Phase Analysis Method of Silver in General Ores

Abstract

The invention belongs to the technical field of physical phase analysis in ores, and specifically relates to a physical phase analysis method for silver in general ores; acetic acid is used as a leaching agent to leach the silver content in smithsonite, sodium chloride and hydroxylamine hydrochloride are used as leaching agents to leach the silver content in iron-manganese-containing minerals, ferric nitrate nonahydrate is used as a leaching agent to leach the silver content in natural silver, thiourea is used as a leaching agent to leach the silver content in silver sulfide, hydrochloric acid and stannous chloride are used as leaching agents to leach the silver content in iron oxides, and then the silver in silicate is determined: the method solves the problems of incomplete classification of silver physical phases, poor wide applicability and backward analysis methods.

Description

Technical Field

[0001] The invention belongs to the technical field of physical phase analysis in ores, and in particular relates to a physical phase analysis method for silver in general ores. Background Art

[0002] Phase analysis refers to the analytical method of determining the mineral composition of materials and their existence state by chemical or physical methods. Chemical phase analysis is a relatively new branch of analytical chemistry. Because it is a relatively unique analytical testing technology formed and developed in the process of studying the material composition of mineral raw materials and smelting intermediates, it is first applied in industrial fields such as mineral processing engineering and metallurgical technology, geological prospecting, process mineralogy and beneficiation experimental research. After research and development, chemical phase analysis has also been widely used in geological prospecting, ore deposit evaluation, beneficiation process research and production practice, new energy material research and development, comprehensive utilization and recovery of mineral resources, monitoring and governance. The application scope of contemporary chemical phase analysis has expanded to disciplines closely related to people's daily lives, such as environment, industry, food, and Chinese herbal medicine, and has made significant progress.

[0003] Ag in geological samples mainly exists in the form of sulfides in the form of independent minerals, such as argentite (Ag2S), argentite, Ag3SbS3, etc. Ag in natural silver (Ag0) and silver intermetallic compounds such as silver-gold ore, gold-silver ore, galena, and copper sulfide minerals can exist in isomorphic or fine inclusion states: under surface conditions, there is secondary mineral argillite (AgCl); some iron-manganese oxides and gangue minerals can also encapsulate or adsorb Ag.

[0004] Currently, there are very few literatures on silver phase analysis, and the classification of silver phases is incomplete, not universal, and has poor wide applicability. The analysis methods are relatively backward and have not been combined with the rapid development of modern testing fields, including a series of problems such as the lack of combination with fast and accurate modern instruments. Summary of the invention

[0005] In order to overcome the above problems, the present invention provides a method for analyzing the physical phases of silver in general ores, which solves the problems of incomplete classification of silver physical phases, poor widespread applicability and backward analysis methods.

[0006] A method for phase analysis of silver in general ores comprises the following steps:

[0007] Step 1: Determination of silver content in smithsonite:

[0008] Weigh 0.1000g-0.2000g of an ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, cover with a watch glass, heat on a 180°C hot plate for 45 minutes, cool to room temperature, filter into a 400mL beaker using a double-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the volume reaches 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid, heat and digest on a hot plate, add hydrochloric acid for leaching after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up the volume, and determine the silver content in the solution by atomic absorption;

[0009] The extractant 1 is 6% acetic acid by volume: 6 mL of glacial acetic acid is added to 94 mL of water and mixed, and shaken well;

[0010] Step 2: Determination of silver in iron-manganese-containing minerals:

[0011] Put the filter residue after filtering in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the volume reaches 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid, and heat and digest on a hot plate. After the digestion is completed, add hydrochloric acid for leaching, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to the volume, and determine the silver content in the solution by ICP;

[0012] The preparation method of the extractant 2 is as follows: 50 g of sodium chloride and 20 g of hydroxylamine hydrochloride are dissolved in 1 liter of water and shaken well;

[0013] Step 3: Determination of natural silver:

[0014] Put the filter residue after filtering in step 2 together with the filter paper into a 150mL conical flask, add 50mL of leaching agent 3, add 5mL of mercuric sulfate solution, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the volume reaches 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid, and heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to the volume, and determine the silver content in the solution by atomic absorption;

[0015] The preparation method of the extractant 3 is as follows: 70 g of ferric nitrate nonahydrate is dissolved in 1 liter of water and shaken well;

[0016] Step 4, determination of silver sulfide:

[0017] The filter residue after filtering in step 3 is placed in a 150mL conical flask together with the filter paper, 100mL of leaching agent 4 is added, and horizontal oscillation is performed for 45 minutes at an oscillation frequency of 180 times / minute; the filtrate is filtered into a 400mL beaker using a single-layer quantitative filter paper, and the volume of the washing filtrate is adjusted to 250-300mL, and the filtrate is concentrated by heating until the volume reaches 50mL, and the filtrate is removed and cooled slightly, 1mL of sulfuric acid is added, and the filtrate is placed on a 180°C electric hot plate, and nitric acid is added to adjust until the solution turns yellow and no more bubbles are generated, and the filtrate is removed and placed on a high-temperature furnace plate at 350°C and steamed until white smoke is emitted, and the filtrate is removed and cooled slightly, 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid are added to the beaker, and the filtrate is heated and digested on the electric hot plate, and after the digestion is completed, hydrochloric acid is added for leaching, so that the mass concentration of hydrochloric acid is 15-20%, and distilled water is added to the volume, and the silver content in the solution is determined by atomic absorption;

