A method for fractionating and extracting barium toxic substances and its application

Abstract

The present invention discloses a graded extraction method for barium toxic substances and its application, which belongs to the field of chemical detection technology. The present invention utilizes a graded extraction method to extract and separate acid-soluble barium in rock cuttings samples, thereby avoiding this part of barium from combining with other substances in the subsequent detection process and reducing the accuracy of the detection; utilizing a composite carbon thermal reduction technology, the barium sulfate in the rock cuttings is reduced and converted into barium chloride detectable by ICP-OES, while the sulfate ions are reduced to soluble sulfides, and no oxidizing agents such as nitric acid are used in the subsequent extraction method, thereby avoiding the sulfide being further oxidized to sulfate ions and reducing the detection accuracy of barium. The graded extraction method of the present invention can separate barium salts of different toxicities in the sample, and realize quantitative analysis and detection of barium toxic substances of different toxicities in the sample.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical detection, and in particular to a method for fractionating and extracting barium toxic substances and an application thereof. Background Art

[0002] The natural gas extraction process generates a large amount of solid waste, including drilling cuttings. With the rapid development of natural gas extraction, particularly shale gas, drilling cuttings and their utilization and disposal are receiving increasing attention. The proper treatment and disposal of oil and gas extraction solid waste is crucial for the healthy and sustainable development of the oil and gas industry, public health, and ecological and environmental protection.

[0003] Barite is widely used in oil and gas exploration and production and barium salt production. It is also one of the main additives in drilling mud, used to adjust the specific gravity of the mud. Its main components are barium sulfate, as well as a small amount of barium carbonate and barium chloride. The large-scale use of barite leads to a high content of barium in drilling cuttings. In addition to barium sulfate, some acid-soluble barium with high toxicity is also brought into the cuttings, thereby increasing the environmental health risks of barium in drilling cuttings. The environmental health risks of barium are mainly reflected in the toxicity of acid-soluble barium compounds. Acid-soluble barium compounds are highly toxic, among which barium chloride, barium oxide, barium carbonate, barium sulfate and other compounds have an oral LD50-LD50 level in rats. 50 All are less than 400mg / kg, barium oxide subcutaneous LD50 in mice 50 Less than 50 mg / kg. Some acid-soluble barium compounds (barium carbonate, barium sulfate, barium chloride, etc.) have been included in the list of toxic substances in the "Hazardous Waste Identification Standard - Identification of Toxic Substance Content" (GB 5085.6-2007).

[0004] Currently, research on analytical methods for different barium salts primarily focuses on the determination of barium sulfate and barium carbonate, primarily leveraging their different solubilities. Commonly used methods include barium sulfate gravimetry, barium chromate volumetry, inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray fluorescence (XRF), energy dispersive X-ray fluorescence spectrometry, and acid-soluble volumetric colorimetry. Of these methods, barium sulfate gravimetry and barium chromate volumetry are classic methods for analyzing barium sulfate in barite. However, their drawbacks include cumbersome and time-consuming procedures, the coprecipitation of lead and strontium, and the potential for sample loss during multiple weighings and transfers of the precipitate, filtration, and precipitate, leading to cumulative errors. Acid-soluble colorimetry improves analysis speed, but remains less streamlined, and analytical accuracy and reproducibility remain suboptimal. Other methods are mostly modifications of classic analytical methods, and the accuracy and reproducibility of their results fall short of those of the classic methods. For example, the ICP method requires two high-temperature melting samples and two filtrations, and the process is still relatively complicated. Although the XRF method is relatively fast and simple, it requires acid treatment to remove interferences such as barium carbonate and lead, which reduces the sample amount and ultimately makes the determination of barium sulfate inaccurate. The atomic absorption method has less interference and high accuracy, but its linear range is narrow, which limits its scope of use for geological samples with large content fluctuations. It is necessary to establish a suitable extraction method to eliminate the interference of other elements, especially calcium salts and silicates with similar properties, optimize existing analytical methods, reduce the accumulation of experimental errors, improve the efficiency of the detection process, and combine the results of different analytical instruments to complete the detection of different barium salts to obtain higher accuracy, precision, reproducibility and timeliness. Summary of the Invention

[0005] In order to solve the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a method for fractionating and extracting barium toxic substances and its application, so as to solve the problems of poor accuracy and reproducibility of the existing detection methods.

