A method for analyzing the chemical phase of mercury in mercury-containing waste

Abstract

The present invention relates to a method for analyzing mercury chemical phases in mercury-containing waste, and belongs to the technical field of chemical phase analysis of metallurgical products. The present invention uses deionized water as a leaching agent to leach mercuric chloride in a mineral and determine its mercury content; then uses maleic acid as a leaching agent to leach mercuric oxide and mercuric sulfate phases in the mineral and determine its mercury content; then uses hydrochloric acid as a leaching agent to leach mercurous chloride in the mineral and determine its mercury content; then uses nitric acid as a leaching agent to leach the metallic mercury phase in the mineral and determine its mercury content; then uses sodium sulfide-sodium hydroxide mixed solution as a leaching agent to leach the mercuric sulfide phase in the mineral and determine its mercury content; the residue is added with alkali and mixed and heated to convert mercuric selenide and mercuric telluride into mercuric oxide, and then uses maleic acid as a leaching agent, that is, mercury in the mercuric selenide and mercuric telluride phases in the mineral, and determines its mercury content. The method of the present invention can accurately analyze the content of multiple mercury phases in a mineral.

Description

Technical Field

[0001] The invention relates to an analysis method of mercury chemical phase in mercury-containing waste, belonging to the technical field of chemical phase analysis of metallurgical products. Background Art

[0002] Mercury recovery and utilization technology is a development trend in the next few years. Identifying the occurrence state of mercury in mercury-containing wastes can provide technical reference and basis for mercury recovery and utilization processes. Phase analysis of mercury is particularly important.

[0003] More than 80% of my country's mercury-containing wastes come from non-ferrous metal smelting enterprises and polyvinyl chloride production enterprises, mainly including acid mud, mercury soot, waste mercury-containing catalysts or copper anode mud. The four types of mercury-containing wastes have a variety of phase compositions with different physical properties. There are no reports on the chemical phase analysis of mercury. The existing analysis of mercury minerals is mostly done by X-ray diffractometers and laser ablation inductively coupled plasma mass spectrometers to analyze the occurrence state of mercury. X-ray diffractometers are not accurate enough in quantitative analysis, and laser ablation inductively coupled plasma mass spectrometers are expensive and cannot perform quantitative analysis. Summary of the invention

[0004] In view of the problem that mercury chemical phases in mercury-containing wastes cannot be quantitatively analyzed at present, the present invention proposes a method for analyzing mercury chemical phases in mercury-containing wastes, which sequentially determines the mercuric chloride phase content, mercuric oxide and mercuric sulfate phase content, mercurous chloride phase content, metallic mercury phase content, mercuric sulfide phase content, mercuric selenide and mercuric telluride phase content in the mineral. The chemical phase analysis method of the present invention can accurately analyze the content of multiple mercury phases in the mineral, and the equipment cost is low.

[0005] A method for analyzing the chemical phase of mercury in mercury-containing waste, the specific steps are as follows:

[0006] (1) Add the mercury-containing waste sample to deionized water and leaching under shaking at room temperature for 8-15 minutes. Liquid-solid separation is performed to obtain filter residue I and filtrate I. The filter residue I is washed with deionized water. After the filtrate I is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the mercuric chloride phase.

[0007] (2) Add the filter residue I to the maleic acid solution and leaching by shaking at room temperature for 15 to 60 min. Liquid-solid separation is performed to obtain filter residue II and filtrate II. The filter residue II is washed with deionized water. After the filtrate II is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the form of mercuric oxide and mercuric sulfate.

[0008] (3) Add the filter residue II to a hydrochloric acid solution and leach at a temperature of 50-80°C for 60-180 min. Perform liquid-solid separation to obtain filter residue III and filtrate III. Wash the filter residue III with deionized water. After the filtrate III is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the mercurous chloride phase.

[0009] (4) Add the filter residue III to a nitric acid solution and leach at a temperature of 50-80°C for 60-120 min. Perform liquid-solid separation to obtain filter residue IV and filtrate IV. Wash the filter residue IV with deionized water. After the filtrate IV is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the metallic mercury phase.

[0010] (5) Add the filter residue IV to a sodium sulfide-sodium hydroxide mixed solution and leach at a temperature of 50-80°C for 60-180 min. Separate the liquid and solid to obtain the filter residue V and the filtrate V. Wash the filter residue V with deionized water. After the filtrate V is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the mercury sulfide phase.

[0011] (6) Add alkaline reagent to the residue V, mix well, heat to 600-850°C and keep warm for 30-120 min, cool to room temperature to obtain solid I, add maleic acid solution to solid I, shake and leach at room temperature for 15-60 min, separate liquid and solid to obtain residue VI and filtrate VI, wash residue VI with deionized water, make filtrate VI constant to volume, and determine the mercury content in the solution, which is the mercury content in the form of mercury selenide and mercury telluride.

[0012] The method for analyzing the chemical phase of mercury in the mercury-containing waste further comprises the following steps:

[0013] Add aqua regia to the same mercury-containing waste sample as in step (1), heat to a temperature of 85-100° C. and react for 8-15 minutes, quickly filter to obtain filter residue VII and filtrate VII, wash the filter residue VII with deionized water, and determine the mercury content in the solution after the filtrate VII is fixed to volume, which is the mercury content in the mercury-containing waste; preferably, the aqua regia is prepared by mixing 4 parts of deionized water, 1 part of hydrochloric acid and 3 parts of nitric acid by mass; the liquid-to-solid ratio of the aqua regia to the mercury-containing waste sample is (60-400):1 in mL:g.

[0014] The mercury-containing waste sample in step (1) is acid mud, mercury soot, waste mercury-containing catalyst or anode mud, and the liquid-solid ratio of deionized water for leaching to the mercury-containing waste sample is (60-400):1.

[0015] Preferably, the concentration of the maleic acid solution in step (2) is 5-15 g / L, and the liquid-to-solid ratio of the maleic acid solution to the mercury-containing waste sample in step (1) is (60-400):1.

[0016] Preferably, the volume concentration of the hydrochloric acid solution in step (3) is 50-70%, and the liquid-to-solid ratio (mL:g) of the hydrochloric acid solution to the mercury-containing waste sample in step (1) is (60-400):1.

[0017] Preferably, the volume concentration of the nitric acid solution in step (4) is 50-70%, and the liquid-to-solid ratio (mL:g) of the nitric acid solution to the mercury-containing waste sample in step (1) is (60-400):1.

[0018] Preferably, the mass concentration of sodium sulfide in the sodium sulfide-sodium hydroxide mixed solution in step (5) is 50-150 g / L, the mass concentration of sodium hydroxide is 50-150 g / L, and the liquid-to-solid ratio (mL:g) of the sodium sulfide-sodium hydroxide mixed solution to the mercury-containing waste sample in step (1) is (60-400):1.

