calcium sulfate compounds, etc.; magnesium hydroxide, calcium carbonate, iron oxide, some inert substances and the like. The invention relates to a rapid identification method for key occurrence phases of heavy metals in such hazardous wastes; similarly, when the phases contained in the critical waste generated in other industries are similar to the critical waste, the method can also be used for identifying and judging the key phases.
Referring to fig. 1 and table 1, in carrying out the present invention, one skilled in the art may proceed as follows:
step 1: and drying and grinding the solid hazardous waste to be detected, and then determining the types and the contents of elements and the types of phases. Wherein, when the heavy metal element species is uncertain, the element determination can be carried out; when the kind of the heavy metal element is clarified, the element measurement may not be performed in the previous stage.
Through determination, if the solid hazardous waste to be detected contains heavy metal-containing phase (such as Na) 2 CrO 4 ，K 2 CrO 4 Etc.), then this phase is a heavy metal key excipient phase; if the heavy metal-containing phase is not present but only non-heavy metal-containing phases (e.g. magnesium salts, calcium salts, etc.), the distinction is made by the following procedure.
Because the invention aims at the solid hazardous waste containing heavy metal generated in the basic chemical raw material manufacturing industry, the heavy metal element in the solid hazardous waste to be detected is usually one and corresponds to the basic chemical raw material; certainly, for special cases or other industries, if the solid hazardous waste contains a plurality of heavy metal elements, the method of the present invention can also be used to identify the key occurrence phases of each heavy metal element, and the heavy metal at this time can be called a certain heavy metal (the name of the heavy metal to be identified) correspondingly.
It should be understood that, in the solid waste corresponding to the basic chemical raw material manufacturing industry, if a heavy metal phase of a certain heavy metal element can be obtained through phase measurement, all the heavy metal phases can be regarded as key occurrence phases of the heavy metal element.
Specifically, the element type and content measurement can be used for judging the type and content of the heavy metal, and XRF (X-ray fluorescence spectrometry) analysis or triacid digestion-ICP (inductively coupled plasma) full-element analysis is recommended to be used for the element type and content measurement.
The phase type test recommends the qualitative analysis by XRD (X-ray diffraction method), and the phase referred to in the invention is the phase which can be measured by XRD.
Step 2: taking the solid hazardous waste to be detected after the drying and grinding (based on 1g of the solid hazardous waste to be detected), and mixing the solid hazardous waste to be detected according to the weight ratio of 1g: adding a saturated calcium sulfate dihydrate solution into the solid-liquid ratio of 20 to 100mL to wash the solid hazardous waste to be detected, and removing free heavy metals and other soluble salts such as NaCl, KCl and Na 2 SO 4 ，K 2 SO 4 And the like. Specifically, the solid residue can be washed for 10 to 30 minutes under the condition of shaking table or magnetic stirring, and then centrifuged or filtered to obtain a washing solution and a solid residue (washing residue).
Wherein, the saturated calcium sulfate dihydrate solution can be prepared by the following method: adding 5g of a calcium sulfate dihydrate reagent into 1L of distilled water, continuously stirring for 1 to 4 hours, standing for 1 to 4 hours, and filtering to obtain a filtrate, namely a saturated calcium sulfate dihydrate solution.
And step 3: adding 200 to 500mL of the solid residue obtained in the step (2) into the solid residue for distillationReacting water in a shaking table or under magnetic stirring for 20 to 60 minutes to dissociate calcium sulfate (including CaSO) 4 ·2H 2 O，CaSO 4 ·0.5H 2 O and CaSO 4 ) Then, the resulting mixture is centrifuged or filtered to obtain a dissociation solution (first dissociation solution) and a solid residue (first residue).
Note: if the calcium sulfate phase does not exist in the solid hazardous waste to be detected, skipping the step; otherwise, it cannot skip.
And 4, step 4: and (4) adding 20-100mL of 0.1-1mol/L ammonium salt solution into the solid residue obtained in the step (step 2 or step 3), reacting in a shaking table or under magnetic stirring for 10-60 minutes to dissociate magnesium hydroxide, and centrifuging or filtering to obtain a dissociation solution (second dissociation solution) and a solid residue (second residue).
Note: if the magnesium hydroxide phase does not exist in the solid hazardous waste to be detected, skipping the step; otherwise, it cannot skip.
The ammonium salt solution comprises one or more of ammonium chloride, ammonium acetate and other ammonium-containing reagents.
And 5: and (3) adding 10 to 50mL of an acid solution with the concentration of 0.01 to 0.1mol/L into the solid residue obtained in the step (step 2, step 3 or step 4), magnetically stirring or ultrasonically reacting for 5 to 20 minutes in a shaking table to dissociate calcium carbonate, and centrifuging or filtering to obtain a dissociation solution (third dissociation solution) and the solid residue (third residue).
