CN116287731A

CN116287731A - Method for selectively separating thallium from thallium-containing waste

Info

Publication number: CN116287731A
Application number: CN202310205228.3A
Authority: CN
Inventors: 闵小波; 柴立元; 伍莞澜; 柯勇; 李云; 彭聪; 王云燕; 梁彦杰; 林璋; 李青竹
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2023-03-02
Filing date: 2023-03-02
Publication date: 2023-06-23

Abstract

The invention provides a method for selectively separating thallium from thallium-containing waste, comprising the following steps: s1, grinding the thallium-containing waste to obtain a grinding product; the thallium-containing waste comprises zinc sulfate; s2, mixing the grinding product with calcium oxide to obtain a pretreatment substance; s3, roasting the pretreated matter, and collecting thallium-containing volatile matters generated in the roasting treatment; the temperature of the roasting treatment is 650-750 ℃, and the duration of the roasting treatment is not less than 1h. The invention realizes selective volatilization of thallium, effectively avoids environmental pollution caused by storage of thallium-containing waste, realizes enrichment and recovery of thallium, and is favorable for promoting harmless and resource development of thallium.

Description

Method for selectively separating thallium from thallium-containing waste

Technical Field

The present invention relates to the treatment of waste, and in particular to a method for selectively separating thallium from thallium-containing waste.

Background

The thallium-containing waste generated in nonferrous metallurgy, ferrous metallurgy and chemical industry production processes brings great risks to the ecological environment, and reduces the resource utilization rate of thallium. In the prior art, in order to realize separation and enrichment of thallium, thallium is usually recovered from thallium-containing waste by wet treatment.

For example, chinese patent publication No. CN112981124a developed a method for separating enriched thallium from thallium-containing oxidized waste residue, which involves pulping, leaching, liquid-solid separation, precipitation, etc., and in a specific operation, alkali is added before acid is added to achieve cobalt thallium separation. Although this patent has a certain thallium separation effect, it has disadvantages of various additives, large consumption, high cost, etc., and is not a preferred choice for selectively separating thallium from thallium-containing waste industrially, so that the prior art has poor applicability in treating thallium-containing waste.

In view of the foregoing, there is a need for a method for selectively separating thallium from thallium-containing waste that solves or alleviates the above-mentioned technical drawbacks of the prior art in terms of poor applicability for the treatment of thallium-containing waste.

Disclosure of Invention

The invention mainly aims to provide a method for selectively separating thallium from thallium-containing waste, and aims to solve the technical problem of poor applicability of thallium-containing waste treatment in the prior art.

To achieve the above object, the present invention provides a method for selectively separating thallium from thallium-containing waste, comprising the steps of:

s1, grinding the thallium-containing waste to obtain a grinding product;

wherein the thallium-containing waste is a solid, and the thallium-containing waste comprises zinc sulfate;

s2, mixing the grinding product with calcium oxide to obtain a pretreatment substance;

s3, roasting the pretreated matter to obtain a thallium-containing volatile matter and thallium-removing slag;

wherein the temperature of the roasting treatment is 650-750 ℃, and the duration of the roasting treatment is not less than 1h.

Further, the thallium-containing waste comprises thallium-containing dust generated during zinc smelting.

Further, the thallium-containing dust has a thallium content of 0.5 to 0.7wt%.

Further, the particle size of the ground product is not greater than 100 mesh.

Further, the thallium-containing solid waste also comprises valuable metal fluorochloride compounds, wherein the valuable metal fluorochloride compounds comprise one or more of lead fluorochloride compounds, zinc fluorochloride compounds and cadmium fluorochloride compounds.

Further, the mass ratio of the calcium oxide in the pretreatment is not less than 5%.

Further, the mass ratio of the calcium oxide in the pretreatment is not less than 10%.

Further, the step S1 further includes: and drying the thallium-containing waste before grinding the thallium-containing waste.

Further, in the step S2, the mixing process includes: grinding the grinding product and the calcium oxide together to obtain a primary mixture; and then, carrying out oscillation treatment on the primary mixture to obtain the pretreated substance.

Further, the baking treatment is performed under an air atmosphere.

Compared with the prior art, the invention has at least the following advantages:

the invention provides a method for selectively separating thallium from thallium-containing waste, which can effectively avoid the pollution of the thallium-containing waste to the environment, and simultaneously selectively separate thallium from the thallium-containing waste to recycle resources to the greatest extent.