[0006] The present invention solves the above technical problems with the following technical solutions: a method for fractionating and extracting barium toxic substances is provided, comprising the following steps:

[0007] (1) Add the sample to pure water, stir at room temperature for 30-60 minutes, then filter, collect the filtrate, and dry the filtered solid to obtain extract 1 and solid 1 to be treated;

[0008] (2) adding an extractant to the solid to be treated 1, stirring at room temperature -40°C for 30-60 minutes, then filtering, collecting the filtrate, and drying the filtered solid to obtain an extract 2 and a solid to be treated 2;

[0009] (3) Charcoal powder and calcium chloride powder are added to the solid to be treated 2, and then sintered. After cooling, the solid is taken out and an extractant is added. The solid is stirred at room temperature for 30-60 minutes, and then filtered. The filtrate is collected to obtain an extract 3.

[0010] Furthermore, the mass ratio of pure water to sample is 40-60:1.

[0011] Furthermore, the extractants in step (2) and step (3) are both 1-2 wt% hydrochloric acid solution or 0.5-1 wt% acetic acid solution.

[0012] Furthermore, in step (2), the mass ratio of the extractant to the sample is 90-110:1.

[0013] Furthermore, the mass ratio of charcoal powder, calcium chloride powder and sample is 1-10:1-5:1.

[0014] Furthermore, the sintering temperature is 1000-1200° C., and the sintering time is 30-50 minutes.

[0015] Furthermore, the volume of the extractant in step (3) is 120-160 mL.

[0016] Specifically, the present invention also provides an application of a fractional extraction method of barium toxic substances in extracting or detecting barium in solid waste, raw materials, auxiliary materials and products containing barium toxic substances.

[0017] The present invention has the following beneficial effects:

[0018] (1) The environmental health risk of barium is mainly reflected in the toxicity of barium ions. Water-soluble barium ions and acid-soluble barium ions are highly toxic and can have serious impacts on human, biological and environmental health. Based on the dissolution characteristics of different barium toxicant compounds, the present invention adopts different extraction agents and extraction methods to achieve the graded extraction of water-soluble barium toxicants (mainly barium chloride) and acid-soluble barium toxicants (excluding soluble toxicants, mainly barium carbonate, barium oxide, etc.) in samples, solving the problem of analyzing and detecting the content of different forms of barium toxicants in samples with complex barium toxicant forms.

[0019] (2) The present invention utilizes a fractional extraction method to extract and separate the acid-soluble barium in the sample, thereby preventing this portion of barium from combining with other substances during subsequent detection and reducing the accuracy of the detection.

[0020] (3) The present invention utilizes composite carbothermal reduction technology, introducing other substances to form a double decomposition reaction based on the carbothermal reduction conversion method, thereby improving the reduction conversion efficiency. The present invention uses calcium chloride as an auxiliary additive, and the product obtained by the composite carbothermal reduction conversion is further converted from barium sulfate to barium chloride, which is less susceptible to oxidation, more soluble, and can be detected by ICP-OES. At the same time, sulfate ions are reduced to soluble sulfides, and oxidizing agents such as nitric acid are not used in the subsequent extraction method, thereby avoiding the reduction of barium detection accuracy due to the further oxidation of sulfides to sulfate ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The extraction rate of barium chloride toxic substances in simulated rock cuttings 1 at different solid-liquid ratios;

[0022] Figure 2 The extraction rates of barium carbonate toxic substances in simulated rock cuttings 2 were obtained by different acid extraction methods;

[0023] Figure 3 The extraction rate of barium carbonate toxic substances in simulated rock cuttings 2 at different solid-liquid ratios;

[0024] Figure 4 is the extraction rate of barium converted from barium sulfate. DETAILED DESCRIPTION

[0025] The following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. In the examples, where specific conditions are not specified, the experiments were performed under conventional conditions or those recommended by the manufacturer. Reagents or instruments used, where the manufacturer is not specified, are commercially available conventional products.