[0019] Preferably, the alkaline reagent in step (6) is calcium oxide, calcium hydroxide, sodium carbonate or sodium hydroxide, and the amount of the alkaline reagent added is 40-60% of the mass of the filter residue V; the concentration of the maleic acid solution is 5-15 g / L, and the liquid-to-solid ratio of the maleic acid solution to the mercury-containing waste sample in step (1) is (60-400):1.

[0020] The chemical phase analysis method of mercury in mercury-containing wastes first uses deionized water as a leaching agent to leach the mercury-containing waste sample. The deionized water can selectively dissolve the mercuric chloride phase in the mineral, and the mercury in other phases remains in the leaching residue. The mercury in the leachate measured is the mercury content in the mercuric chloride phase; then maleic acid is used as a leaching agent to selectively dissolve the mercuric oxide and mercuric sulfate phases, and the mercury in other phases remains in the leaching residue. The mercury in the leachate measured is the mercury content in the mercuric oxide and mercuric sulfate phases; then hydrochloric acid is added under heating conditions to selectively dissolve the mercurous chloride phase, and the mercury in other phases remains in the leaching residue. The mercury in the leachate measured is the mercury content in the mercurous chloride phase; then Nitric acid is added under heating conditions to selectively dissolve the metallic mercury phase, while mercury in other phases remains in the leaching residue. The mercury in the leachate is measured to be the mercury content in the metallic mercury phase. Subsequently, a sodium sulfide-sodium hydroxide mixed solution is added under heating conditions to selectively leach the mercury sulfide phase, while mercury in other phases remains in the leaching residue. The mercury in the leachate is measured to be the mercury content in the mercury sulfide phase. For mercury selenide and mercury telluride in the waste, the phases are extremely stable compounds, and acid leaching has almost no effect. Phase conversion is required before leaching. Alkaline reagents are added and mixed and heated to convert mercury selenide and mercury telluride into mercuric oxide, which is then leached with maleic acid solution. The mercury in the leachate is the mercury content in the mercury selenide and mercury telluride phases.

[0021] The total mercury content in the equal amount of waste sample is measured and compared with the sum of the mercury content of each phase measured step by step in steps (1) to (6) to determine whether the mercury content separated by the chemical phase analysis method is accurate.

[0022] The beneficial effects of the present invention are:

[0023] (1) The method for analyzing the chemical phase of mercury in mercury-containing waste of the present invention comprises the following steps: using deionized water as an leaching agent to leach mercuric chloride in the mineral and determine the mercury content; then using maleic acid as an leaching agent to leach mercuric oxide and mercuric sulfate phases in the mineral and determine the mercury content; then using hydrochloric acid as an leaching agent to leach mercurous chloride in the mineral and determine the mercury content; then using nitric acid as an leaching agent to leach metallic mercury phases in the mineral and determine the mercury content; then using sodium sulfide-sodium hydroxide mixed solution as an leaching agent to leach mercuric sulfide phases in the mineral and determine the mercury content; adding alkali to the residue, mixing and heating, converting mercuric selenide and mercuric telluride into mercuric oxide, then using maleic acid as an leaching agent to extract mercury in the mercuric selenide and mercuric telluride phases in the mineral and determine the mercury content;

[0024] (2) The present invention can accurately analyze the contents of various mercury phases in metallurgical products, solving the shortcomings of instrumental methods such as inaccurate X-ray diffraction and expensive laser ablation inductively coupled plasma mass spectrometry.

[0025] (3) The chemical phase analysis method of the present invention is particularly suitable for the phase analysis of mercury in acid mud, mercury soot, waste mercury-containing catalysts, and anode mud, and the phase separation is accurate. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0027] The present invention is further described in detail below in conjunction with specific implementation modes, but the protection scope of the present invention is not limited to the described contents.

[0028] The method for determining the content of mercury in each step of the embodiment of the present invention (using sodium diethylaminodithiocarbamate titration method) includes the following specific steps:

[0029] 1) Add a mixed solution of tartaric acid and copper chloride to the mercury-containing liquid to be tested, adjust the pH to 8-11 with ammonia water, add 1-3 mL of carbon tetrachloride to form a pre-titration solution, and titrate with a standard solution of sodium diethylaminodithiocarbamate until the inorganic layer shows a light yellow color that is not easy to disappear. Continue to oscillate horizontally for 6-10 times until the organic layer shows a stable yellow color as the end point, and calculate the mercury concentration of the mercury-containing liquid to be tested;

[0030] 2) Calculate the content of mercury in the phase of the mercury-containing waste sample based on the mercury concentration of the mercury-containing liquid to be tested, the fixed volume, the dilution factor and the mass of the mercury-containing waste sample;

[0031] 3) Using 0.001 g / mL mercury ion standard solution, calibrate the mercury titer of sodium diethylaminodithiocarbamate standard solution according to the method in step 1). The calculation method is:

[0032] ;

[0033] Wherein, T is the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury, g / mL; v0 is the measured volume of mercury ion standard solution, mL; V1 is the volume of sodium diethylaminodithiocarboxylate consumed during titration, mL; V0 is the volume of sodium diethylaminodithiocarboxylate consumed during blank titration, mL;

[0034] In the step 2), the concentration of the sodium diethylaminodithiocarboxylate standard solution is 0.001-0.01 mol / L, and 0.3-0.5 g of sodium hydroxide and 1-3 g of sodium sulfite are added to the solution per unit volume (L) to prevent the sodium diethylaminodithiocarboxylate from decomposing and becoming ineffective;

[0035] Method for calculating the content of mercury in the mercury-containing waste

[0036] ;

[0037] Wherein, ω is the mass fraction of mercury, %; T is the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury, g / mL; V2 is the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution, mL; V0 is the volume of sodium diethylaminodithiocarboxylate consumed during blank titration, mL; v2 is the measured volume of the test solution, mL; v1 is the fixed volume of the test solution, mL; m is the mass of the mercury-containing waste sample, in g.