Note: if no calcium carbonate phase exists in the solid hazardous waste to be detected, skipping the step; otherwise, it cannot skip.
The acid solution includes one or more of common acidic reagents such as acetic acid, hydrochloric acid, nitric acid, etc. (the acid solution described below is the same in composition).
Step 6: taking the solid residue obtained in the step (step 2 or step 3 or step 4 or step 5), adding 20-200mL of an acid solution with a concentration of 0.5-2mol/L, heating and stirring at 50-70 ℃ for 10-30 minutes to dissociate iron oxide (Fe) 2 O 3 ，Fe 3 O 4 ) (ii) a Then centrifuging or filtering to obtain dissociation solution (fourth dissociation solution) and solid residue(fourth residue).
Note: if no iron oxide exists in the solid hazardous waste to be detected, skipping the step; otherwise, it cannot skip.
And 7: carrying out ICP test on heavy metal elements to obtain the concentration of the heavy metal in each step dissociation liquid, and calculating the content W of the heavy metal in the step dissociation liquid according to the following formula 1 i 。
Except for the free state/soluble salt, judging the non-heavy metal phase corresponding to the dissociation liquid with the highest heavy metal content (such as the highest heavy metal content mass) as the key occurrence phase of the heavy metal in the solid hazardous waste.
Equation 1: w is a group of i =C i *V i
In the formula:
C i the unit of the concentration of the heavy metal in the step dissociation liquid is mg/L;
V i the volume of the gradient dissociation liquid is shown as L.
In addition, on the basis of the formula 1, a formula 2 can be adopted to calculate the mass ratio H of the heavy metals contained in the heavy metal key occurrence phase in the solid hazardous waste to be detected, and the treatment mode of the solid hazardous waste to be detected is determined according to the ratio H.
Of course, the heavy metal mass ratio H of other non-heavy metal phases can also be calculated according to equation 2, in which case W in equation 2 i The method can be used for indicating the heavy metal content in the cascade dissociation liquid corresponding to the heavy metal key occurrence matters, and can also be used for indicating the heavy metal content in the cascade dissociation liquid corresponding to other non-heavy metal matters.
Equation 2: h = (W) i /m o ）*100%
In the formula:
W i the heavy metal content in the cascade dissociation liquid corresponding to the non-heavy metal phase is mg;
m 0 the unit is mg of the mass (dry basis) of the solid hazardous waste to be detected.
Note: in the present invention, the content of 10mg/g corresponds to 1% regardless of the above-mentioned mass ratio or the description of the element content.
As a description of the above steps, it is understood that the solid residue taken in each dissociation step is derived from the step closest thereto; it should be further understood that the purpose of each dissociation step is to effectively dissociate the corresponding phase, and in the process, whether dissociation is completed can be determined by observing the reaction state of the dissociation reaction, and residues obtained in each step can be determined by XRD qualitative analysis to verify whether the corresponding phase is effectively dissociated; in addition, when a solid residue is completely dissolved after a certain dissociation step is completed, the residue of the dissociation step after the dissociation is completed is only a conceptual description convenient for those skilled in the art to understand, and does not correspond to an entity.
The correspondence among the phase, dissociation agent, and dissociation liquid according to the present invention is shown in table 1:
table 1 industry categories: basic chemical feedstock manufacture
To facilitate understanding of the invention by those skilled in the art, there will now be illustrated:
example 1
Taking waste residue generated in the process of preparing chromate in a certain factory for analysis:
XRF test is carried out on the obtained waste residue after drying and grinding, and the result shows that: wherein the heavy metal element is Cr (content 6.7%); the XRD test was performed again, and the results are shown in FIG. 2.
Analysis of the results indicated the presence of a double salt phase of sodium chromate and sodium sulfate. Therefore, sodium chromate and sodium sulfate double salt is a key excipient phase of chromium in the hazardous waste.
Example 2
Taking waste residue generated in the process of preparing chlorate in a certain factory for analysis:
step 1: drying and grinding the obtained waste residues to obtain a sample S1; the obtained alloy was subjected to an ICP test and an XRD test, and the Cr content thereof was about 1.61%.
As shown in FIG. 3, XRD test results show that the phases contained in the composite material are sodium chloride, sodium chlorate, calcium sulfate dihydrate and calcium carbonate.