[0026] Barite is widely used in oil and gas exploration and production and barium salt production. It is also one of the main additives in drilling mud and is used to adjust the specific gravity of the mud. Its main components are barium sulfate, as well as a small amount of barium carbonate and barium chloride. Based on the dissolution characteristics of different barium toxicant compounds, the present invention adopts different extractants and extraction methods to achieve quantitative analysis and detection of the content of water-soluble barium toxic substances (mainly barium chloride), acid-soluble barium toxic substances (except soluble toxic substances, mainly barium carbonate, barium oxide, etc.) and barium sulfate in drilling cuttings samples. Among them, water-soluble barium toxic substances can be directly extracted with pure water; acid-soluble barium toxic substances are extracted with acetic acid and hydrochloric acid; barium sulfate uses calcium chloride as an auxiliary additive, and the composite carbon thermal reduction conversion method is used to further convert barium sulfate into barium chloride that is not easily oxidized and more soluble. The present invention relates to a method for extracting water-soluble barium toxic substances, a method for extracting acid-soluble barium toxic substances, a method for extracting barium sulfate, and parameters for a detection method for the total amount of barium. Influencing factors include different solid-liquid ratios of samples and pure water, acid types, different solid-liquid ratios of acid and rock cuttings, the ratio of charcoal powder and calcium chloride powder, extraction conditions, extraction time, etc., and these influencing factors are screened and verified.

[0027] Example 1: Effect of different solid-liquid ratios of rock cuttings and pure water on the extraction of water-soluble barium toxic substances

[0028] Using silicon dioxide, calcium carbonate and barium sulfate as the main matrix, the three compounds were configured with a mass ratio of Ba:Ca:Si of 2:1:2, and barium carbonate, barium chloride and barium oxide toxic substances were added at a mass ratio of Ba (barium sulfate): Ba (barium carbonate): Ba (barium oxide): Ba (barium chloride) of 8:1:0.5:0.5 to prepare simulated rock cuttings 1, in which the contents of Ba (barium sulfate), Ba (barium carbonate), Ba (barium oxide) and Ba (barium chloride) were 15.89%, 1.99%, 0.99% and 0.99% respectively. Simulated rock cuttings 1 and pure water were added at a solid-liquid ratio of 1:5, 1:10, 1:20 and 1:50 respectively, and stirred for 30 minutes at room temperature to extract the barium chloride toxic substance in the simulated rock cuttings 1. The extraction effect is as follows: Figure 1 shown.

[0029] The results showed that when the solid-to-liquid ratio of simulated rock cuttings 1 to pure water was 1:5, 1:10, 1:20, and 1:50, the extraction accuracy of pure water for water-soluble barium toxicants was 66%, 66.5%, 110.77%, and 94.93%, respectively. The absolute values of the differences from 100% accuracy were 34%, 33.5%, 10.77%, and 5.07%, respectively. At a solid-to-liquid ratio of 1:50, pure water showed the best dissolution accuracy for water-soluble barium toxicants in simulated rock cuttings 1.

[0030] Example 2: Effect of different acids on the extraction of toxic substances from barium carbonate

[0031] Using silicon dioxide, calcium carbonate, and barium sulfate as the main matrix, the three compounds were configured with a mass ratio of Ba:Ca:Si of 2:1:2, and barium carbonate toxic substances were added at a mass ratio of Ba (barium sulfate):Ba (barium carbonate) of 9:1 to prepare simulated rock cuttings 2, in which the Ba (barium carbonate) content was 1.97%. Pure water, hydrochloric acid, nitric acid, acetic acid, and mixed acid were selected to dissolve the simulated rock cuttings 2, and the extraction effect was as follows: Figure 2 As shown. The results show that acetic acid has the best dissolution effect on barium carbonate, followed by hydrochloric acid. At the same time, analytical pure barium sulfate was dissolved with different concentrations of acetic acid and hydrochloric acid. The results showed that the dissolution concentration of barium sulfate with acetic acid of 0.5%-5% mass concentration was less than 4 mg / L, and the dissolution concentration of barium sulfate with hydrochloric acid of less than 2% mass concentration was less than 10 mg / L. Both were significantly lower than the dissolution concentration of barium sulfate with nitric acid, indicating that these two acids have low dissolution background values for the barium sulfate matrix in rock cuttings. In summary, acetic acid and hydrochloric acid can be selected as extractants for barium carbonate toxic substances.