[0038] Example 1: A method for analyzing the chemical phase of mercury in mercury-containing waste (see Figure 1 ), the specific steps are as follows:

[0039] (1) 0.1 g of mercury-containing waste sample was added to 40 ml of deionized water, and the mixture was shaken and leached at room temperature for 8 min. The residue I and filtrate I were separated by liquid-solid separation. The residue I was washed with deionized water. The filtrate I was fixed to volume and the content of mercury in the solution was determined by sodium diethylaminodithiocarbamate titration method, i.e., the content of mercury in the form of mercuric chloride. Specifically, the method for determining the content of mercury in the solution is as follows: a mixed solution of tartaric acid and copper chloride was added to the mercury-containing liquid to be tested, the pH was adjusted to 8 with ammonia water, 1 mL of carbon tetrachloride was added to form a pre-titration solution, and the solution was titrated with sodium diethylaminodithiocarbamate standard solution until the inorganic layer showed a light yellow color that was not easy to disappear, and then Continue to vibrate horizontally for 6 times until the organic layer shows a stable yellow color as the end point, calculate the mercury concentration of the mercury-containing liquid to be tested, the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury is 0.001g / mL, and the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 0.985mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the liquid to be tested (0.985mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.002mL), the measured volume of the solution to be tested (10mL), the fixed volume of the solution to be tested (50mL), and the mass of the mercury-containing waste sample (0.1g),

[0040] Calculation method for the content of mercury in this phase of mercury-containing waste samples

[0041] ;

[0042] Wherein, ω is the mass fraction of mercury, %; T is the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury, g / mL; V2 is the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution, mL; V0 is the volume of sodium diethylaminodithiocarboxylate consumed during blank titration, mL; v2 is the measured volume of the test solution, mL; v1 is the fixed volume of the test solution, mL; m is the mass of the mercury-containing waste sample, in g;

[0043] The content of mercury in this phase in the mercury-containing waste sample of this example is 4.91%, and the content of mercury is the content of mercury in the form of mercuric chloride;

[0044] (2) Add the residue I (0.0946 g calculated on a dry basis) to a 5 g / L maleic acid solution (40 ml), shake and leach at room temperature for 15 min, and separate the liquid and solid to obtain the residue II and filtrate II. Wash the residue II with deionized water, and make up the volume of filtrate II. Then use the diethylaminodithiocarboxylic acid sodium titration method to determine the mercury content in the solution, that is, the mercury content in the form of mercuric oxide and mercuric sulfate. The titer of the standard solution of diethylaminodithiocarboxylic acid is 0.001 g / mL, and the consumption of diethylaminodithiocarboxylic acid is 0.001 g / mL. The volume of sodium dithiocarboxylate standard solution is 0.008 mL. Based on the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (0.008 mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.008 mL), the measured volume of the test solution (50 mL), the fixed volume of the test solution (20 mL), and the mass of the mercury-containing waste sample (0.1 g), the content of mercury in this phase in the mercury-containing waste sample is calculated (0%). The content of mercury is the content of mercury in the form of mercuric oxide and mercuric sulfate phases;

[0045] (3) Add the filter residue II (calculated on a dry basis, 0.0750 g) to a 50% volume concentration hydrochloric acid solution (40 mL), and leach at a temperature of 50°C for 60 min. The filter residue III and the filtrate III are separated by liquid-solid separation. The filter residue III is washed with deionized water. After the filtrate III is fixed to volume, the content of mercury in the solution is determined by the sodium diethylaminodithiocarbamate titration method, that is, the content of mercury in the mercurous chloride phase; the titration degree of the sodium diethylaminodithiocarbamate standard solution for mercury is 0.001 g / mL, and the consumption of diethylaminodithiocarbamate is 0.001 g / mL. The volume of sodium diethylaminodithiocarbamate standard solution is 0.135 mL. According to the volume of sodium diethylaminodithiocarbamate consumed when titrating the test solution (0.135 mL), the volume of sodium diethylaminodithiocarbamate consumed during blank titration (0.005 mL), the measured volume of the test solution (10 mL), the fixed volume of the test solution (50 mL), and the mass of the mercury-containing waste sample (0.1 g), the content of mercury in this phase in the mercury-containing waste sample (0.65%) is calculated. The content of mercury is the content of mercury in the mercurous chloride phase;

[0046] (4) Add the filter residue III (calculated on a dry basis, 0.0743 g) to a nitric acid solution (40 ml) with a volume concentration of 50%, and leaching at a temperature of 50°C for 60 min. Liquid-solid separation is performed to obtain filter residue IV and filtrate IV. The filter residue IV is washed with deionized water. After the filtrate IV is fixed to volume, the mercury content in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, that is, the mercury content in the metallic mercury phase; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.001 g / mL, and the consumption of diethylaminodithiocarboxylate is 0.001 g / mL. The volume of sodium dithiocarbamate standard solution is 0.027 mL. Based on the volume of sodium diethylaminodithiocarbamate consumed when titrating the test solution (0.027 mL), the volume of sodium diethylaminodithiocarbamate consumed during blank titration (0.001 mL), the measured volume of the test solution (50 mL), the fixed volume of the test solution (50 mL), and the mass of the mercury-containing waste sample (0.1 g), the content of mercury in this phase in the mercury-containing waste sample is calculated (0.026%). The content of mercury is the content of mercury in the metallic mercury phase.

[0047] (5) Add the filter residue IV (calculated on a dry basis, 0.0742 g) into 40 mL of a sodium sulfide-sodium hydroxide mixed solution (sodium sulfide mass concentration is 50 g / L, sodium hydroxide mass concentration is 50 g / L), and leaching is carried out at a temperature of 50°C for 60 min. The filter residue V and the filtrate V are separated by liquid-solid separation. The filter residue V is washed with deionized water. After the filtrate V is fixed to volume, the mercury content in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, that is, the mercury content in the mercuric sulfide phase; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.001 g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 4.387mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (4.387mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.010mL), the measured volume of the test solution (50mL), the fixed volume of the test solution (5mL), and the mass of the mercury-containing waste sample (0.1g), the content of mercury in this phase in the mercury-containing waste sample (43.77%) is calculated. The content of mercury is the content of mercury in the mercuric sulfide phase;

[0048] (6) Add alkaline reagent calcium oxide (the amount of alkaline reagent calcium oxide added is 40% of the mass of the residue V) to the residue V (calculated on a dry basis, 0.0261 g) and mix well, then heat to 600°C and keep warm for 30 min, cool to room temperature to obtain solid I, add 5 g / L maleic acid solution (40 mL) to solid I, shake and leach at room temperature for 15 min, and separate the liquid and solid to obtain residue VI and filtrate VI. The residue VI is washed with deionized water, and the filtrate VI is fixed to volume. The mercury content in the solution is determined by diethylaminodithiocarboxylic acid titration method, that is, the mercury content in the form of mercuric selenide and mercuric telluride. The titration degree of sodium thioformate standard solution on mercury is 0.001g / mL, and the volume of sodium diethylaminodithioformate standard solution consumed is 1.069mL. According to the volume of sodium diethylaminodithioformate consumed when titrating the test solution (1.069mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.008mL), the measured volume of the test solution (50mL), the fixed volume of the test solution (20mL), and the mass of the mercury-containing waste sample (0.1g), the content of mercury in this phase in the mercury-containing waste sample is calculated (2.65%). The content of mercury is the content of mercury in the form of mercury selenide and mercury telluride phases;

[0049] (7) Add 5 ml of aqua regia (based on mass, aqua regia is a mixture of 4 parts of deionized water, 1 part of hydrochloric acid and 3 parts of nitric acid) to the same mercury-containing waste sample (0.1 g) as in step (1), heat to 85°C and react for 8 min, quickly filter to obtain a residue VII and a filtrate VII, wash the residue VII twice with deionized water, and determine the mercury content in the solution by titration with sodium diethylaminodithiocarboxylate after the filtrate VII is fixed to volume, which is the mercury content in the mercury-containing waste; the titration degree of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.00 1g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 3.479mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (3.479mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.012mL), the measured volume of the test solution (1mL), the fixed volume of the test solution (15mL), and the mass of the mercury-containing waste sample (0.1g), the content of mercury in this phase in the mercury-containing waste sample is calculated (52.01%). The content of mercury is the total content of mercury in the mercury-containing waste.