[0018] The preparation method of the extractant 4 is as follows: 60 g of thiourea is dissolved in 995 mL of distilled water, 50 mL of sulfuric acid is slowly added, and after cooling to room temperature, the mixture is shaken well;

[0019] Step 5, determination of silver in iron oxides:

[0020] Put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 580mL of leaching agent 5, and heat on an electric hot plate at 80°C for 40 minutes; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate until the volume reaches 50mL, take it out and cool it slightly, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on an electric hot plate, add hydrochloric acid to leach after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to the volume, and determine the silver content in the solution by atomic absorption;

[0021] The preparation method of the extractant 5 is as follows: take 100 mL of hydrochloric acid, add 200 mL of distilled water, add 3 g of stannous chloride, and shake well after dissolving;

[0022] Step 6, determination of silver in silicate:

[0023] Put the filter residue after filtering in step 5 together with the filter paper into a 100 mL corundum crucible, put it into a methane fluoride furnace at room temperature, and heat it to 700° C. for ashing. After the ashing is completed, add 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid, and heat and digest on a hot plate. After the digestion is completed, add hydrochloric acid for leaching, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to volume, and determine the silver content in the solution by atomic absorption;

[0024] Step 7: Calculate the concentration of the silver phase corresponding to any one of steps 1 to 6 according to the following formula:

[0025]

[0026] Where: W(Ag)—mass fraction of silver phase corresponding to any item, %;

[0027] C—Silver concentration obtained from the working curve, in μg / mL;

[0028] C0—blank concentration obtained from the working curve, in μg / mL;

[0029] V—fixed volume, mL;

[0030] d—the dilution factor of the fixed volume solution in each phase;

[0031] m—mass of sample, g.

[0032] In the step 3, the preparation method of mercuric sulfate is: weigh 0.080 g of mercuric sulfate and dissolve it in 50 mL of 70 g / L ferric nitrate solution, and then dilute it to 1 L with distilled water.

[0033] Beneficial effects of the present invention:

[0034] 1) The present invention reasonably selects various existing forms of silver that may exist in general ores, and scientifically and reasonably selects the leaching agent for each phase, thereby ensuring that the leaching agent of the upper phase will not leach the silver of the lower phases, thereby ensuring the accurate determination of each phase.

[0035] 2) Acetic acid was innovatively used as the leaching agent to leach silver from smithsonite.

[0036] 3) The innovative use of ferric nitrate to dissolve mercuric sulfate, because mercuric sulfate cannot be dissolved in water, adding acid to dissolve it will affect the leaching of the next phase, so acid dissolution cannot be used; this method uses ferric nitrate to dissolve mercuric sulfate, and ferric nitrate is also a leaching agent and does not affect the determination, ensuring that mercuric sulfate can be added quantitatively, because if the solid is added directly, the amount added is too little to be weighed, and adding too much will affect the leaching effect.

[0037] 4) Thiourea sulfuric acid solution is used in the determination process of silver sulfide, which can ensure the complete leaching of silver sulfide, but at the same time, excessive thiourea will affect the determination and must be removed. This method innovatively adopts the following method: add 1mL of sulfuric acid, put it on a 180℃ hot plate, add concentrated nitric acid to adjust until the solution turns yellow and no longer produces a large number of bubbles, remove it and put it on a high-temperature furnace at 350℃ to steam until white smoke is emitted, thereby removing excessive thiourea and eliminating interference.

[0038] 5) The invention innovatively adopts the method of adding 1% stannous chloride to hydrochloric acid (1+2) to leach silver from iron oxide.

[0039] 6) In this method, all reactions that require heating are heated by electric heating plates, which is simple to operate and suitable for batch operations. DETAILED DESCRIPTION

[0040] The present invention will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than to limit the present invention.

[0041] A method for phase analysis of silver in general ores comprises the following steps:

[0042] Step 1: Determination of silver content in smithsonite:

[0043] Weigh 0.1000g-0.2000g of an ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, cover with a watch glass, heat on a 180°C hot plate for 45 minutes, cool to room temperature, filter into a 400mL beaker using a double-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the concentrated volume is about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid for leaching after digestion, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up the volume according to the silver ion content in the solution, and measure the silver content in the solution by atomic absorption;

[0044] Step 2: Determination of silver in iron-manganese-containing minerals:

[0045] The filter residue filtered in step 1 is placed together with the filter paper in a 150mL conical flask, 25mL of leaching agent 2 is added, and the mixture is horizontally oscillated for 25 minutes at a frequency of 180 times / minute; the mixture is filtered into a 400mL beaker using a single-layer quantitative filter paper, and the volume of the washed filtrate is adjusted to 150-200mL, and the filtrate is concentrated by heating until the concentrated volume is about 20mL; 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid are added to the beaker, and the mixture is heated and digested on a hot plate; after the digestion is completed, hydrochloric acid is added for leaching, so that the mass concentration of the hydrochloric acid is 15-20%, and distilled water is added to the volume according to the silver ion content in the solution, and the silver content in the solution is determined by ICP;

[0046] Step 3: Determination of natural silver:

[0047] Put the filter residue after filtering in step 2 together with the filter paper into a 150mL conical flask, add 50mL of leaching agent 3, add 5mL of mercuric sulfate solution, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate until the volume is 150-200mL, heat and concentrate the filtrate until the concentrated volume is about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on an electric hot plate, add hydrochloric acid for leaching after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up the volume according to the silver ion content in the solution, and determine the silver content in the solution by atomic absorption;

[0048] Step 4, determination of silver sulfide:

[0049] The filter residue after filtering in step 3 is placed in a 150mL conical flask together with the filter paper, 100mL of leaching agent 4 is added, and horizontal oscillation is performed for 45 minutes at an oscillation frequency of 180 times / minute; a single-layer quantitative filter paper is used to filter into a 400mL beaker, and the volume of the washing filtrate is up to 250-300mL, and the filtrate is concentrated by heating until the concentrated volume reaches about 50mL, and then the filtrate is removed and cooled slightly, 1mL of sulfuric acid is added, and the filtrate is placed on a 180°C hot plate, and nitric acid is added to adjust until the solution turns yellow and no more bubbles are generated, and then the filtrate is removed and placed on a high-temperature furnace plate at 350°C and steamed until white smoke is emitted, and then the filtrate is removed and cooled slightly, 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid are added to the beaker, and the mixture is heated and digested on the hot plate, and after the digestion is completed, hydrochloric acid is added for leaching, so that the mass concentration of hydrochloric acid is 15-20%, and distilled water is added to the volume according to the silver ion content in the solution, and the silver content in the solution is determined by atomic absorption;

[0050] Note: Nitric acid should be added dropwise during the adjustment process and should not be added in large quantities quickly.

[0051] Step 5, determination of silver in iron oxides:

[0052] The filter residue after filtering in step 4 is placed in a 150mL conical flask together with the filter paper, 580mL of leaching agent 5 is added, and the mixture is heated on a hot plate at 80°C for 40 minutes; a single-layer quantitative filter paper is used to filter the mixture into a 400mL beaker, and the volume of the washed filtrate is adjusted to 250-300mL, and the filtrate is concentrated by heating until the concentrated volume reaches about 50mL, and then the mixture is cooled slightly, 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid are added to the beaker, and the mixture is heated and digested on a hot plate, and hydrochloric acid is added after the digestion is completed to leach the mixture, so that the mass concentration of the hydrochloric acid is 15-20%, and distilled water is added to make up the volume according to the silver ion content in the solution, and the silver content in the solution is determined by atomic absorption;

[0053] Step 6, determination of silver in silicate:

[0054] The filter residue after filtering in step 5 is placed together with the filter paper in a 100 mL corundum crucible, and placed in a methane fluoride furnace at room temperature, and heated to 700° C. for ashing. After the ashing is completed, 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of commercially available high-concentration hydrofluoric acid, and 3 mL of perchloric acid are added to the crucible, and heated on a hot plate for digestion. After the digestion is completed, hydrochloric acid is added for leaching, so that the mass concentration of hydrochloric acid is 15-20%, and distilled water is added to make up the volume according to the silver ion content in the solution, and the silver content in the solution is determined by atomic absorption;

[0055] Determination of total silver - used to verify whether the silver content measured in steps 1 to 6 above is accurate:

[0056] For the same sample, weigh 0.1g to 0.5g of the same ore sample as the ore sample taken in step 1 into a polytetrafluoro crucible, add water to moisten, add 15mL of hydrochloric acid, 10mL of nitric acid, 5mL of hydrofluoric acid, and 3mL of perchloric acid into the crucible, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up the volume according to the silver ion content in the solution, and determine the silver content in the solution by atomic absorption, which is the total amount of silver in the ore sample;

[0057] Step 7: Calculate the concentration of the silver phase corresponding to any one of steps 1 to 6 according to the following formula:

[0058]

[0059] Where: W(Ag)—mass fraction of silver phase corresponding to any item, %;

[0060] C—Silver concentration (atomic absorption or ICP) obtained from the working curve, in μg / mL;

[0061] C0—blank concentration (atomic absorption or ICP) obtained from the working curve, in μg / mL;

[0062] V—fixed volume, mL;

[0063] d—the dilution factor of the fixed volume solution in each phase;

[0064] m—mass of sample, g.

[0065] In the step 1, the extractant 1 is acetic acid with a volume fraction of 6%: 6 mL of glacial acetic acid is added to 94 mL of water, mixed, and shaken.

[0066] In the step 2, the preparation method of the leaching agent 2 is as follows: 50 g of sodium chloride and 20 g of hydroxylamine hydrochloride are dissolved in 1 liter of water and shaken well.

[0067] In the step 3, the preparation method of the leaching agent 3 is as follows: 70 g of ferric nitrate nonahydrate is dissolved in 1 liter of water and shaken well;

[0068] The preparation method of mercuric sulfate is as follows: weigh 0.080g of mercuric sulfate and dissolve it in 50mL of 70g / L ferric nitrate solution, and then dilute the volume to 1L with distilled water.

[0069] In the step 4, the preparation method of the leaching agent 4 is as follows: 60 g of thiourea is dissolved in 995 mL of distilled water, 50 mL of sulfuric acid is slowly added, and the mixture is cooled to room temperature and shaken well.

[0070] In the step 5, the preparation method of the leaching agent 5 is as follows: take 100 mL of hydrochloric acid, add 200 mL of distilled water, add 3 g of stannous chloride, and shake well after dissolving.

[0071] The hydrochloric acid mentioned above is commercially available concentrated hydrochloric acid, the nitric acid is commercially available concentrated nitric acid, and the perchloric acid is commercially available analytically pure perchloric acid.