[0032] Example 3: Effect of different solid-liquid ratios of acid and cuttings on the extraction of barium carbonate toxic substances

[0033] 1% hydrochloric acid, 3% hydrochloric acid, 0.5% acetic acid and 1% acetic acid were added to the simulated rock cuttings 2 (the same as the simulated rock cuttings 2 in Example 2) at a solid-liquid ratio of 1:10, 1:20, 1:50 and 1:100, respectively, and the simulated rock cuttings 2 were dissolved. The extraction effect was as follows: Figure 3 The results showed that hydrochloric acid and acetic acid had good extraction accuracy for barium carbonate at a solid-liquid ratio of 1:50 and 1:100, and can be used to extract toxic substances from barium carbonate.

[0034] Example 4: Effect of different ratios of charcoal powder and calcium chloride powder on the extraction of barium sulfate

[0035] Using silicon dioxide, calcium carbonate, and barium sulfate as the main matrices, the three compounds were prepared with a Ba:Ca:Si elemental mass ratio of 2:1:2 to simulate rock chips 3. Accurately weigh 0.5 g of simulated rock chips 3, dry it, and place it in a crucible. Then, add charcoal powder and calcium chloride powder. The mass ratios of simulated rock chips 3:charcoal:calcium chloride were 3:1:3, 3:1:6, 3:1:9, 3:1:15, 1:1:1, 1:1:2, 1:1:3, 1:1:5, 1:5:1, 1:5:2, 1:5:3, 1:5:5, 1:10:1, 1:10:2, 1:10:3, and 1:10:5, respectively. After mixing evenly, place it in a muffle furnace and calcine it at 1100℃ for 30 minutes. After taking out the crucible, use 1% hydrochloric acid (the mass ratio of simulated rock cuttings 3 to hydrochloric acid is 1:200) to extract and detect the barium in the remaining solid, and finally calculate the accuracy of the reduction conversion method. Three parallel samples were made for each sample, and the results are as follows Figure 4 shown.

[0036] The results showed that when the mixing ratio of rock cuttings: charcoal: calcium chloride was 1:1:2, the conversion efficiency was the highest, and the detection accuracy reached over 95%, which was 95.44%±3.13%. This detection accuracy is close to 100% and can be used to establish a method for detecting the total amount of barium in rock cuttings.

[0037] Example 5: A method for fractionating and extracting barium toxic substances from natural gas drilling cuttings

[0038] (1) drying the natural gas drilling cuttings at 105° C. to constant weight, grinding them through a 200-mesh sieve, and accurately weighing 0.5 g of the natural gas drilling cuttings; placing the natural gas drilling cuttings in a container, adding pure water, and placing them in a horizontal shaker or magnetic stirrer for shaking or stirring at room temperature for 30 minutes. After standing, filtering the solution with a microporous filter membrane, collecting the filtrate, and placing the filtered solid in a drying oven at 105° C. to obtain an extract 1 and a solid to be treated 1, wherein the mass ratio of pure water to the natural gas drilling cuttings is 50:1;

[0039] (2) A 2% hydrochloric acid solution is prepared as an extractant, and the solid to be treated 1 is placed in a container, the extractant is added, and the container is placed in a horizontal shaker or a magnetic stirrer for shaking or stirring at room temperature for 30 minutes. After standing, the solution is filtered using a microporous filter membrane, the filtrate is collected, and the filtered solid is placed in a drying oven and dried at 105° C. to obtain an extract 2 and a solid to be treated 2, wherein the mass ratio of the extractant to the natural gas drilling cuttings is 100:1.

[0040] (3) The solid 2 to be treated is placed in a ceramic crucible, charcoal powder and calcium chloride powder are added, and the mixture is evenly mixed in the crucible. The mixture is placed in a muffle furnace, heated to 1000°C, and sintered for 30 minutes. The crucible is then removed after cooling. An extractant is measured and the remaining solid in the crucible is washed three times with the extractant, with the amount of extractant used for each wash being 20 mL. After washing, the remaining extractant is added, and the mixture is placed in a horizontal shaker or magnetic stirrer and shaken or stirred at room temperature for 30 minutes. After standing, the solution is filtered using a microporous filter membrane, and the filtrate is collected to obtain an extract 3, wherein the mass ratio of the extractant to the natural gas drilling cuttings is 200:1.