Specifically, calcium oxide is used as a phase conversion agent, and is assisted by high-temperature treatment at about 700 ℃, so that the structure of a thallium-containing phase is destroyed, volatilization of other metals is inhibited, and selective separation of thallium is realized. Compared with other treatment methods, the method provided by the invention avoids round-trip folding of the wet method, and has the advantages of lower treatment cost and higher volatilization efficiency. The thallium-removed slag obtained after volatilization can be returned to a lead-zinc smelting system for secondary utilization, separation and recovery of thallium are realized, and meanwhile, the environmental risk of thallium-containing waste is greatly reduced.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.

FIG. 1 is an XRD pattern of thallium-containing soot in example 1 of the present invention;

FIG. 2 is a graph showing the chemical phase analysis results of the water-soluble zinc and the zinc oxide according to the change of the roasting temperature and the change rule of the thallium volatilization rate in the embodiment 2 of the present invention;

FIG. 3 is a graph showing the results of chemical phase analysis of the change of lead in chloride form, lead in sulfate form and lead in oxide form with the firing temperature and the change of thallium volatilization rate in example 2 of the present invention;

FIG. 4 is a graph showing the chemical phase analysis results of the water-soluble zinc and the zinc oxide according to the oxygen concentration and the thallium volatilization rate in example 3;

FIG. 5 is a graph showing the chemical phase analysis results of the change in the concentration of oxygen and the change in the volatilization rate of thallium of example 3 of the present invention.

The achievement of the object, functional features and advantages of the present invention will be further described with reference to the drawings in connection with the embodiments.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.

Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.

It is to be understood that thallium is a typical rare dispersing element found in nature, widely found in primary metal minerals. Thallium has various characteristics of improving alloy strength, improving alloy hardness, enhancing alloy corrosion resistance and the like, and thallium-containing alloy has potential application value in the aspects of optical fibers, superconducting materials, infrared optical materials, radiation shielding materials, catalysts and the like.

At present, smelting enterprises face the problems of high pollution of thallium-containing waste, high disposal cost and selective separation and recovery of thallium in slag. The treatment of thallium-containing waste in the prior art is not entirely suitable for industrial applications and is not very specific for the particular thallium-containing waste (no treatment of thallium-containing waste residues is known to involve thallium-containing fumes).

Based on the above, in order to realize the selective separation of thallium in thallium-containing waste on the premise of being applicable to industrial application, the invention provides a method for selectively separating thallium from thallium-containing waste, which comprises the following steps:

s1, grinding the thallium-containing waste to obtain a grinding product.

Wherein the ground product may be in the form of particles, and the particle size of the ground product may be, for example, not more than 100 mesh, and may be, specifically, 100 to 400 mesh.

The thallium-containing waste contains thallium element; the thallium-containing waste may further contain one or more of lead element, zinc element and cadmium element.

In the specific phase category, the thallium-containing solid waste comprises zinc sulfate, and thallium element is added in the zinc sulfate, namely, the thallium-containing solid waste comprises or is the zinc sulfate; one or more of lead sulfate and cadmium sulfate can be also included in the thallium-containing solid waste.

Further, the thallium-containing solid waste can also comprise valuable metal fluorochloride; and valuable metal oxides can be also included in the thallium-containing solid waste. The valuable metal in the present invention means a metal other than thallium.

The valuable metal fluorochloride may include or be one or more of lead fluorochloride, zinc fluorochloride, and cadmium fluorochloride; the fluorine-chlorine compound may contain one or both of fluorine and chlorine, or may contain both of fluorine and chlorine. The metal oxide may include or be one or more of lead-based oxides, zinc-based oxides, and cadmium-based oxides.

The thallium-containing waste is a solid, and specifically may include or be thallium-containing dust generated in a zinc smelting process, the thallium-containing dust may include or be thallium-containing high fluorine chlorine dust, the thallium content in the thallium-containing high fluorine chlorine dust (thallium-containing dust) may be 0.5 to 0.7wt%, and typically 0.6 to 0.7wt%, the thallium in the thallium-containing high fluorine chlorine dust is substantially contained in zinc sulfate, and the thallium element in the thallium-containing high fluorine chlorine dust includes or is monovalent thallium.

It should be noted that, when thallium-containing high fluorine chlorine dust or other wastes contain thallium with other valence states, the implementation of the application is not affected.