[0050] The mercury content detected in this embodiment in the form of mercuric chloride phase is 4.91%, the mercury content in the form of mercuric oxide and mercuric sulfate phase is 0%, the mercury content in the form of mercurous chloride phase is 0.65%, the mercury content in the form of metallic mercury phase is 0.026%, the mercury content in the form of HgS phase is 43.77%, and the mercury content in the form of mercuric selenide and mercuric telluride phase is 2.65%. The total mercury content in the mercury-containing waste sample detected in step (7) is 52.01%. Therefore, the difference between the total mercury content detected in each phase and the total mercury content in the mercury-containing waste sample detected in step (7) is only 0.004%, which proves that the chemical phase analysis method has a very high accuracy in detecting the mercury content in phases.

[0051] Example 2: A method for analyzing the chemical phase of mercury in mercury-containing waste (see Figure 1 ), the specific steps are as follows:

[0052] (1) 0.500 g of mercury-containing waste sample was added to 50 ml of deionized water, and the mixture was shaken and leached at room temperature for 10 min. The residue I and filtrate I were separated by liquid-solid separation. The residue I was washed with deionized water. The filtrate I was fixed to volume and the content of mercury in the solution was determined by sodium diethylaminodithiocarbamate titration method, that is, the content of mercury in the form of mercuric chloride. Specifically, the method for determining the content of mercury in the solution is as follows: a mixed solution of tartaric acid and copper chloride was added to the mercury-containing liquid to be tested, the pH was adjusted to 9 with ammonia water, 2 mL of carbon tetrachloride was added to form a pre-titration solution, and the solution was titrated with sodium diethylaminodithiocarbamate standard solution until the inorganic layer showed a light yellow color that was not easy to disappear, and then Continue to oscillate vigorously in the horizontal direction for 8 times until the organic layer presents a stable yellow color as the end point, calculate the mercury concentration of the mercury-containing liquid to be tested, the titration degree of sodium diethylaminodithiocarboxylate standard solution for mercury is 0.005g / mL, and the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 0.002mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the liquid to be tested (0.002mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.002mL), the measured volume of the solution to be tested (60mL), the fixed volume of the solution to be tested (60mL), and the mass of the mercury-containing waste sample (0.500g),

[0053] Calculation method for the content of mercury in this phase of mercury-containing waste samples

[0054] ;

[0055] Wherein, ω is the mass fraction of mercury, %; T is the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury, g / mL; V2 is the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution, mL; V0 is the volume of sodium diethylaminodithiocarboxylate consumed during blank titration, mL; v2 is the measured volume of the test solution, mL; v1 is the fixed volume of the test solution, mL; m is the mass of the mercury-containing waste sample, in g;

[0056] The content of mercury in this phase in the mercury-containing waste sample of this example is 0%, and the content of mercury is the content of mercury in the form of mercuric chloride;

[0057] (2) Add the filter residue I (0.485 g calculated on a dry basis) to a 5 g / L maleic acid solution (50 ml), shake and leach at room temperature for 30 min, and separate the liquid and solid to obtain the filter residue II and filtrate II. Wash the filter residue II with deionized water, and after the filtrate II is fixed to volume, use the sodium diethylaminodithiocarboxylate titration method to determine the mercury content in the solution, that is, the mercury content in the form of mercuric oxide and mercuric sulfate. The titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.005 g / mL, and the consumption of diethylaminodithiocarboxylate is 0.005 g / mL. The volume of sodium thioformate standard solution is 0.763 mL. Based on the volume of sodium diethylaminodithioformate consumed when titrating the test solution (0.763 mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.011 mL), the measured volume of the test solution (5 mL), the fixed volume of the test solution (60 mL), and the mass of the mercury-containing waste sample (0.5 g), the content of mercury in this phase in the mercury-containing waste sample (9.02%) is calculated. The content of mercury is the content of mercury in the form of mercuric oxide and mercuric sulfate phases;

[0058] (3) Add the filter residue II (calculated on a dry basis, 0.431 g) to a 60% volume concentration hydrochloric acid solution (50 mL), and leaching at a temperature of 65°C for 120 min. Liquid-solid separation is performed to obtain filter residue III and filtrate III. The filter residue III is washed with deionized water. After the filtrate III is fixed to volume, the content of mercury in the solution is determined by sodium diethylaminodithiocarbamate titration method, that is, the content of mercury in the mercurous chloride phase; the titer of sodium diethylaminodithiocarbamate standard solution for mercury is 0.005 g / mL, and the consumption of diethylaminodithiocarbamate is 0.005 g / mL. The volume of sodium diethylaminodithiocarbamate standard solution is 0.444 mL. According to the volume of sodium diethylaminodithiocarbamate consumed when titrating the test solution (0.444 mL), the volume of sodium diethylaminodithiocarbamate consumed during blank titration (0.005 mL), the measured volume of the test solution (20 mL), the fixed volume of the test solution (60 mL), and the mass of the mercury-containing waste sample (0.5 g), the content of mercury in this phase in the mercury-containing waste sample (1.32%) is calculated. The content of mercury is the content of mercury in the mercurous chloride phase;

[0059] (4) Add the filter residue III (0.418 g calculated on a dry basis) to a nitric acid solution (50 ml) with a volume concentration of 60%, and leach it at a temperature of 65°C for 90 min. The filter residue IV and the filtrate IV are separated by liquid-solid separation. The filter residue IV is washed with deionized water. After the filtrate IV is fixed to volume, the mercury content in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, that is, the mercury content in the metallic mercury phase; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.005 g / mL, and the consumption of diethylaminodithiocarboxylate is 0.005 g / mL. The volume of sodium dithiocarbamate standard solution is 1.303 mL. Based on the volume of sodium diethylaminodithiocarbamate consumed when titrating the test solution (1.303 mL), the volume of sodium diethylaminodithiocarbamate consumed during blank titration (0.001 mL), the measured volume of the test solution (5 mL), the fixed volume of the test solution (60 mL), and the mass of the mercury-containing waste sample (0.5 g), the content of mercury in this phase in the mercury-containing waste sample is calculated (15.62%). The content of mercury is the content of mercury in the metallic mercury phase.

