CN104232920A - Separation method of various precious metals - Google Patents
Separation method of various precious metals Download PDFInfo
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- CN104232920A CN104232920A CN201410461779.7A CN201410461779A CN104232920A CN 104232920 A CN104232920 A CN 104232920A CN 201410461779 A CN201410461779 A CN 201410461779A CN 104232920 A CN104232920 A CN 104232920A
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Abstract
The invention discloses a separation method of various precious metals. The separation method comprises the following steps: (1) pyropenic process; (2) pretreatment before distillation; (3) pretreatment before iridium extraction: neutralizing distillation residual liquid, washing with water of 70-80DEG C to remove salt for later use, and delivering to an iridium station; (4) iridium extraction; (5) sequential recovery of platinum, palladium and rhodium from iridium precipitation mother liquid; (6) separation of platinum by adopting a solvent extraction method; (7) separation of palladium by adopting a xanthate precipitation method; and (8) separation of rhodium by adopting a copper powder substitution method. The separation method is simple in technology, energy-saving and environment-friendly, does not generate pollutants, and can be used for effectively separating various heavy metals.
Description
Technical field
The present invention relates to a kind of chemical separation method, particularly relate to the separation method of one kind of multiple precious metals.
Background technology
In the removal process of waste and old noble metal materials, often can run into the complex feedstock containing more than three kinds (as: platinum, palladium, rhodium, iridium, osmium and ruthenium) precious metals.Technique is in the past only for a certain precious metal, and maximum three kinds, and technique imperfection, be not easy to operation, separating effect and yield are also undesirable.Precious metal composition should be allowed in process of production to be separated from each other thoroughly, allow it be convenient to reclaim again, and yield to be more high better.This just needs improve or change original methods involving.
Material first by pyrogenic process, all melts by this technique, for reducing the loss of volatile material, reducing temperature, shorten smelting time when pyrogenic process.Going out osmium and ruthenium by fractionation by distillation, considering from production safety angle, add pre-treatment link: pre-treatment before distillation, is removing unnecessary alkali, avoiding producing a large amount of reaction heat and salinity instantaneously during distillation, cause system jams.
Consider from environmental protection and economic angle, the sodium chlorate that novel process have employed less contamination makees distillation oxygenant, for ensureing that the quality of osmium adopts hydrazine hydrate to make absorption agent.Vinasse is used for being separated iridium, is production safety and improves the yield of iridium, also will carry out pre-treatment, in and raffinate, wash away salinity.The raffinate isolating iridium is used for extracting platinum, palladium and rhodium etc.Find after deliberation, the waste residue platiniferous in iridium treating process, available ammonium chloride method reclaims platinum.This also increases the yield of platinum.
At present, lack a kind of can the separation method of multiple precious metal of good separating effect.
Summary of the invention
The object of this invention is to provide a kind of separation method of multiple precious metal of good separating effect.
To achieve these goals, the present invention's scheme realization by the following method: the separation method of one kind of multiple precious metals, comprises the steps:
(1) pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, load in crucible be heated to temperature be 700-800 DEG C, 2-3h after material melts completely, take out in crucible and cool;
(2) pre-treatment before distillation: by the water-soluble pulp of frit of cooling, pass into sulfurous gas, to neutral; For subsequent use with the washing freshen of 70-80 DEG C;
Fractionation by distillation osmium and ruthenium: above-mentioned slag is proceeded in reactor in batches and distills; Do medium with sulfuric acid, sodium chlorate makees oxygenant, absorbs ruthenium with the ethanolic soln that the hydrochloric acid soln of 1:1 and mass concentration are 0.5%; With mass concentration be 30% hydrazine hydrate solution and mass concentration be 0.5% ethanolic soln absorb osmium;
Ruthenium absorption liquid send ruthenium post to continue to be processed into the finished product; Osmium absorption liquid send osmium post to continue to be processed into the finished product;
(3) pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 70-80 DEG C, send iridium post;