[0072] Example 1

[0073] A method for phase analysis of silver in general ores comprises the following steps:

[0074] Step 1, determination of silver content in smithsonite: weigh 0.1000g of ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, i.e. 6% acetic acid, cover with a watch glass, heat on a hot plate at 180°C for 45 minutes, cool to room temperature, filter into a 400mL beaker using double-layer quantitative filter paper, wash the filtrate until the volume is 150-200mL, heat and concentrate the filtrate until the volume is about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, control the acidity at 15-20%, fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0075] Measured value: 0.51 Blank measured value: 0.00

[0076] According to the calculation formula, the silver content in smithsonite is: 0.051%

[0077] Step 2, determination of silver in iron-manganese-containing minerals: put the filter residue filtered in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by ICP absorption.

[0078] Measured value: 0.68 Blank measured value: 0.01

[0079] According to the calculation formula, the silver content in iron-manganese minerals is: 0.067%

[0080] Step 3, determination of natural silver: put the filter residue after filtering in step 2 together with filter paper into a 150mL conical flask, add 50mL leaching agent 3, add 5mL mercuric sulfate solution, horizontally oscillate for 25 minutes, and the oscillation frequency is 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL hydrochloric acid, 10mL nitric acid, and 3mL perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0081] Measured value: 0.48 Blank measured value: 0.02

[0082] According to the calculation formula, the silver content in iron-manganese minerals is: 0.046%

[0083] Step 4, the determination of silver sulfide: the filter residue after filtering in step 3 is put into 150mL conical flask together with filter paper, 100mL leaching agent 4 is added, horizontal vibration is 45 minutes, oscillation frequency 180 times / minute. Adopt single-layer quantitative filter paper to filter in the beaker of 400mL, wash filtrate volume till 250-300mL, heat and concentrate filtrate, when concentrated volume is to about 50mL, take off slightly cold, add 1mL sulfuric acid, put on 180 ℃ electric hot plate, add concentrated nitric acid and adjust to solution and become yellow, no longer produce a large amount of bubbles, take off and put on 350 ℃ high temperature furnace plate and steam to white smoke, take off slightly cold, add 15mL hydrochloric acid, 10mL nitric acid, 3mL perchloric acid in beaker, heat and digest on electric hot plate, add hydrochloric acid to leach after digestion, acidity is controlled at 15-20%, constant volume sample is in 100mL volumetric flask, therefrom draw 5mL constant volume in 100mL volumetric flask, atomic absorption determination sample.

[0084] Note: Nitric acid should be added dropwise during the adjustment process and should not be added in large quantities quickly.

[0085] Measured value: 2.58 Blank measured value: 0.01

[0086] According to the calculation formula, the silver content in iron-manganese-containing minerals is: 5.14%

[0087] Step 5, determination of silver in iron oxide: put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 5 80mL of leaching agent, and heat on a hot plate at 80°C for 40 minutes. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate, and when the concentrated volume is about 50mL, remove it and cool it slightly. Add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid to the beaker, and heat and digest on the hot plate. After the digestion is completed, add hydrochloric acid for leaching, and control the acidity at 15-20%. The volume of the sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0088] Measured value: 1.45 Blank measured value: 0.01

[0089] According to the calculation formula, the silver content in iron-manganese minerals is: 0.144%

[0090] Step 6, determination of silver in silicate: put the filter residue filtered in step 5 together with the filter paper into a 100mL corundum crucible, put it into a muffle furnace at low temperature, and raise it to 700°C. After the ashing is completed, 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid are added to the crucible, and heated on a hot plate for digestion. After the digestion is completed, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%. The sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0091] Measured value: 0.55 Blank measured value: 0.01

[0092] According to the calculation formula, the silver content in iron-manganese minerals is: 0.054%

[0093] Step 7, determination of total silver:

[0094] Weigh 0.1g-0.5g of ore sample into a polytetrafluoroethylene crucible, add water to moisten it, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid into the crucible, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, and control the acidity at 15-20%. The sample is fixed to a 100mL volumetric flask, and 1mL is taken from it and fixed to a 50mL volumetric flask, and the sample is determined by atomic absorption. This is the total amount of silver in the ore sample.

[0095] Measured value: 1.11 Blank measured value: 0.01

[0096] According to the calculation formula, the total silver content is: 5.50%

[0097] The total amount of silver in each phase is 5.50%, and the total amount is 5.50%, which proves that this method is accurate and reliable.

[0098] Example 2

[0099] A method for phase analysis of silver in general ores comprises the following steps:

[0100] Step 1, determination of silver content in smithsonite: weigh 0.1000g of ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, i.e. 6% acetic acid, cover with a watch glass, heat on a hot plate at 180°C for 45 minutes, cool to room temperature, filter into a 400mL beaker using double-layer quantitative filter paper, wash the filtrate until the volume is 150-200mL, heat and concentrate the filtrate until the volume is about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, control the acidity at 15-20%, fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0101] Measured value: 0.32 Blank measured value: 0.00

[0102] According to the calculation formula, the silver content in smithsonite is: 0.032%

[0103] Step 2, determination of silver in iron-manganese-containing minerals: put the filter residue filtered in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by ICP absorption.