[0060] (5) Add the filter residue IV (0.300 g calculated on a dry basis) to 50 mL of a sodium sulfide-sodium hydroxide mixed solution (sodium sulfide mass concentration is 100 g / L, sodium hydroxide mass concentration is 100 g / L), and leaching is carried out at a temperature of 65°C for 120 min. The filter residue V and the filtrate V are separated by liquid-solid separation. The filter residue V is washed with deionized water. After the filtrate V is fixed to volume, the mercury content in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, that is, the mercury content in the mercury sulfide phase; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0 05g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 0.009mL, according to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (0.009mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.009mL), the measured volume of the test solution (60mL), the fixed volume of the test solution (30mL), and the mass of the mercury-containing waste sample (0.5g), the content of mercury in this phase in the mercury-containing waste sample is calculated (0%), and the content of mercury is the content of mercury in the mercury sulfide phase;

[0061] (6) Add alkaline reagent calcium oxide (the amount of alkaline reagent calcium oxide added is 50% of the mass of the residue V) to the filter residue V (calculated on a dry basis, 0.114 g) and mix well, then heat to 750°C and keep warm for 90 min, cool to room temperature to obtain solid I, add 10 g / L maleic acid solution (50 mL) to solid I, shake and leach at room temperature for 30 min, and separate the liquid and solid to obtain filter residue VI and filtrate VI. The filter residue VI is washed with deionized water, and the filtrate VI is fixed to volume. The mercury content in the solution is determined by diethylaminodithiocarboxylic acid titration method, that is, the mercury content in the form of mercuric selenide and mercuric telluride; diethylaminodithiocarboxylic acid The titration degree of sodium thioformate standard solution on mercury is 0.005 g / mL, and the volume of sodium diethylaminodithioformate standard solution consumed is 0.366 mL. According to the volume of sodium diethylaminodithioformate consumed when titrating the test solution (0.366 mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.008 mL), the measured volume of the test solution (30 mL), the fixed volume of the test solution (60 mL), and the mass of the mercury-containing waste sample (0.5 g), the content of mercury in this phase in the mercury-containing waste sample (0.72%) is calculated. The content of mercury is the content of mercury in the form of mercury selenide and mercury telluride phases;

[0062] (7) Add 10 ml of aqua regia (based on mass, aqua regia is a mixture of 4 parts of deionized water, 1 part of hydrochloric acid and 3 parts of nitric acid) to the same mercury-containing waste sample (0.5 g) as in step (1), heat to 92°C and react for 10 min, quickly filter to obtain a residue VII and a filtrate VII, wash the residue VII with deionized water 4 times, and determine the mercury content in the solution by titration with sodium diethylaminodithiocarboxylate after the filtrate VII is fixed to volume, which is the mercury content in the mercury-containing waste; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0 05g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 1.346mL, according to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (1.346mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.012mL), the measured volume of the test solution (1mL), the fixed volume of the test solution (20mL), and the mass of the mercury-containing waste sample (0.5g), the content of mercury in this phase in the mercury-containing waste sample is calculated (26.68%), and the content of mercury is the total content of mercury in the mercury-containing waste;

[0063] The mercury content detected in this embodiment in the form of mercuric chloride phase is 0%, the mercury content in the form of mercuric oxide and mercuric sulfate phase is 9.02%, the mercury content in the form of mercurous chloride phase is 1.32%, the mercury content in the form of metallic mercury phase is 15.62%, the mercury content in the form of mercuric sulfide phase is 0%, the mercury content in the form of mercuric selenide and mercuric telluride phase is 0.72%, and the total mercury content in the mercury-containing waste sample detected in step (7) is 26.68%. Therefore, the difference between the total mercury content detected in each phase and the total mercury content in the mercury-containing waste sample detected in step (7) is only 0%, which proves that the chemical phase analysis method has a very high accuracy rate in detecting mercury content in phases.

[0064] Example 3: A method for analyzing the chemical phase of mercury in mercury-containing waste (see Figure 1 ), the specific steps are as follows:

[0065] (1) 0.8 g of mercury-containing waste sample was added to 55 ml of deionized water, and the mixture was shaken and leached at room temperature for 12 min. The residue I and filtrate I were separated by liquid-solid separation. The residue I was washed with deionized water. The filtrate I was fixed to volume and the content of mercury in the solution was determined by sodium diethylaminodithiocarbamate titration method, i.e., the content of mercury in the form of mercuric chloride. Specifically, the method for determining the content of mercury in the solution was as follows: a mixed solution of tartaric acid and copper chloride was added to the mercury-containing liquid to be tested, the pH was adjusted to 10 with ammonia water, 2.5 mL of carbon tetrachloride was added to form a pre-titration solution, and the solution was titrated with sodium diethylaminodithiocarbamate standard solution until the inorganic layer showed a light yellow color that was not easy to disappear. , continue to oscillate vigorously in the horizontal direction for 9 times until the organic layer presents a stable yellow color as the end point, calculate the mercury concentration of the mercury-containing liquid to be tested, the titration degree of sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0005g / mL, and the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 2.305mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the liquid to be tested (2.305mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.009mL), the measured volume of the solution to be tested (5mL), the fixed volume of the solution to be tested (65mL), and the mass of the mercury-containing waste sample (0.8g),

[0066] Calculation method for the content of mercury in this phase of mercury-containing waste samples

[0067] ;

[0068] Wherein, ω is the mass fraction of mercury, %; T is the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury, g / mL; V2 is the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution, mL; V0 is the volume of sodium diethylaminodithiocarboxylate consumed during blank titration, mL; v2 is the measured volume of the test solution, mL; v1 is the fixed volume of the test solution, mL; m is the mass of the mercury-containing waste sample, in g;

[0069] The content of mercury in this phase in the mercury-containing waste sample of this example is 1.86%, and the content of mercury is the content of mercury in the form of mercuric chloride;

[0070] (2) Add the filter residue I (0.778 g calculated on a dry basis) to a 12 g / L maleic acid solution (55 ml), shake and leach at room temperature for 50 min, and separate the liquid and solid to obtain the filter residue II and filtrate II. Wash the filter residue II with deionized water, and make up the volume of filtrate II. Then use the diethylaminodithiocarboxylic acid sodium titration method to determine the mercury content in the solution, that is, the mercury content in the form of mercuric oxide and mercuric sulfate. The titer of the standard solution of diethylaminodithiocarboxylic acid for mercury is 0.0005 g / mL, and the consumption of diethylaminodithiocarboxylic acid is 0.0005 g / mL. The volume of sodium thioformate standard solution is 0.541 mL. Based on the volume of sodium diethylaminodithioformate consumed when titrating the test solution (0.541 mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.011 mL), the measured volume of the test solution (20 mL), the fixed volume of the test solution (65 mL), and the mass of the mercury-containing waste sample (0.8 g), the content of mercury in this phase in the mercury-containing waste sample (0.11%) is calculated. The content of mercury is the content of mercury in the form of mercuric oxide and mercuric sulfate phases;