(4) carry iridium: above-mentioned recrement, employing mass ratio is solid: liquid=1:5, adds 4N hydrochloric acid heating for dissolving; Described solid is recrement, and described liquid is 4N hydrochloric acid; Filtered by dissolving with hydrochloric acid liquid, dissolving with hydrochloric acid liquid catches up with acid repeatedly, and filter residue reclaims and returns pyrogenic process; To the hydrochloric acid soln of iridium, namely add oxygenant in filtrate, make iridium change IV valency into, then add ammonium chloride, generate black ammonium iridichloride precipitation; Concentrated mother liquor also adds oxygenant until without ammonium iridichloride Precipitation; With the ammonium chloride solution repetitive scrubbing ammonium iridichloride that mass concentration is 15%, filter after standing sedimentation; Iridium salt is separated with mother liquor; Thick ammonium iridichloride send iridium purification post to continue to purify;
(5) heavy iridium mother liquor is used for reclaiming platinum, palladium, rhodium successively;
(6) Solvent Extraction Separation of Platinum: adopt tributyl phosphate Extraction of Platinum from heavy iridium mother liquor; Keep solution be 3-5mol/l hydrochloric acid, with account for liquor capacity 0.5% sulfuric acid; Use calcium phosphate+ forage platinum, then go out platinum with the back extraction of 0.5-1.5mol/l sodium hydroxide solution, send platreating to purify;
(7) xanthate precipitator method separate palladium: solution control ph is 0.5-1.5, add the 1-3 Bei Yellow medicine of theoretical amount under room temperature, the reaction times is 30-60min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine;
(8) copper powder substitution method separate rhodium: solution being heated to temperature is 95 DEG C, adds copper powder, constantly stirs, until react completely, obtains thick rhodium powder and send rhodium refining purification.
The separation method of the multiple precious metal of another kind of the present invention, comprises the steps:
(1) pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, load in crucible be heated to temperature be 700-800 DEG C, 2-3h after material melts completely, take out in crucible and cool;
(2) pre-treatment before distillation: by the water-soluble pulp of frit of cooling, pass into sulfurous gas, to neutral; For subsequent use with the washing freshen of 70-80 DEG C;
Fractionation by distillation osmium and ruthenium: above-mentioned slag is proceeded in reactor in batches and distills; Do medium with sulfuric acid, sodium chlorate makees oxygenant, absorbs ruthenium with the ethanolic soln that the hydrochloric acid soln of 1:1 and mass concentration are 0.5%; With mass concentration be 30% hydrazine hydrate solution and mass concentration be 0.5% ethanolic soln absorb osmium;
Ruthenium absorption liquid send ruthenium post to continue to be processed into the finished product; Osmium absorption liquid send osmium post to continue to be processed into the finished product;
(3) pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 70-80 DEG C, send iridium post;
(4) carry iridium: above-mentioned recrement, employing mass ratio is solid: liquid=1:5, adds 4N hydrochloric acid heating for dissolving; Described solid is recrement, and described liquid is 4N hydrochloric acid; Filtered by dissolving with hydrochloric acid liquid, dissolving with hydrochloric acid liquid catches up with acid repeatedly, and filter residue reclaims and returns pyrogenic process; To the hydrochloric acid soln of iridium, namely add oxygenant in filtrate, make iridium change IV valency into, then add ammonium chloride, generate black ammonium iridichloride precipitation;
Concentrated mother liquor also adds oxygenant until without ammonium iridichloride Precipitation; With the ammonium chloride solution repetitive scrubbing ammonium iridichloride that mass concentration is 15%, filter after standing sedimentation; Iridium salt is separated with mother liquor; Thick ammonium iridichloride send iridium purification post to continue to purify;
(5) heavy iridium mother liquor is used for reclaiming platinum, palladium, rhodium successively;
(6) carry the waste residue that iridium produces, with aqua regia dissolution, chloride precipitation method extracts platinum, obtains ammonium chloroplatinate and send platreating;
(7) xanthate precipitator method separate palladium: solution control ph is 0.5-1.5, add the 1-3 Bei Yellow medicine of theoretical amount under room temperature, the reaction times is 30-60min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine;
(8) copper powder substitution method separate rhodium: solution being heated to temperature is 95 DEG C, adds copper powder, constantly stirs, until react completely, obtains thick rhodium powder and send rhodium refining purification.