Step 2: taking 1g of the sample, and adding 80mL of saturated calcium sulfate dihydrate solution; mixing, and reacting under shaking table for 20min to dissociate soluble salt (NaCl, naClO) 3 ) After the reaction, the reaction mixture was centrifuged to obtain a supernatant L2 (washing solution) and a solid residue S2 (washing residue), which were subjected to ICP and XRD tests, respectively.
And 3, step 3: taking the solid residue S2, and adding 200mL of distilled water; after mixing well, the mixture is reacted for 30 minutes under magnetic stirring to dissociate calcium sulfate dihydrate (CaSO) 4 ·2H 2 O), reaction, and centrifugation to obtain supernatant L3 (first dissociation solution) and solid residue S3 (first residue), which were subjected to ICP and XRD tests, respectively.
And 4, step 4: the solid residue S3 was taken out and added with 20mL of 0.1mol/L nitric acid solution to dissociate calcium carbonate, and the solid was completely dissolved after the reaction in this step (reaction under a shaker for 20 min), and a supernatant L4 (third dissociation solution) was obtained.
The calculation results are shown in table 2, and the results show that the chromium content in the calcium sulfate phase is highest, up to 34.46%, except in the free state. Calcium sulfate is therefore a key phase for chromium.
XRD (X-ray diffraction) tests are carried out on the residues obtained after the step dissociation, and the results show that the corresponding dissociating agent can effectively dissociate the target phase. And the recovery rate of Cr in the dissociation solution is 104.35%, which proves the feasibility of the scheme.
TABLE 2 calculation of chromium content and ratio in phases
Example 3
Taking a certain factory to analyze waste residues generated in the treatment of the chromium-containing waste salt solution:
step 1: drying and grinding the obtained waste residues to obtain a sample S1; it was subjected to an ICP test and an XRD test, wherein the Cr content was about 0.39%.
As shown in FIG. 4, XRD test results show that the phases contained in the material are magnesium hydroxide, calcium carbonate and ferric oxide.
And 2, step: taking 1g of the sample, and adding 100mL of ammonium chloride solution with the concentration of 0.5 mol/L; mixing, reacting for 20min in a shaking table, and performing ultrasonic treatment for 10min to decompose magnesium hydroxide (Mg (OH) 2 ) After the reaction, the reaction mixture was centrifuged to obtain a supernatant L2 (second dissociation solution) and a solid residue S2 (second residue), and the filtrate was subjected to an ICP test.
And 3, step 3: taking the solid residue S2, and adding 50mL of nitric acid solution with the concentration of 0.1 mol/L; mixing, reacting in a shaking table for 10min, and performing ultrasonic treatment for 10min to dissociate calcium carbonate (CaCO) 3 ) After the reaction, the reaction mixture was centrifuged to obtain a supernatant L3 (third dissociation solution) and a solid residue S3 (third residue), and the filtrate was subjected to an ICP test.
And 4, step 4: adding 200mL of 1mol/L nitric acid solution into the solid residue S3, mixing, reacting at 50 deg.C for 10min, and performing ultrasonic treatment for 10min to dissociate ferric oxide (Fe) 2 O 3 ) In this step, the solid was completely dissolved after the reaction to obtain a supernatant L4 (fourth dissociation solution), and the filtrate was subjected to ICP measurement.
The calculation results are shown in Table 3, and the results show that the chromium content in the magnesium hydroxide phase is the highest, and reaches 88.54%. Thus, magnesium hydroxide is a key phase for chromium.