[0071] (3) Add the filter residue II (calculated on a dry basis, 0.776 g) to a 65% volume concentration hydrochloric acid solution (55 mL), and leach at 70°C for 150 min. Liquid-solid separation is performed to obtain filter residue III and filtrate III. The filter residue III is washed with deionized water. After the filtrate III is fixed to volume, the content of mercury in the solution is determined by sodium diethylaminodithiocarbamate titration method, that is, the content of mercury in the mercurous chloride phase; the titer of sodium diethylaminodithiocarbamate standard solution for mercury is 0.0005 g / mL, and the consumption of diethylaminodithiocarbamate is 0.0005 g / mL. The volume of sodium diethylaminodithiocarbamate standard solution is 1.778 mL. According to the volume of sodium diethylaminodithiocarbamate consumed when titrating the test solution (1.778 mL), the volume of sodium diethylaminodithiocarbamate consumed during blank titration (0.005 mL), the measured volume of the test solution (10 mL), the fixed volume of the test solution (65 mL), and the mass of the mercury-containing waste sample (0.8 g), the content of mercury in this phase in the mercury-containing waste sample (0.72%) is calculated. The content of mercury is the content of mercury in the mercurous chloride phase;

[0072] (4) Add the filter residue III (0.764 g calculated on a dry basis) to a nitric acid solution (55 ml) with a volume concentration of 65%, and leach it at a temperature of 75°C for 110 min. The filter residue IV and the filtrate IV are separated by liquid-solid separation. The filter residue IV is washed with deionized water. After the filtrate IV is fixed to volume, the mercury content in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, that is, the mercury content in the metallic mercury phase; the titration degree of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0005 g / mL, and the consumption of diethylaminodithiocarboxylate is 0.0005 g / mL. The volume of sodium diethylaminodithioformate standard solution is 1.297 mL. According to the volume of sodium diethylaminodithioformate consumed when titrating the test solution (1.297 mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.001 mL), the measured volume of the test solution (10 mL), the fixed volume of the test solution (65 mL), and the mass of the mercury-containing waste sample (0.8 g), the content of mercury in this phase in the mercury-containing waste sample (0.53%) is calculated. The content of mercury is the content of mercury in the metallic mercury phase;

[0073] (5) Add the filter residue IV (0.756 g calculated on a dry basis) into 55 mL of a sodium sulfide-sodium hydroxide mixed solution (sodium sulfide mass concentration is 120 g / L, sodium hydroxide mass concentration is 120 g / L), and leaching is carried out at 70°C for 150 min. Liquid-solid separation is performed to obtain a filter residue V and a filtrate V. The filter residue V is washed with deionized water, and the filtrate V is fixed to volume and then the mercury content in the solution is determined by titration with sodium diethylaminodithiocarboxylate, i.e., the mercury content in the mercury sulfide phase. The titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.000. 5g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 0.676mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (0.676mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.009mL), the measured volume of the test solution (30mL), the fixed volume of the test solution (65mL), and the mass of the mercury-containing waste sample (0.8g), the content of mercury in this phase in the mercury-containing waste sample (0.090%) is calculated. The content of mercury is the content of mercury in the mercuric sulfide phase;

[0074] (6) Add alkaline reagent calcium oxide (the amount of alkaline reagent calcium oxide added is 55% of the mass of the residue V) to the filter residue V (calculated on a dry basis, 0.754 g) and mix well, then heat to 750°C and keep warm for 100 min, cool to room temperature to obtain solid I, add 12 g / L maleic acid solution (55 mL) to solid I, shake and leach at room temperature for 45 min, and separate the liquid and solid to obtain filter residue VI and filtrate VI. The filter residue VI is washed with deionized water, and the filtrate VI is fixed to volume. The mercury content in the solution is determined by diethylaminodithiocarboxylic acid titration method, that is, the mercury content in the form of mercuric selenide and mercuric telluride. The titration degree of sodium diethylaminodithioformate standard solution on mercury is 0.0005 g / mL, and the volume of sodium diethylaminodithioformate standard solution consumed is 0.008 mL. According to the volume of sodium diethylaminodithioformate consumed when titrating the test solution (0.008 mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.008 mL), the measured volume of the test solution (30 mL), the fixed volume of the test solution (65 mL), and the mass of the mercury-containing waste sample (0.8 g), the content of mercury in this phase in the mercury-containing waste sample is calculated (0%). The content of mercury is the content of mercury in the form of mercury selenide and mercury telluride phases;

[0075] (7) Add 12 ml of aqua regia (based on mass, aqua regia is a mixture of 4 parts of deionized water, 1 part of hydrochloric acid and 3 parts of nitric acid) to the same mercury-containing waste sample (0.8 g) as in step (1), heat to 95°C and react for 12 min, quickly filter to obtain a residue VII and a filtrate VII, wash the residue VII with deionized water 5 times, and determine the mercury content in the solution by titration with sodium diethylaminodithiocarboxylate after the filtrate VII is fixed to volume, which is the mercury content in the mercury-containing waste; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0 005g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 2.660mL, according to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (2.660mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.012mL), the measured volume of the test solution (1mL), the fixed volume of the test solution (20mL), and the mass of the mercury-containing waste sample (0.8g), the content of mercury in this phase in the mercury-containing waste sample is calculated (3.31%), and the content of mercury is the total content of mercury in the mercury-containing waste;

[0076] The mercury content detected in this embodiment in the form of mercuric chloride phase is 1.86%, the mercury content in the form of mercuric oxide and mercuric sulfate phase is 0.11%, the mercury content in the form of mercurous chloride phase is 0.72%, the mercury content in the form of metallic mercury phase is 0.53%, the mercury content in the form of mercuric sulfide phase is 0.090%, the mercury content in the form of mercuric selenide and mercuric telluride phase is 0%, and the total mercury content in the mercury-containing waste sample detected in step (7) is 3.31%. Therefore, the difference between the total mercury content detected in each phase and the total mercury content in the mercury-containing waste sample detected in step (7) is only 0%, which proves that the chemical phase analysis method has a very high accuracy rate in detecting mercury content in phases.