[0104] Measured value: 0.23 Blank measured value: 0.01

[0105] According to the calculation formula, the silver content in iron-manganese minerals is: 0.022%

[0106] Step 3, determination of natural silver: put the filter residue after filtering in step 2 together with filter paper into a 150mL conical flask, add 50mL leaching agent 3, add 5mL mercuric sulfate solution, horizontally oscillate for 25 minutes, and the oscillation frequency is 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL hydrochloric acid, 10mL nitric acid, and 3mL perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0107] Measured value: 0.58 Blank measured value: 0.02

[0108] According to the calculation formula, the silver content in iron-manganese minerals is: 0.056%

[0109] Step 4, the determination of silver sulfide: the filter residue after filtering in step 3 is put into 150mL conical flask together with filter paper, 100mL leaching agent 4 is added, horizontal vibration is 45 minutes, oscillation frequency 180 times / minute. Adopt single-layer quantitative filter paper to filter in the beaker of 400mL, wash filtrate volume till 250-300mL, heat and concentrate filtrate, when concentrated volume is to about 50mL, take off slightly cold, add 1mL sulfuric acid, put on 180 ℃ electric hot plate, add concentrated nitric acid and adjust to solution and become yellow, no longer produce a large amount of bubbles, take off and put on 350 ℃ high temperature furnace plate and steam to white smoke, take off slightly cold, add 15mL hydrochloric acid, 10mL nitric acid, 3mL perchloric acid in beaker, heat and digest on electric hot plate, add hydrochloric acid to leach after digestion, acidity is controlled at 15-20%, constant volume sample is in 100mL volumetric flask, therefrom draw 5mL constant volume in 100mL volumetric flask, atomic absorption determination sample.

[0110] Note: Nitric acid should be added dropwise during the adjustment process and should not be added in large quantities quickly.

[0111] Measured value: 0.98 Blank measured value: 0.01

[0112] According to the calculation formula, the silver content in iron-manganese-containing minerals is: 1.94%

[0113] Step 5, determination of silver in iron oxide: put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 5 80mL of leaching agent, and heat on a hot plate at 80°C for 40 minutes. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate, and when the concentrated volume is about 50mL, remove it and cool it slightly. Add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid to the beaker, and heat and digest on the hot plate. After the digestion is completed, add hydrochloric acid for leaching, and control the acidity at 15-20%. The volume of the sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0114] Measured value: 1.15 Blank measured value: 0.01

[0115] According to the calculation formula, the silver content in iron-manganese minerals is: 0.114%

[0116] Step 6, determination of silver in silicate: put the filter residue filtered in step 5 together with the filter paper into a 100mL corundum crucible, put it into a muffle furnace at low temperature, and raise it to 700°C. After the ashing is completed, 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid are added to the crucible, and heated on a hot plate for digestion. After the digestion is completed, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%. The sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0117] Measured value: 0.65 Blank measured value: 0.01

[0118] According to the calculation formula, the silver content in iron-manganese minerals is: 0.064%

[0119] Step 7, determination of total silver:

[0120] Weigh 0.1g-0.5g of ore sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid into the crucible, heat and digest on a hot plate, add hydrochloric acid for leaching after digestion, control the acidity at 15-20%, dilute the sample into a 100mL volumetric flask, draw 2mL from it and dilute it into a 50mL volumetric flask, and measure the sample by atomic absorption. This is the total amount of silver in the ore sample.

[0121] Measured value: 0.90 Blank measured value: 0.01

[0122] According to the calculation formula, the total silver content is: 2.23%

[0123] The total amount of silver in each phase is: 2.23% and the total amount is determined to be: 2.23%.

[0124] Example 3

[0125] A method for phase analysis of silver in general ores comprises the following steps:

[0126] Step 1, determination of silver content in smithsonite: weigh 0.2000g of ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, i.e. 6% acetic acid, cover with a watch glass, heat on a hot plate at 180°C for 45 minutes, cool to room temperature, filter into a 400mL beaker using double-layer quantitative filter paper, wash the filtrate until the volume is 150-200mL, heat and concentrate the filtrate until the volume is about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, control the acidity at 15-20%, fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0127] Measured value: 0.22 Blank measured value: 0.00

[0128] According to the calculation formula, the silver content in smithsonite is: 0.011%

[0129] Step 2, determination of silver in iron-manganese-containing minerals: put the filter residue filtered in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by ICP absorption.

[0130] Measured value: 0.35 Blank measured value: 0.01

[0131] According to the calculation formula, the silver content in iron-manganese minerals is: 0.017%

[0132] Step 3, determination of natural silver: put the filter residue after filtering in step 2 together with filter paper into a 150mL conical flask, add 50mL leaching agent 3, add 5mL mercuric sulfate solution, horizontally oscillate for 25 minutes, and the oscillation frequency is 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL hydrochloric acid, 10mL nitric acid, and 3mL perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0133] Measured value: 0.28 Blank measured value: 0.02

[0134] According to the calculation formula, the silver content in iron-manganese minerals is: 0.013%

[0135] Step 4, the mensuration of silver sulfide: the filter residue after filtering in step 3 is put into 150mL conical flask together with filter paper, 100mL leaching agent 4 is added, horizontal vibration is 45 minutes, oscillation frequency 180 times / minute. Adopt single-layer quantitative filter paper to filter in the beaker of 400mL, wash filtrate volume till 250-300mL, heat and concentrate filtrate, when concentrated volume is to about 50mL, take off slightly cold, add 1mL sulfuric acid, put on 180 ℃ electric hot plate, add concentrated nitric acid and adjust to solution and become yellow, no longer produce a large amount of bubbles, take off and put on 350 ℃ high temperature furnace plate and steam to white smoke, take off slightly cold, add 15mL hydrochloric acid, 10mL nitric acid, 3mL perchloric acid in beaker, heat and digest on electric hot plate, add hydrochloric acid to leach after digestion finishes, acidity is controlled at 15-20%, constant volume sample is in 100mL volumetric flask, atomic absorption determination sample.