Further, in step (4), described oxygenant is hydrogen peroxide or nitric acid.
Further, in step (4), filter flask or filter vat is adopted to filter.
Beneficial effect: present invention process is simple, and energy-conserving and environment-protective, do not produce pollutent, effectively can be separated various heavy.
Tool of the present invention has the following advantages: material first by pyrogenic process, all melts by (1), for reducing the loss of volatile material, reducing temperature, shorten smelting time when pyrogenic process.
(2) going out osmium and ruthenium by fractionation by distillation, considering from production safety angle, add pre-treatment link: pre-treatment before distillation, is removing unnecessary alkali, avoiding producing a large amount of reaction heat and salinity instantaneously during distillation, cause system jams.
(3) through above-mentioned separation sequence and separation method, can be thorough by various precious metal separation, and accomplish high-recovery, fully realize the value of the recycling of waste and old precious metal.
(4) consider from environmental protection and economic angle, the sodium chlorate that novel process have employed less contamination makees distillation oxygenant.For ensureing that the quality of osmium adopts hydrazine hydrate to make absorption agent.Employing hydrazine hydrate absorbs, and be absorbed with several advantage compared to sodium hydroxide: first, it can not bring sodium ion into, and osmium powder can not exceed standard by sodium; Secondly, yield is high, reaches 99%.When sodium hydroxide absorbs, the osmium having about 10% remains in the solution, needs repeatedly to reclaim.The yield of additive method is lower.
(5) vinasse is used for being separated iridium, is production safety and improves the yield of iridium, also will carry out pre-treatment, in and raffinate, wash away salinity.The raffinate isolating iridium is used for extracting platinum, palladium and rhodium etc.Find after deliberation, the waste residue platiniferous in iridium treating process, available ammonium chloride method reclaims platinum.This also increases the yield of platinum.
Embodiment
Further specific descriptions will be done by specific embodiment to the present invention below, but can not be interpreted as it is limiting the scope of the present invention.
Embodiment 1
The separation method of one kind of multiple precious metals of the present invention, comprises the steps:
(1) pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, loads that to be heated to temperature in crucible be 700 DEG C, and 2h, after material melts completely, takes out and cools in crucible;
(2) pre-treatment before distillation: by the water-soluble pulp of frit of cooling, pass into sulfurous gas, to neutral; For subsequent use with the washing freshen of 70 DEG C; By this step pre-treatment, when avoiding next step to distill, pipeline is blocked by salinity, decreases the content of sodium ion in ruthenium and osmium absorption liquid.So, both ensure that production safety, in turn ensure that the quality product of ruthenium and osmium.
Fractionation by distillation osmium and ruthenium: above-mentioned slag is proceeded in reactor in batches and distills;
Do medium with sulfuric acid, sodium chlorate makees oxygenant, absorbs ruthenium with the ethanolic soln that the hydrochloric acid soln of 1:1 and mass concentration are 0.5%; With mass concentration be 30% hydrazine hydrate solution and mass concentration be 0.5% ethanolic soln absorb osmium;
Ruthenium absorption liquid send ruthenium post to continue to be processed into the finished product; Osmium absorption liquid send osmium post to continue to be processed into the finished product;
(3) pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 70 DEG C, send iridium post; When this step can prevent heavy iridium, iridium is difficult to be separated by salinity parcel, causes the yield of iridium on the low side.
(4) carry iridium: above-mentioned recrement, adopt mass ratio to be solid: liquid=1:5, adds 4N hydrochloric acid heating for dissolving; Described solid is recrement, and described liquid is 4N hydrochloric acid;
Dissolving with hydrochloric acid liquid filters, and liquid catches up with acid repeatedly, and filter residue reclaims and returns pyrogenic process;
In the hydrochloric acid soln (i.e. filtrate) of iridium, add oxygenant, make iridium change IV valency into, then add ammonium chloride, generate black ammonium iridichloride precipitation; Concentrated mother liquor also adds oxygenant until without ammonium iridichloride Precipitation;
Mass concentration be 15% ammonium chloride solution washing ammonium iridichloride, leave standstill, sedimentation, filtration.