[0077] Example 4: A method for analyzing the chemical phase of mercury in mercury-containing waste (see Figure 1 ), the specific steps are as follows:

[0078] (1) Add 1 g of mercury-containing waste sample to 60 ml of deionized water, shake and leach at room temperature for 15 min, and separate the liquid and solid to obtain filter residue I and filtrate I. The filter residue I is washed with deionized water. After the filtrate I is fixed to volume, the content of mercury in the solution is determined by sodium diethylaminodithiocarbamate titration method, that is, the content of mercury in the form of mercuric chloride phase. Specifically, the method for determining the content of mercury in the solution is as follows: add a mixed solution of tartaric acid and copper chloride to the mercury-containing liquid to be tested, adjust the pH to 11 with ammonia water, add 3 mL of carbon tetrachloride to form a pre-titration solution, and titrate with sodium diethylaminodithiocarbamate standard solution until the inorganic layer appears a light yellow color that is not easy to disappear, and then Continue to oscillate vigorously in the horizontal direction for 10 times until the organic layer presents a stable yellow color as the end point, calculate the mercury concentration of the mercury-containing liquid to be tested, the titration degree of sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0001g / mL, and the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 0.009mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the liquid to be tested (0.009mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.009mL), the measured volume of the solution to be tested (30mL), the fixed volume of the solution to be tested (70mL), and the mass of the mercury-containing waste sample (1g),

[0079] Calculation method for the content of mercury in this phase of mercury-containing waste samples

[0080] ;

[0081] Wherein, ω is the mass fraction of mercury, %; T is the titration degree of sodium diethylaminodithiocarboxylate standard solution on mercury, g / mL; V2 is the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution, mL; V0 is the volume of sodium diethylaminodithiocarboxylate consumed during blank titration, mL; v2 is the measured volume of the test solution, mL; v1 is the fixed volume of the test solution, mL; m is the mass of the mercury-containing waste sample, in g;

[0082] The mercury content of this phase in the mercury-containing waste sample is 0%, and the mercury content is the mercury content in the form of mercuric chloride;

[0083] (2) Add the filter residue I (0.935 g calculated on a dry basis) to a 15 g / L maleic acid solution (60 ml), shake and leach at room temperature for 60 min, and separate the liquid and solid to obtain the filter residue II and filtrate II. Wash the filter residue II with deionized water, and make up the volume of filtrate II. Then use the diethylaminodithiocarboxylic acid sodium titration method to determine the mercury content in the solution, that is, the mercury content in the form of mercuric oxide and mercuric sulfate. The titer of the standard solution of diethylaminodithiocarboxylic acid is 0.0001 g / mL, and the consumption of diethylaminodithiocarboxylic acid is 0.0001 g / mL. The volume of sodium thioformate standard solution is 0.365 mL. According to the volume of sodium diethylaminodithioformate consumed when titrating the test solution (0.365 mL), the volume of sodium diethylaminodithioformate consumed during blank titration (0.011 mL), the measured volume of the test solution (30 mL), the fixed volume of the test solution (70 mL), and the mass of the mercury-containing waste sample (1 g), the content of mercury in this phase in the mercury-containing waste sample (0.0083%) is calculated. The content of mercury is the content of mercury in the form of mercuric oxide and mercuric sulfate phases;

[0084] (3) Add the residue II (0.935 g calculated on a dry basis) to a 70% volume concentration hydrochloric acid solution (60 mL), and leach at 80°C for 180 min. Liquid-solid separation is performed to obtain the residue III and the filtrate III. The residue III is washed with deionized water. After the filtrate III is fixed to volume, the content of mercury in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, i.e., the content of mercury in the mercurous chloride phase. The titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0001 g / mL, and the consumption of diethylaminodithiocarboxylate is 0.0001 g / mL. The volume of sodium ethylaminodithiocarboxylate standard solution is 0.553 mL. According to the volume of sodium ethylaminodithiocarboxylate consumed when titrating the test solution (0.553 mL), the volume of sodium ethylaminodithiocarboxylate consumed during blank titration (0.005 mL), the measured volume of the test solution (30 mL), the fixed volume of the test solution (70 mL), and the mass of the mercury-containing waste sample (1 g), the content of mercury in this phase in the mercury-containing waste sample is calculated (0.013%). The content of mercury is the content of mercury in the mercurous chloride phase;

[0085] (4) Add the filter residue III (0.934 g calculated on a dry basis) to a 70% volume concentration nitric acid solution (60 ml), and leach at 80°C for 120 min. Liquid-solid separation is performed to obtain filter residue IV and filtrate IV. The filter residue IV is washed with deionized water. After the filtrate IV is fixed to volume, the mercury content in the solution is determined by sodium diethylaminodithiocarboxylate titration method, i.e., the mercury content in the metallic mercury phase. The titer of sodium diethylaminodithiocarboxylate standard solution for mercury is 0.0001 g / mL, and the consumption of diethylaminodithiocarboxylate is 0.0001 g / mL. The volume of sodium ethylaminodithiocarboxylate standard solution is 0.001 mL. According to the volume of sodium ethylaminodithiocarboxylate consumed when titrating the test solution (0.001 mL), the volume of sodium ethylaminodithiocarboxylate consumed during blank titration (0.001 mL), the measured volume of the test solution (30 mL), the fixed volume of the test solution (70 mL), and the mass of the mercury-containing waste sample (1 g), the content of mercury in this phase in the mercury-containing waste sample (0%) is calculated. The content of mercury is the content of mercury in the metallic mercury phase;

[0086] (5) Add the filter residue IV (0.934 g calculated on a dry basis) into 60 mL of a sodium sulfide-sodium hydroxide mixed solution (sodium sulfide mass concentration is 150 g / L, sodium hydroxide mass concentration is 150 g / L), and leaching is carried out at a temperature of 80°C for 180 min. The filter residue V and the filtrate V are separated by liquid-solid separation. The filter residue V is washed with deionized water. After the filtrate V is fixed to volume, the mercury content in the solution is determined by the sodium diethylaminodithiocarboxylate titration method, that is, the mercury content in the mercury sulfide phase; the titer of the sodium diethylaminodithiocarboxylate standard solution for mercury is 0.00 01g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 1.696mL, according to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (1.696mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.009mL), the measured volume of the test solution (20mL), the fixed volume of the test solution (70mL), and the mass of the mercury-containing waste sample (1g), the content of mercury in this phase in the mercury-containing waste sample (0.059%) is calculated, and the content of mercury is the content of mercury in the mercuric sulfide phase;