In order to facilitate the treatment of the thallium containing waste, the step S1 may further comprise: drying the thallium-containing waste to a constant weight before grinding the thallium-containing waste; the temperature of the drying treatment may be 60-100 ℃, such as 80 ℃.

S2, mixing the grinding product with calcium oxide to obtain a pretreated substance.

In order to ensure the release of thallium and the conversion of valuable metals, the mass ratio of the calcium oxide in the pretreatment may be not less than 5%; preferably, the mass ratio of the calcium oxide in the pretreatment may be not less than 10%, and may be, for example, 10 to 20%.

In order to ensure adequate contact of the thallium containing waste and the calcium oxide, in the step S2, the mixing process comprises: grinding the grinding product and calcium oxide together to obtain a primary mixture; and then, carrying out oscillation treatment on the primary mixture to obtain the pretreated substance. Wherein the particle size of the primary mixture may be consistent with the milled product, and the duration of the shaking may be not less than 0.5 hours, preferably may be 0.5 to 3 hours.

And S3, roasting the pretreated matter to obtain separated thallium-containing volatile matter and thallium-removed slag (baked slag). Specifically, thallium-containing volatiles generated in the calcination process can be collected simultaneously during the calcination process, thereby recovering separated thallium.

The collecting process may be: the volatiles are sent to a condenser tube or other condensing device to condense the volatiles, thereby obtaining a thallium containing recycle.

In order to ensure selective separation of thallium, the temperature of the calcination treatment is 650-750 ℃, preferably can be 700 ℃; the duration of the calcination treatment is not less than 1h, and may preferably be 1 to 3h. In addition, the roasting treatment is generally performed in a furnace body, and the temperature rising process of the pretreated matter and the temperature lowering process of the residues can be a mode of rising temperature along with the furnace and falling temperature along with the furnace.

In order to ensure that the reaction proceeds during the calcination, the calcination treatment cannot be performed under a reducing atmosphere, and the calcination treatment may be generally performed under an air atmosphere or an inert atmosphere.

The main principle related to the invention comprises:

in order to achieve selective volatilization of thallium, the conditions for volatilization of thallium compounds are thermodynamically and kinetically met, i.e., the critical temperature for volatilization of thallium-containing compounds is reached, while allowing release of thallium present in other compounds. Therefore, the reaction, roasting temperature and roasting time in the thallium-containing smoke must be regulated, and the relevant conditions and parameters are controlled, so as to realize selective volatilization of thallium.

1. The main reasons for determining the additive to be CaO in the invention include:

1) Thallium in thallium-containing high-fluorine chlorine smoke dust (thallium-containing waste) has strong correlation with zinc sulfate, and thallium release and selective volatilization can be realized by destroying the zinc sulfate structure. And CaO can react with zinc sulfate to be converted into zinc oxide and calcium sulfate, so as to realize the release of thallium.

Although other substances are also present in the thallium-containing high-fluorine-chlorine dust, since zinc sulfate has a strong correlation with thallium in the thallium-containing dust (zinc sulfate and thallium), thallium in the thallium-containing high-fluorine-chlorine dust is basically assigned to zinc sulfate, and therefore, conversion to zinc sulfate is required to release thallium efficiently.

2) The volatilization point of the valuable metal fluorochloride is low, caO can react with the valuable metal fluorochloride to convert the valuable metal fluorochloride into oxide, and the volatilization rate of the valuable metal in the roasting process is reduced.

2. The main reasons for determining the roasting temperature to be 650-750 ℃ in the invention include:

1) Thallium begins to volatilize above 600 ℃ and volatilizes in large amounts at 700 ℃.

2) Valuable metals such as lead, zinc, cadmium and the like are converted into oxides, and a large amount of volatilization occurs after the temperature is higher than 700 ℃ (the specific volatilization effect is based on the examples and the comparative examples).

To facilitate a detailed understanding of the invention by those skilled in the art, reference will now be made to the accompanying drawings, in which:

example 1

Sampling analysis of thallium-containing soot

And (3) taking thallium-containing high-fluorine chlorine smoke dust (thallium-containing smoke dust) generated in the zinc smelting process, drying (80 ℃ air blast drying box) to constant weight, grinding (grinding to 100-mesh sieve), digesting the ground thallium-containing smoke dust, measuring the element content in the thallium-containing smoke dust, and carrying out phase analysis.