TABLE 3 calculation of chromium content and ratio in each phase
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (7)
1. A method for judging a key occurrence phase of heavy metals in solid hazardous waste is characterized by comprising the following steps:
s1, performing phase measurement on solid hazardous waste to be measured to obtain phase composition in the solid hazardous waste to be measured;
the method comprises the following steps of (1) obtaining solid hazardous waste to be detected, wherein the solid hazardous waste to be detected is solid hazardous waste containing heavy metals generated in the basic chemical raw material manufacturing industry;
s2, when the obtained phase contains a heavy metal phase, judging a key occurrence phase of the heavy metal in the solid hazardous waste to be detected according to the heavy metal phase;
s3, when the phase does not contain a heavy metal phase, carrying out step dissociation treatment on the solid hazardous waste to be detected according to the obtained non-heavy metal phase to obtain a step dissociation liquid corresponding to the non-heavy metal phase after dissociation; wherein the step dissociation process comprises:
s31, mixing the solid dangerous waste to be detected with a saturated calcium sulfate dihydrate solution, and then carrying out solid-liquid separation operation to obtain a washing liquid and washing residues;
s32, when the non-heavy metal phase contains a calcium sulfate phase, mixing the washing residue with water, then carrying out solid-liquid separation operation to obtain a first dissociation solution and a first residue, and then executing the step S33;
when the non-heavy metal phase does not contain a calcium sulfate phase, directly executing a step S33;
s33, when the non-heavy metal phase contains a magnesium hydroxide phase, mixing the washing residue or the first residue with an ammonium salt solution with the concentration of 0.1-1mol/L, then carrying out solid-liquid separation operation to obtain a second dissociation liquid and a second residue, and then executing the step S34;
the ammonium salt solution is one or more of ammonium chloride solution and ammonium acetate solution;
when the non-heavy metal phase does not contain the magnesium hydroxide phase, directly executing the step S34;
s34, when the non-heavy metal phase contains a calcium carbonate phase, mixing the washing residue or the first residue or the second residue with a first acid solution with the concentration of 0.01-0.1mol/L, then carrying out solid-liquid separation operation to obtain a third dissociation liquid and a third residue, and then executing the step S35;
the first acid solution is one or more of acetic acid solution, hydrochloric acid solution and nitric acid solution;
when the non-heavy metal phase does not contain a calcium carbonate phase, directly executing a step S35;
s35, when the non-heavy metal phase contains an iron oxide phase, mixing the washing residues or the first residues or the second residues or the third residues with a second acid solution with the concentration of 0.5-2mol/L, then carrying out solid-liquid separation operation to obtain a fourth dissociation solution and fourth residues, and finishing the step dissociation treatment;
the second acid solution is one or more of an acetic acid solution, a hydrochloric acid solution and a nitric acid solution; the mixing process in the step S35 is carried out at a temperature of 50 to 70 ℃;
when the non-heavy metal phase does not contain an iron oxide phase, directly finishing the step dissociation treatment;
and S4, judging the non-heavy metal phase corresponding to the step dissociation liquid with the highest heavy metal content as the key occurrence phase of the heavy metal in the solid hazardous waste.
2. The method for determining the key occurrence phases of the heavy metals in the solid hazardous waste according to claim 1, wherein the heavy metal content W in the step dissociation solution i The calculation formula of (2) is as follows:
W i =C i *V i
in the formula:
C i the concentration of the heavy metal in the step dissociation liquid is mg/L;
V i the volume of the gradient dissociation liquid is shown as L.
3. The method for determining the key occurrence phases of the heavy metals in the solid hazardous waste according to claim 2, wherein the step S4 further comprises: calculating the mass ratio H of the heavy metals contained in the heavy metal key occurrence phases in the solid hazardous waste to be detected, and determining the treatment mode of the solid hazardous waste to be detected according to the ratio H;
the formula for calculating the mass ratio H is:
H=（W i /m o ）*100%
in the formula:
W i the heavy metal content in the cascade dissociation liquid corresponding to the non-heavy metal phase is mg;
m 0 the unit is mg of the mass of the solid hazardous waste to be detected.
4. The method for determining the key occurrence phases of the heavy metals in the solid-dangerous waste according to claim 1, wherein the solid-to-liquid ratio of the solid-dangerous waste to be detected to the saturated calcium sulfate dihydrate solution is 1g:20 to 100mL;
the solid-liquid ratio of the solid hazardous waste to be detected to the water is 1g:200 to 500mL;
the solid-liquid ratio of the solid hazardous waste to be detected to the ammonium salt solution is 1g:20 to 100mL;
the solid-liquid ratio of the solid dangerous waste to be detected to the first acid solution is 1g:10 to 50mL;
the solid-liquid ratio of the solid hazardous waste to be detected to the second acid solution is 1g:20 to 200mL.
5. The method for determining the key occurrence phases of the heavy metals in the solid hazardous waste according to claim 1, wherein the mixing time in the step S31 is 10 to 30min; the mixing time in the step S32 is 20 to 60min; the mixing time in the step S33 is 10 to 60min; the mixing time in the step S34 is 5 to 20min; the mixing time in the step S35 is 10 to 30min.
6. The method for determining the key occurrence phases of heavy metals in solid hazardous waste according to claim 1, wherein the preparation process of the saturated calcium sulfate dihydrate solution comprises the following steps: adding calcium sulfate dihydrate into distilled water according to a preset proportion, and continuously stirring for 1 to 4 hours after adding the calcium sulfate dihydrate; standing for 1 to 4 hours after the stirring operation is finished; then filtering is carried out, and the obtained filtrate is the saturated calcium sulfate dihydrate solution.
7. The method for determining the key occurrence phases of the heavy metals in the solid hazardous waste according to any one of claims 1 to 6, wherein in the step S1, before the phase determination is performed on the solid hazardous waste to be detected, the solid hazardous waste is subjected to drying treatment and grinding treatment.
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