[0087] (6) Add alkaline reagent calcium oxide (the amount of alkaline reagent calcium oxide added is 60% of the mass of the residue V) to the filter residue V (calculated on a dry basis, 0.933 g) and mix well, then heat to 850°C and keep warm for 120 min, cool to room temperature to obtain solid I, add 15 g / L maleic acid solution (60 mL) to solid I, shake and leach at room temperature for 60 min, and separate the liquid and solid to obtain filter residue VI and filtrate VI. The filter residue VI is washed with deionized water, and the filtrate VI is fixed to volume. The mercury content in the solution is determined by diethylaminodithiocarboxylic acid titration method, that is, the mercury content in the form of mercuric selenide and mercuric telluride. The titration degree of sodium dithiocarboxylate standard solution on mercury is 0.0001g / mL, and the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 2.222mL. According to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (2.222mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.008mL), the measured volume of the test solution (5mL), the fixed volume of the test solution (70mL), and the mass of the mercury-containing waste sample (1g), the content of mercury in this phase in the mercury-containing waste sample (0.31%) is calculated. The content of mercury is the content of mercury in the HgSe and HgTe phases;

[0088] (7) Add 15 ml of aqua regia (based on mass, aqua regia is a mixture of 4 parts of deionized water, 1 part of hydrochloric acid and 3 parts of nitric acid) to the same mercury-containing waste sample (1 g) as in step (1), heat to 100°C and react for 15 min, quickly filter to obtain a filter residue VII and a filtrate VII, wash the filter residue VII with deionized water for 6 times, and determine the mercury content in the solution by titration with sodium diethylaminodithiocarboxylate after the filtrate VII is fixed to volume, which is the mercury content in the mercury-containing waste; the titration degree of sodium diethylaminodithiocarboxylate standard solution for mercury is 0. 0001g / mL, the volume of sodium diethylaminodithiocarboxylate standard solution consumed is 1.962mL, according to the volume of sodium diethylaminodithiocarboxylate consumed when titrating the test solution (1.962mL), the volume of sodium diethylaminodithiocarboxylate consumed during blank titration (0.012mL), the measured volume of the test solution (1mL), the fixed volume of the test solution (20mL), and the mass of the mercury-containing waste sample (1g), the content of mercury in this phase in the mercury-containing waste sample (0.39%) is calculated, and the content of mercury is the total content of mercury in the mercury-containing waste;

[0089] The mercury content detected in this embodiment in the form of mercuric chloride phase is 0%, the mercury content in the form of mercuric oxide and mercuric sulfate phase is 0.0083%, the mercury content in the form of mercurous chloride phase is 0.013%, the mercury content in the form of metallic mercury phase is 0%, the mercury content in the form of mercuric sulfide phase is 0.059%, the mercury content in the form of mercuric selenide and mercuric telluride phase is 0.31%, and the total mercury content in the mercury-containing waste sample detected in step (7) is 0.39%. Therefore, the difference between the total mercury content detected in each phase and the total mercury content in the mercury-containing waste sample detected in step (7) is only 0.0003%, which proves that the accuracy of phase separation mercury content detection by the chemical phase analysis method is very high.

[0090] The specific implementation modes of the present invention are described in detail above, but the present invention is not limited to the above implementation modes, and various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. A method for analyzing the chemical phase of mercury in mercury-containing waste, characterized in that: The specific steps are as follows: (1) Add the mercury-containing waste sample to deionized water and leaching under shaking at room temperature for 8-15 minutes. Liquid-solid separation is performed to obtain filter residue I and filtrate I. The filter residue I is washed with deionized water. After the filtrate I is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the mercuric chloride phase. (2) Add the filter residue I to the maleic acid solution and leaching by shaking at room temperature for 15 to 60 min. Liquid-solid separation is performed to obtain filter residue II and filtrate II. The filter residue II is washed with deionized water. After the filtrate II is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the form of mercuric oxide and mercuric sulfate. (3) Add the filter residue II to a hydrochloric acid solution and leach at a temperature of 50-80°C for 60-180 min. Perform liquid-solid separation to obtain filter residue III and filtrate III. Wash the filter residue III with deionized water. After the filtrate III is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the mercurous chloride phase. (4) Add the filter residue III to a nitric acid solution and leach at a temperature of 50-80°C for 60-120 min. Perform liquid-solid separation to obtain filter residue IV and filtrate IV. Wash the filter residue IV with deionized water. After the filtrate IV is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the metallic mercury phase. (5) Add the filter residue IV to a sodium sulfide-sodium hydroxide mixed solution and leach at a temperature of 50-80°C for 60-180 min. Separate the liquid and solid to obtain the filter residue V and the filtrate V. Wash the filter residue V with deionized water. After the filtrate V is fixed to volume, the mercury content in the solution is determined, which is the mercury content in the mercury sulfide phase. (6) Add alkaline reagent to the residue V, mix well, heat to 600-850°C and keep warm for 30-120 min, cool to room temperature to obtain solid I, add maleic acid solution to solid I, shake and leach at room temperature for 15-60 min, separate liquid and solid to obtain residue VI and filtrate VI, wash residue VI with deionized water, make filtrate VI constant to volume, and determine the mercury content in the solution, which is the mercury content in the form of mercury selenide and mercury telluride.

2. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: The following steps are also included: Add aqua regia to the same mercury-containing waste sample as in step (1), heat to a temperature of 85-100°C and react for 8-15 minutes, quickly filter to obtain filter residue VII and filtrate VII, wash the filter residue VII with deionized water, and determine the mercury content in the solution after the filtrate VII is fixed to volume, which is the mercury content in the mercury-containing waste.

3. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: Step (1) The mercury-containing waste sample is acid mud, mercury soot, waste mercury-containing catalyst or anode mud, and the liquid-solid ratio of deionized water for leaching to the mercury-containing waste sample is (60-400):1 in mL:g.

4. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: The concentration of the maleic acid solution in step (2) is 5-15 g / L, and the liquid-to-solid ratio of the maleic acid solution to the mercury-containing waste sample in step (1) is (60-400):

1.

5. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: The volume concentration of the hydrochloric acid solution in step (3) is 50-70%, and the liquid-to-solid ratio of the hydrochloric acid solution to the mercury-containing waste sample in step (1) is (60-400):

1.

6. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: The volume concentration of the nitric acid solution in step (4) is 50-70%, and the liquid-to-solid ratio of the nitric acid solution to the mercury-containing waste sample in step (1) is (60-400):

1.

7. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: The mass concentration of sodium sulfide in the sodium sulfide-sodium hydroxide mixed solution of step (5) is 50-150 g / L, the mass concentration of sodium hydroxide is 50-150 g / L, and the liquid-to-solid ratio of the sodium sulfide-sodium hydroxide mixed solution to the mercury-containing waste sample of step (1) is (60-400):

1.

8. The method for analyzing the chemical phase of mercury in mercury-containing waste according to claim 1, characterized in that: The alkaline reagent in step (6) is calcium oxide, calcium hydroxide, sodium carbonate or sodium hydroxide, and the amount of the alkaline reagent added is 40-60% of the mass of the filter residue V; the concentration of the maleic acid solution is 5-15 g / L, and the liquid-to-solid ratio of the maleic acid solution to the mercury-containing waste sample in step (1) is (60-400):1.

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