In this example, the thallium content of the thallium-containing soot was measured to be 0.66wt%. The thallium element in the thallium-containing high-fluorine chlorine smoke dust is unevenly distributed, the thallium content of the whole smoke dust is between 0.6 and 0.7 weight percent, and the calculation of the volatilization rate of thallium in the subsequent examples and comparative examples takes the content obtained by digestion as a calculation standard.

The specific analysis results are as follows:

1. referring to fig. 1 and chemical phase analysis, in this example, the phases in which thallium-containing smoke mainly exists include zinc oxide, lead oxide, zinc sulfate (water-soluble zinc), lead sulfate, lead chloride, zinc chloride, and the like, and the existence forms include crystalline and amorphous states.

2. In this example, the mass percentages of the main elements in the thallium-containing smoke are shown in the following table:

element(s)	Zn	Pb	S	Cd	Fe	F	Tl	Cl	O
										Content (%)	38.1	17.75	6.135	1.98	3.22	0.93	0.66	4.87	22.5

As can be seen from the above table, the thallium-containing dust mainly contains valuable metal elements such as Zn and Pb.

3. In this example, the chemical phase analysis results (mass%) of Zn are shown with reference to the following table:

4. in this example, the chemical phase analysis results (mass percent) of Pb are shown with reference to the following table:

example 2

Temperature single factor test

1kg of a sample of thallium-containing dust (same as in example 1) dried (80 ℃ C. Forced air drying oven) to a constant weight was ground (to a 100 mesh sieve) to obtain a ground product.

The ground product was calcined at 600 ℃,700 ℃, 800 ℃, 900 ℃, 1000 ℃ and 1100 ℃ respectively.

The process of each roasting is as follows: 15g of ground product is put into a vertical tube furnace for roasting under the air atmosphere; the temperature of each roasting is controlled to be respectively the above temperatures, the heat preservation time of each roasting is 1h, and the baked slag is cooled to the room temperature along with the furnace after the roasting.

In this example, the results of chemical phase analysis of water-soluble zinc and zinc oxide in the post-baking slag as a function of baking temperature (mass ratio in the post-baking slag), and the law of change in thallium volatilization rate (as a function of baking temperature) are shown in FIG. 2.

The results of chemical phase analysis of the change of the chlorinated lead, the sulfuric acid lead and the oxidized lead with the roasting temperature (the mass ratio in the slag after roasting) and the change rule of the thallium volatilization rate (the change with the roasting temperature) in the slag after roasting are shown in fig. 3.

Example 3

Oxygen concentration single factor experiment

The ground product was calcined at oxygen concentrations of 0%, 10%, 20%, 30%, 40% and 50%, respectively.

Each roasting process is as follows: taking 15g of ground product and roasting in a vertical tube furnace under the oxygen concentration; the roasting temperature is controlled to be 900 ℃, the heat preservation time of each roasting is 1h, and the slag after roasting is cooled to room temperature along with the furnace.

In this example, the results of chemical phase analysis of water-soluble zinc and zinc oxide in the post-baking slag as a function of oxygen concentration (mass ratio in the post-baking slag), and the law of change in thallium volatilization rate as a function of oxygen concentration are shown in FIG. 4.

The results of chemical phase analysis of the change in oxygen concentration of chlorinated lead, sulfuric acid lead and oxidized lead in the post-baking slag (mass ratio in the post-baking slag), and the change law of thallium volatilization rate (change with oxygen concentration) are shown in fig. 5.

Example 4

Water immersion test

Weighing 0.2000g of ground product, placing into a centrifuge tube, adding 50ml of deionized water into the centrifuge tube, placing into a water bath shaking table (150 r/min) at normal temperature, oscillating for 2 hours, taking out, centrifuging, separating solid from liquid, and taking supernatant to test thallium and zinc content.

The leaching rate is calculated by combining the two, and the mass leaching rate is shown in the following table:

thallium leaching Rate (%)	Leaching rate of zinc in water-soluble state (%)
		98.61	100

Analytical example 1

Analysis of thallium-occupiant phases in connection with examples 1-4

1. Referring to fig. 2-5, in the analysis and test results of the two single factor experiments, thallium volatilization rates all show obvious correlation with zinc-containing phases, but have weaker correlation with lead-containing phases, and regularity is not obvious. It is therefore assumed that thallium presence has a certain correlation with zinc phase.