[0136] Note: Nitric acid should be added dropwise during the adjustment process and should not be added in large quantities quickly.

[0137] Measured value: 0.65 Blank measured value: 0.01

[0138] According to the calculation formula, the silver content in iron-manganese minerals is: 0.032%

[0139] Step 5, determination of silver in iron oxide: put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 5 80mL of leaching agent, and heat on a hot plate at 80°C for 40 minutes. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate, and when the concentrated volume is about 50mL, remove it and cool it slightly. Add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid to the beaker, and heat and digest on the hot plate. After the digestion is completed, add hydrochloric acid for leaching, and control the acidity at 15-20%. The volume of the sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0140] Measured value: 1.25 Blank measured value: 0.01

[0141] According to the calculation formula, the silver content in iron-manganese minerals is: 0.062%

[0142] Step 6, determination of silver in silicate: put the filter residue filtered in step 5 together with the filter paper into a 100mL corundum crucible, put it into a muffle furnace at low temperature, and raise it to 700°C. After the ashing is completed, 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid are added to the crucible, and heated on a hot plate for digestion. After the digestion is completed, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%. The sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0143] Measured value: 0.69 Blank measured value: 0.01

[0144] According to the calculation formula, the silver content in iron-manganese minerals is: 0.034%

[0145] Step 7, determination of total silver:

[0146] Weigh 0.1g-0.5g of ore sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid into the crucible, heat and digest on a hot plate, add hydrochloric acid for leaching after digestion, control the acidity at 15-20%, dilute the sample into a 100mL volumetric flask, draw 10mL from it and dilute it into a 50mL volumetric flask, and measure the sample by atomic absorption. This is the total amount of silver in the ore sample.

[0147] Measured value: 0.68 Blank measured value: 0.01

[0148] According to the calculation formula, the total silver content is: 0.17%

[0149] The total amount of silver in each phase is 0.17% and the total amount is 0.17%.

[0150] Example 4

[0151] A method for phase analysis of silver in general ores comprises the following steps:

[0152] Step 1, determination of silver content in smithsonite: weigh 0.1500g of ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, i.e. 6% acetic acid, cover with a watch glass, heat on a hot plate at 180°C for 45 minutes, cool to room temperature, filter into a 400mL beaker using double-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate to a volume of about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, control the acidity at 15-20%, fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0153] Measured value: 0.15 Blank measured value: 0.00

[0154] According to the calculation formula, the silver content in smithsonite is: 0.010%

[0155] Step 2, determination of silver in iron-manganese-containing minerals: put the filter residue filtered in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by ICP absorption.

[0156] Measured value: 0.65 Blank measured value: 0.01

[0157] According to the calculation formula, the silver content in iron-manganese-containing minerals is: 0.043%

[0158] Step 3, determination of natural silver: put the filter residue after filtering in step 2 together with filter paper into a 150mL conical flask, add 50mL leaching agent 3, add 5mL mercuric sulfate solution, horizontally oscillate for 25 minutes, and the oscillation frequency is 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL hydrochloric acid, 10mL nitric acid, and 3mL perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0159] Measured value: 0.49 Blank measured value: 0.02

[0160] According to the calculation formula, the silver content in iron-manganese minerals is: 0.031%

[0161] Step 4, the mensuration of silver sulfide: the filter residue after filtering in step 3 is put into 150mL conical flask together with filter paper, 100mL leaching agent 4 is added, horizontal vibration is 45 minutes, oscillation frequency 180 times / minute. Adopt single-layer quantitative filter paper to filter in the beaker of 400mL, wash filtrate volume till 250-300mL, heat and concentrate filtrate, when concentrated volume is to about 50mL, take off slightly cold, add 1mL sulfuric acid, put on 180 ℃ electric hot plate, add concentrated nitric acid and adjust to solution and become yellow, no longer produce a large amount of bubbles, take off and put on 350 ℃ high temperature furnace plate and steam to white smoke, take off slightly cold, add 15mL hydrochloric acid, 10mL nitric acid, 3mL perchloric acid in beaker, heat and digest on electric hot plate, add hydrochloric acid to leach after digestion finishes, acidity is controlled at 15-20%, constant volume sample is in 100mL volumetric flask, atomic absorption determination sample.

[0162] Note: Nitric acid should be added dropwise during the adjustment process and should not be added in large quantities quickly.

[0163] Measured value: 0.45 Blank measured value: 0.01

[0164] According to the calculation formula, the silver content in iron-manganese minerals is: 0.029%

[0165] Step 5, determination of silver in iron oxide: put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 5 80mL of leaching agent, and heat on a hot plate at 80°C for 40 minutes. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate, and when the concentrated volume is about 50mL, remove it and cool it slightly. Add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid to the beaker, and heat and digest on the hot plate. After the digestion is completed, add hydrochloric acid for leaching, and control the acidity at 15-20%. The volume of the sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0166] Measured value: 0.25 Blank measured value: 0.01

[0167] According to the calculation formula, the silver content in iron-manganese minerals is: 0.016%

[0168] Step 6, determination of silver in silicate: put the filter residue filtered in step 5 together with the filter paper into a 100mL corundum crucible, put it into a muffle furnace at low temperature, and raise it to 700°C. After the ashing is completed, 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid are added to the crucible, and heated on a hot plate for digestion. After the digestion is completed, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%. The sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0169] Measured value: 0.28 Blank measured value: 0.01

[0170] According to the calculation formula, the silver content in iron-manganese-containing minerals is: 0.018%

[0171] Step 7, determination of total silver:

[0172] Weigh 0.1g-0.5g of ore sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid into the crucible, heat and digest on a hot plate, add hydrochloric acid for leaching after digestion, control the acidity at 15-20%, dilute the sample into a 100mL volumetric flask, and measure the sample by atomic absorption. This is the total amount of silver in the ore sample.