[0041] Example 6: A method for fractionating and extracting barium toxic substances from natural gas drilling cuttings

[0042] (1) drying the natural gas drilling cuttings at 105° C. to constant weight, grinding them through a 200-mesh sieve, and accurately weighing 0.5 g of the natural gas drilling cuttings; placing the natural gas drilling cuttings in a container, adding pure water, and placing them in a horizontal shaker or magnetic stirrer for shaking or stirring at room temperature for 30 minutes. After standing, filtering the solution with a microporous filter membrane, collecting the filtrate, and placing the filtered solid in a drying oven at 105° C. to obtain an extract 1 and a solid to be treated 1, wherein the mass ratio of pure water to the natural gas drilling cuttings is 50:1;

[0043] (2) A 1% acetic acid solution is prepared as an extractant, and the solid to be treated 1 is placed in a container, the extractant is added, and the container is placed in a horizontal shaker or a magnetic stirrer for shaking or stirring at room temperature for 30 minutes. After standing, the solution is filtered using a microporous filter membrane, the filtrate is collected, and the filtered solid is placed in a drying oven and dried at 105° C. to obtain an extract 2 and a solid to be treated 2, wherein the mass ratio of the extractant to the natural gas drilling cuttings is 100:1.

[0044] (3) The solid 2 to be treated is placed in a ceramic crucible, charcoal powder and calcium chloride powder are added, and the mixture is evenly mixed in the crucible. The mixture is placed in a muffle furnace, heated to 1000°C, and sintered for 30 minutes. The crucible is then removed after cooling. An extractant is measured and the remaining solid in the crucible is washed three times with the extractant, with the amount of extractant used for each wash being 20 mL. After washing, the remaining extractant is added, and the mixture is placed in a horizontal shaker or magnetic stirrer and shaken or stirred at room temperature for 30 minutes. After standing, the solution is filtered using a microporous filter membrane, and the filtrate is collected to obtain an extract 3, wherein the mass ratio of the extractant to the natural gas drilling cuttings is 200:1.

[0045] Example 7: Method for Detecting the Total Amount of Barium in Natural Gas Drilling Cuttings

[0046] The barium content in extract 1 (water-soluble barium toxic substance), extract 2 (acid-soluble barium toxic substance), and extract 3 (barium sulfate) obtained in Example 5 was quantitatively detected using an inductively coupled plasma optical emission spectrometer (ICP-OES). The detection process followed the general method for detecting the barium content in the solution by ICP-OES, or the extracts were detected with reference to the "Determination of Metal Elements in Solid Waste by Inductively Coupled Plasma Mass Spectrometry" (HJ 766-2015), and the barium element concentrations C1, C2, and C3 in the three extracts were obtained, respectively.

[0047] Calculate the result according to the following formula.

[0048] (1) Water-soluble barium toxicity content (mg / kg): W1 = C1 * 50

[0049] Where C1: concentration of barium element in extract 1 (mainly barium chloride), mg / L;

[0050] (2) Acid-soluble barium toxic substance content (mg / kg): W2 = C2 * 100

[0051] Where C2: concentration of barium element in extract 2 (mainly barium carbonate, barium oxide, etc.), mg / L;

[0052] (3) Barium sulfate content (mg / kg): W3 = C3*200*(233.4 / 137.3)

[0053] Where C3: concentration of barium in extract 3, mg / L.

[0054] (4) Total barium content: W4 = W1 + W2 + W3

[0055] Test Example: Accuracy and Precision of Extraction Method for Acid-Soluble Barium Toxic Substances

[0056] (1) Detection limit of the acid-soluble barium toxic substance extraction method: The detection limit of the acid-soluble barium toxic substance extraction method was calculated using a reagent blank. The results showed that the barium content in the reagent blank was not detected on the ICP-OES. Therefore, the barium detection limit of 0.06 mg / L of the ICP-OES detection method was used as the detection value, and the detection limit of the acid-soluble barium toxic substance extraction method was converted to 6 mg / kg.

[0057] (2) Preparation of simulated rock cuttings: Using silicon dioxide, calcium carbonate, and barium sulfate as the main matrix, the three compounds were prepared with a mass ratio of Ba:Ca:Si of 2:1:2, and barium carbonate toxic substances were added with a mass ratio of Ba (barium sulfate):Ba (barium carbonate) of 19:1 to prepare simulated rock cuttings 4, in which the Ba (barium carbonate) content was 0.98%.