Further, referring specifically to fig. 2, as the temperature increases, the water-soluble zinc phase decreases, the zinc oxide phase increases, and the thallium volatilization rate increases, presumably during the temperature increase, the water-soluble zinc phase converts to the zinc oxide phase and simultaneously releases thallium.

Referring specifically to fig. 4, in the oxygen concentration single factor experiment, the water-soluble zinc phase increases and then decreases, while the oxidation state zinc phase and thallium volatilization rate decrease and then increase, and it is also presumed that the inter-phase transformation between the water-soluble zinc phase and the oxidation state zinc phase results.

As is clear from the data of the water leaching experiment, in the water leaching process, the water-soluble zinc is completely dissolved, and thallium is almost completely dissolved, and analysis shows that the thallium existing in the water leaching process is released due to the destruction of the water-soluble zinc phase structure in the water leaching process, so that the thallium is dissolved simultaneously.

Since the dissolution relationship between water-soluble zinc and thallium and the change law in the roasting process are strongly correlated, the occurrence of thallium is considered to have a strong correlation with the water-soluble zinc phase.

2. In combination with the main elements involved in thallium-containing smoke dust, the water-soluble zinc involved in the invention should be zinc chloride and zinc sulfate. Wherein, the volatilization temperature of the zinc chloride phase is lower (about 500 ℃ is obviously volatilized), and the decomposition temperature of the zinc sulfate phase is higher (about 500-600 ℃ is dissociated and 930 ℃ is dissociated violently).

In the temperature single factor experiment, along with the temperature rise, the water-soluble zinc phase is continuously reduced after the temperature exceeds 500 ℃, the water-soluble zinc phase is obviously reduced in the range of 900-1000 ℃ (the severe dissociation temperature of zinc sulfate), and meanwhile, the thallium volatilization rate is obviously improved.

Therefore, the occurrence of thallium is considered to be correlated with the zinc sulfate phase, and the occurrence phase of thallium in the thallium-containing dust is considered to be zinc sulfate.

Example 5

13.5g of ground product (thallium-containing smoke dust after grinding) and 1.5g of calcium oxide are weighed, and the weighed ground product and the calcium oxide are added into a mortar together for grinding and mixing to obtain a primary mixture (the primary mixture can pass through a 100-mesh sieve); placing the initial mixture into a plastic bottle with a cover, and placing on a turnover oscillator (30 r/min) for oscillating for 2h to obtain a pretreated substance.

And (3) filling the obtained pretreated matter into a corundum crucible, and placing the corundum crucible into a vertical tube furnace for roasting in an air atmosphere. In the roasting process, the roasting temperature is controlled to be 700 ℃, and the heat preservation time is 1h; after roasting, the slag after roasting is cooled to room temperature along with the furnace.

And (3) digesting the baked slag, and measuring the contents of thallium, lead, zinc and cadmium in the digestion liquid.

Calculated, in this example, the mass volatilization rate of thallium is 90.06%, and the mass volatilization rates of lead, zinc and cadmium are 2.42%, 10.20% and 10.35%, respectively.

Example 6

In this example, the amount of the ground product was adjusted to 12g and the amount of the calcium oxide was adjusted to 3g, as compared with example 5, and the other conditions were kept unchanged.

Calculated, in this example, the mass volatilization rate of thallium was 95%, and the mass volatilization rates of lead, zinc and cadmium were 1.51%, 5.21% and 4.13%, respectively.

Comparative example 1

In this comparative example, the firing temperature was adjusted to 900 ℃ alone, and other conditions were kept unchanged as compared with example 5.

Calculated, in the comparative example, the mass volatilization rate of thallium is 98.39%, and the mass volatilization rates of lead, zinc and cadmium are 2.30%, 59.41% and 56.79%, respectively.

Comparative example 2

In this comparative example, the firing temperature was adjusted to 800℃as compared with example 5, and other conditions were kept unchanged.

Calculated, in the comparative example, the mass volatilization rate of thallium is 94.51%, and the mass volatilization rates of lead, zinc and cadmium are 3.79%, 42.12% and 32.53%, respectively.

Analytical example 2

Based on comparative examples 1-2, it can be seen that:

when the temperature is too high, the thallium-containing phase is destroyed and thallium is completely released, but the valuable metal is severely volatilized at high temperature, and selective separation cannot be realized.