[0173] Measured value: 2.21 Blank measured value: 0.01

[0174] According to the calculation formula, the total silver content is: 0.15%

[0175] The total amount of silver in each phase is 0.15% and the total amount is 0.15%.

[0176] Example 5

[0177] A method for phase analysis of silver in general ores comprises the following steps:

[0178] Step 1, determination of silver content in smithsonite: weigh 0.1000g of ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, i.e. 6% acetic acid, cover with a watch glass, heat on a hot plate at 180°C for 45 minutes, cool to room temperature, filter into a 400mL beaker using double-layer quantitative filter paper, wash the filtrate until the volume is 150-200mL, heat and concentrate the filtrate until the volume is about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, control the acidity at 15-20%, fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0179] Measured value: 0.65 Blank measured value: 0.00

[0180] According to the calculation formula, the silver content in smithsonite is: 0.065%

[0181] Step 2, determination of silver in iron-manganese-containing minerals: put the filter residue filtered in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by ICP absorption.

[0182] Measured value: 0.27 Blank measured value: 0.01

[0183] According to the calculation formula, the silver content in iron-manganese minerals is: 0.026%

[0184] Step 3, determination of natural silver: put the filter residue after filtering in step 2 together with filter paper into a 150mL conical flask, add 50mL leaching agent 3, add 5mL mercuric sulfate solution, horizontally oscillate for 25 minutes, and the oscillation frequency is 180 times / minute. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate, concentrate the volume to about 20mL, add 15mL hydrochloric acid, 10mL nitric acid, and 3mL perchloric acid into the beaker, heat and digest on a hot plate, add hydrochloric acid to leach after digestion, control the acidity at 15-20%, and fix the sample to a 100mL volumetric flask, and measure the sample by atomic absorption.

[0185] Measured value: 0.41 Blank measured value: 0.02

[0186] According to the calculation formula, the silver content in iron-manganese-containing minerals is: 0.039%

[0187] Step 4, the mensuration of silver sulfide: the filter residue after filtering in step 3 is put into 150mL conical flask together with filter paper, 100mL leaching agent 4 is added, horizontal vibration is 45 minutes, oscillation frequency 180 times / minute. Adopt single-layer quantitative filter paper to filter in the beaker of 400mL, wash filtrate volume till 250-300mL, heat and concentrate filtrate, when concentrated volume is to about 50mL, take off slightly cold, add 1mL sulfuric acid, put on 180 ℃ electric hot plate, add concentrated nitric acid and adjust to solution and become yellow, no longer produce a large amount of bubbles, take off and put on 350 ℃ high temperature furnace plate and steam to white smoke, take off slightly cold, add 15mL hydrochloric acid, 10mL nitric acid, 3mL perchloric acid in beaker, heat and digest on electric hot plate, add hydrochloric acid to leach after digestion finishes, acidity is controlled at 15-20%, constant volume sample is in 100mL volumetric flask, atomic absorption determination sample.

[0188] Note: Nitric acid should be added dropwise during the adjustment process and should not be added in large quantities quickly.

[0189] Measured value: 0.15 Blank measured value: 0.01

[0190] According to the calculation formula, the silver content in iron-manganese-containing minerals is: 0.014%

[0191] Step 5, determination of silver in iron oxide: put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 5 80mL of leaching agent, and heat on a hot plate at 80°C for 40 minutes. Use a single-layer quantitative filter paper to filter into a 400mL beaker, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate, and when the concentrated volume is about 50mL, remove it and cool it slightly. Add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid to the beaker, and heat and digest on the hot plate. After the digestion is completed, add hydrochloric acid for leaching, and control the acidity at 15-20%. The volume of the sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0192] Measured value: 0.31 Blank measured value: 0.01

[0193] According to the calculation formula, the silver content in iron-manganese minerals is: 0.010%

[0194] Step 6, determination of silver in silicate: put the filter residue filtered in step 5 together with the filter paper into a 100mL corundum crucible, put it into a muffle furnace at low temperature, and raise it to 700°C. After the ashing is completed, 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid are added to the crucible, and heated on a hot plate for digestion. After the digestion is completed, hydrochloric acid is added for leaching, and the acidity is controlled at 15-20%. The sample is fixed to a 100mL volumetric flask, and the sample is determined by atomic absorption.

[0195] Measured value: 0.38 Blank measured value: 0.01

[0196] According to the calculation formula, the silver content in iron-manganese minerals is: 0.037%

[0197] Step 7, determination of total silver:

[0198] Weigh 0.1g-0.5g of ore sample into a polytetrafluoroethylene crucible, moisten with water, add 15mL hydrochloric acid, 10mL nitric acid, 5mL hydrofluoric acid, and 3mL perchloric acid into the crucible, heat and digest on a hot plate, add hydrochloric acid for leaching after digestion, control the acidity at 15-20%, dilute the sample into a 100mL volumetric flask, and measure the sample by atomic absorption. This is the total amount of silver in the ore sample.

[0199] Measured value: 1.91 Blank measured value: 0.01

[0200] According to the calculation formula, the total silver content is: 0.19%

[0201] The total amount of silver in each phase is 0.19% and the total amount is 0.19%.