[0058] (3) Accuracy and precision of the acid-soluble barium toxic substance extraction method: Since there is currently no standard substance for barium toxic substances in rock cuttings, the accuracy of the acid-soluble barium toxic substance extraction method was determined by preparing simulated rock cuttings. Simulated rock cuttings 2 (the same as simulated rock cuttings 2 in Example 2) and simulated rock cuttings 4 were used. Simulated rock cuttings 2 and simulated rock cuttings 4 were tested 7 times respectively to determine the precision and accuracy (relative deviation between the measured value and the standard value). The results are shown in Table 1. The results show that the determination accuracy of the acid-soluble barium toxic substance extraction method is generally high, with a deviation of only about 3%; the determination precision is less than 5%, which is at a good level and meets the requirements for method establishment.

[0059] Table 1 Accuracy and precision of extraction methods for acid-soluble barium toxic substances

[0060]

[0061]

[0062] The above method was used to detect acid-soluble barium toxic substances in Example 5 and Example 6, and the results are shown in Table 2. The results show that the extraction precision of Example 5 and Example 6 is less than 5%, which is at a good level and meets the requirements of the method establishment.

[0063] Table 2 Acid-soluble barium toxic substance extraction method for Example 5 and Example 6 Determination precision

[0064] Measured value Example 5 Example 6 1 197.59 191.21 2 195.88 200.45 3 194.80 197.05 4 197.01 198.97 5 203.56 200.39 6 200.70 190.06 7 220.63 189.28 Determine the average value 20145.29 19534.43 Determination precision 4.45％ 2.55％

[0065] (4) Recovery rate of spiked acid-soluble barium toxic substances extraction method

[0066] To further verify the reliability of the acid-soluble barium toxic substance extraction method, simulated rock cuttings 2, Example 5, and Example 6 were used to perform spiked recovery tests by adding barium carbonate (GR) at mass ratios of 5%, 10%, 15%, and 20%. Four parallel samples were made for each sample. The results showed that for simulated rock cuttings 2, the spiked recovery rate remained within the range of 90% to 110% at the four spiked concentrations, which was a good level. For Examples 5 and 6, since the barium carbonate toxic substance content in them was less than 0.1%, and the spiked amount was much greater than 3 times the recommended spiked recovery value in the spiked recovery test, the recovery rate was lower than that of simulated rock cuttings 2, but most of them still reached more than 85%. Therefore, the acid-soluble barium toxic substance extraction method has a good spiked recovery effect.

[0067] Table 3 Recovery of spiked acid-soluble barium toxic substances extraction method

[0068]

[0069] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for detecting the total amount of barium in natural gas drilling cuttings, characterized in that: The following steps are involved: (1) Add the sample to pure water, stir at room temperature for 30-60 min, then filter, collect the filtrate, and dry the filtered solid to obtain a first extract and a first solid to be treated; (2) adding an extractant to the first solid to be treated, stirring at room temperature to 40°C for 30-60 min, then filtering, collecting the filtrate, and drying the filtered solid to obtain a second extract and a second solid to be treated; (3) adding charcoal powder and calcium chloride powder to the second solid to be treated, then sintering, cooling, taking out, adding an extractant, stirring at room temperature for 30-60 minutes, then filtering, collecting the filtrate, and obtaining a third extract; (4) Quantitatively testing the barium content in the first extract, the second extract, and the third extract; The extracting agents in step (2) and step (3) are both 1-2 wt% hydrochloric acid solution or 0.5-1 wt% acetic acid solution.

2. The detection method according to claim 1, wherein The mass ratio of the pure water to the sample is 40-60:

1.

3. The detection method according to claim 1, wherein In step (2), the mass ratio of the extractant to the sample is 90-110:

1.

4. The detection method according to claim 1, wherein The mass ratio of the charcoal powder, calcium chloride powder and sample is 1-10:1-5:

1.

5. The detection method according to claim 1, wherein The sintering temperature is 1000-1200 ℃, and the sintering time is 30-50 min.

6. The detection method according to claim 1, characterized in that The volume of the extractant in step (3) is 120-160 mL.

7. Use of the detection method according to any one of claims 1 to 6 in detecting barium in solid waste, raw materials and products containing barium toxic substances.

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