Therefore, ensuring the roasting temperature around 700 ℃ is very critical for destroying the structure of thallium-containing phases and realizing the selective volatilization of thallium.

Comparative example 3

In this comparative example, the firing temperature was adjusted to 600℃as compared with example 5, and other conditions were kept unchanged.

Calculated, in the comparative example, the mass volatilization rate of thallium is 29.40%, and the mass volatilization rates of lead, zinc and cadmium are 2.64%, 7.41% and 9.35%, respectively.

Comparative example 4

In this comparative example, the firing temperature was adjusted to 500℃as compared with example 5, and other conditions were kept unchanged.

Calculated, in the comparative example, the mass volatilization rate of thallium is 8.53%, and the mass volatilization rates of lead, zinc and cadmium are 2.18%, 2.45% and 2.53%, respectively.

Analytical example 3

Based on comparative examples 3 to 4, it can be seen that:

when the temperature is too low, the structure of the thallium-containing phase is not destroyed, thallium is not completely released, and the thallium volatilization rate is low.

Therefore, ensuring the firing temperature at around 700 ℃ is necessary to destroy the structure of the thallium-containing phase and to achieve selective volatilization of thallium.

Comparative example 5

In this comparative example, the amount of the ground product was adjusted to 14.5g and the amount of calcium oxide was adjusted to 0.5g, as compared with example 5, and the other conditions were maintained.

Calculated, in the comparative example, the mass volatilization rate of thallium is 20.79%, and the mass volatilization rates of lead, zinc and cadmium are 2.10%, 13.79% and 12.73%, respectively.

Based on the comparative example, it can be seen that:

when the addition ratio of calcium oxide is low, the structure of the thallium-containing phase is not destroyed, thallium is not completely released, and the thallium volatilization rate is low.

Therefore, ensuring the calcium oxide ratio is necessary to destroy the structure of the thallium-containing phase and to achieve selective volatilization of thallium.

Comparative example 6

In this comparative example, the calcium oxide was replaced with sodium carbonate alone, and the other conditions were kept unchanged as compared with example 5.

Calculated, in the comparative example, the mass volatilization rate of thallium is 75.23%, and the mass volatilization rates of lead, zinc and cadmium are 9.11%, 0.86% and 11.66%, respectively.

Based on the comparative example, it can be seen that:

calcium oxide has a specific reaction mechanism in the present application, and if calcium oxide is replaced with sodium carbonate at a firing temperature of 700 ℃, the volatilization rate of thallium is reduced.

In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the content of the present invention under the technical concept of the present invention, or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for selectively separating thallium from thallium-containing waste, comprising the steps of:

s1, grinding the thallium-containing waste to obtain a grinding product;

2. A method of selectively separating thallium from thallium-containing waste according to claim 1, characterized in that the thallium-containing waste comprises thallium-containing fumes generated during zinc smelting.

3. A method for the selective separation of thallium from thallium containing waste according to claim 2, characterized in that the thallium content of the thallium containing flue dust is 0.5 to 0.7wt%.

4. A method of selectively separating thallium from thallium containing waste as in claim 1, wherein the ground product has a particle size of no greater than 100 mesh.

5. A method of selectively separating thallium from thallium-containing waste as in claim 1, further comprising a valuable metal fluorochloride compound in the thallium-containing solid waste, the valuable metal fluorochloride compound comprising one or more of a lead fluorochloride compound, a zinc fluorochloride compound, and a cadmium fluorochloride compound.

6. A method for selectively separating thallium from thallium containing waste according to claim 1, characterized in that the mass ratio of the calcium oxide in the pretreatment is not less than 5%.

7. A method for selectively separating thallium from thallium containing waste as in claim 6, wherein the calcium oxide comprises no less than 10% by mass of the pretreatment.

8. A method for selectively separating thallium from thallium-containing waste as in claim 1, wherein the step S1 further comprises: and drying the thallium-containing waste before grinding the thallium-containing waste.

9. A method for selectively separating thallium from thallium containing waste according to claim 1, characterized in that in the step S2 the mixing process comprises: grinding the grinding product and the calcium oxide together to obtain a primary mixture; and then, carrying out oscillation treatment on the primary mixture to obtain the pretreated substance.

10. A method for the selective separation of thallium from thallium containing waste according to any one of claims 1 to 9, characterized in that the roasting treatment is performed under an air atmosphere.