[0202] The preferred embodiments of the present invention are described in detail above. However, the protection scope of the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention. These simple variations all belong to the protection scope of the present invention.

[0203] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0204] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for phase analysis of silver in general ores, characterized in that The steps include: Step 1: Determination of silver content in smithsonite: Weigh 0.1000g-0.2000g of an ore sample with a particle size less than 0.075mm into a 150mL conical flask, add 50mL of leaching agent 1, cover with a watch glass, heat on a 180°C hot plate for 45 minutes, cool to room temperature, filter into a 400mL beaker using a double-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the volume reaches 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid, heat and digest on a hot plate, add hydrochloric acid for leaching after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up the volume, and determine the silver content in the solution by atomic absorption; The extractant 1 is 6% acetic acid by volume: 6 mL of glacial acetic acid is added to 94 mL of water and mixed, and shaken well; Step 2: Determination of silver in iron-manganese-containing minerals: Put the filter residue after filtering in step 1 together with the filter paper into a 150mL conical flask, add 25mL of leaching agent 2, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the volume reaches 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid, and heat and digest on a hot plate. After the digestion is completed, add hydrochloric acid for leaching, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to the volume, and determine the silver content in the solution by ICP; The preparation method of the extractant 2 is as follows: 50 g of sodium chloride and 20 g of hydroxylamine hydrochloride are dissolved in 1 liter of water and shaken well; Step 3: Determination of natural silver: Put the filter residue after filtering in step 2 together with the filter paper into a 150mL conical flask, add 50mL of leaching agent 3, add 5mL of mercuric sulfate solution, and oscillate horizontally for 25 minutes at an oscillation frequency of 180 times / minute; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate to a volume of 150-200mL, heat and concentrate the filtrate until the volume reaches 20mL, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid, and heat and digest on a hot plate, add hydrochloric acid to leach after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to the volume, and determine the silver content in the solution by atomic absorption; The preparation method of the extractant 3 is as follows: 70 g of ferric nitrate nonahydrate is dissolved in 1 liter of water and shaken well; Step 4, determination of silver sulfide: The filter residue after filtering in step 3 is placed in a 150mL conical flask together with the filter paper, 100mL of leaching agent 4 is added, and horizontal oscillation is performed for 45 minutes at an oscillation frequency of 180 times / minute; the filtrate is filtered into a 400mL beaker using a single-layer quantitative filter paper, and the volume of the washing filtrate is adjusted to 250-300mL, and the filtrate is concentrated by heating until the volume reaches 50mL, and the filtrate is removed and cooled slightly, 1mL of sulfuric acid is added, and the filtrate is placed on a 180°C electric hot plate, and nitric acid is added to adjust until the solution turns yellow and no more bubbles are generated, and the filtrate is removed and placed on a high-temperature furnace plate at 350°C and steamed until white smoke is emitted, and the filtrate is removed and cooled slightly, 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid are added to the beaker, and the filtrate is heated and digested on the electric hot plate, and after the digestion is completed, hydrochloric acid is added for leaching, so that the mass concentration of hydrochloric acid is 15-20%, and distilled water is added to the volume, and the silver content in the solution is determined by atomic absorption; The preparation method of the extractant 4 is as follows: 60 g of thiourea is dissolved in 995 mL of distilled water, 50 mL of sulfuric acid is slowly added, and after cooling to room temperature, the mixture is shaken well; Step 5, determination of silver in iron oxides: Put the filter residue after filtering in step 4 together with the filter paper into a 150mL conical flask, add 580mL of leaching agent 5, and heat on an electric hot plate at 80°C for 40 minutes; filter into a 400mL beaker using a single-layer quantitative filter paper, wash the filtrate to a volume of 250-300mL, heat and concentrate the filtrate until the volume reaches 50mL, take it out and cool it slightly, add 15mL of hydrochloric acid, 10mL of nitric acid, and 3mL of perchloric acid into the beaker, heat and digest on an electric hot plate, add hydrochloric acid to leach after the digestion is completed, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to the volume, and determine the silver content in the solution by atomic absorption; The preparation method of the extractant 5 is as follows: take 100 mL of hydrochloric acid, add 200 mL of distilled water, add 3 g of stannous chloride, and shake well after dissolving; Step 6, determination of silver in silicate: Put the filter residue after filtering in step 5 together with the filter paper into a 100 mL corundum crucible, put it into a methane fluoride furnace at room temperature, and heat it to 700° C. for ashing. After the ashing is completed, add 15 mL of hydrochloric acid, 10 mL of nitric acid, 5 mL of hydrofluoric acid, and 3 mL of perchloric acid, and heat and digest on a hot plate. After the digestion is completed, add hydrochloric acid for leaching, so that the mass concentration of hydrochloric acid is 15-20%, add distilled water to make up to volume, and determine the silver content in the solution by atomic absorption; Step 7: Calculate the concentration of the silver phase corresponding to any one of steps 1 to 6 according to the following formula: Where: W(Ag)—mass fraction of silver phase corresponding to any item, %; C—Silver concentration obtained from the working curve, in μg / mL; C0—blank concentration obtained from the working curve, in μg / mL; V—fixed volume, mL; d—the dilution factor of the fixed volume solution in each phase; m—mass of sample, g; In the step 3, the preparation method of mercuric sulfate is: weigh 0.080 g of mercuric sulfate and dissolve it in 50 mL of 70 g / L ferric nitrate solution, and then dilute it to 1 L with distilled water.

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