Iridium salt is separated with mother liquor; Thick ammonium iridichloride send iridium purification post to continue to purify; Described oxygenant is hydrogen peroxide or nitric acid.Filter flask or filter vat is adopted to filter.
(5) heavy iridium mother liquor is used for reclaiming platinum, palladium, rhodium successively; Traditional separation method first dissolves raw material with chloroazotic acid, first separating platinum and palladium, but for the low raw material of platinum palladium content, cost is high again, and yield is low again.Be separated platinum, palladium, rhodium in this step better, along with osmium, ruthenium and iridium are separated, platinum, palladium, rhodium obtains enrichment, and yield can improve much naturally.
(6) Solvent Extraction Separation of Platinum: adopt tributyl phosphate Extraction of Platinum from heavy iridium mother liquor;
Keep solution be 3mol/l hydrochloric acid, with account for liquor capacity 0.5% sulfuric acid;
Use calcium phosphate+ forage platinum, then go out platinum with the back extraction of 0.5mol/l sodium hydroxide solution, send platreating to purify;
(7) xanthate precipitator method separate palladium: solution control ph is 0.5, add 1 Bei Yellow medicine of theoretical amount under room temperature, the reaction times is 30min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine;
(8) copper powder substitution method separate rhodium: solution being heated to temperature is 95 DEG C, adds copper powder, constantly stirs, until react completely, obtains thick rhodium powder and send rhodium refining purification.
Present invention process is simple, and energy-conserving and environment-protective, do not produce pollutent, effectively can be separated various heavy.
Tool of the present invention has the following advantages: material first by pyrogenic process, all melts by (1), for reducing the loss of volatile material, reducing temperature, shorten smelting time when pyrogenic process.
(2) going out osmium and ruthenium by fractionation by distillation, considering from production safety angle, add pre-treatment link: pre-treatment before distillation, is removing unnecessary alkali, avoiding producing a large amount of reaction heat and salinity instantaneously during distillation, cause system jams.
(3) through above-mentioned separation sequence and separation method, can be thorough by various precious metal separation, and accomplish high-recovery, fully realize the value of the recycling of waste and old precious metal.
(4) consider from environmental protection and economic angle, the sodium chlorate that novel process have employed less contamination makees distillation oxygenant.For ensureing that the quality of osmium adopts hydrazine hydrate to make absorption agent.Employing hydrazine hydrate absorbs, and be absorbed with several advantage compared to sodium hydroxide: first, it can not bring sodium ion into, and osmium powder can not exceed standard by sodium; Secondly, yield is high, reaches 99%.When sodium hydroxide absorbs, the osmium having about 10% remains in the solution, needs repeatedly to reclaim.The yield of additive method is lower.
(5) vinasse is used for being separated iridium, is production safety and improves the yield of iridium, also will carry out pre-treatment, in and raffinate, wash away salinity.The raffinate isolating iridium is used for extracting platinum, palladium and rhodium etc.Find after deliberation, the waste residue platiniferous in iridium treating process, available ammonium chloride method reclaims platinum.This also increases the yield of platinum.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1: the separation method of one kind of multiple precious metals of the present invention, comprises the steps:
In step (1), pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, loads that to be heated to temperature in crucible be 750 DEG C, and 2.5h, after material melts completely, takes out and cools in crucible;
In step (2), for subsequent use with the washing freshen of 75 DEG C;
In step (3), pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 75 DEG C, send iridium post;
In step (6), solution is kept to be 4mol/l hydrochloric acid; Use calcium phosphate+ forage platinum, then go out platinum with the back extraction of 1mol/l sodium hydroxide solution, send platreating to purify;
In step (7), xanthate precipitator method separate palladium: solution control ph is 1, add 2 Bei Yellow medicines of theoretical amount under room temperature, the reaction times is 40min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1: the separation method of one kind of multiple precious metals of the present invention, comprises the steps:
In step (1), being heated to temperature in loading crucible is 800 DEG C, and 3h, after material melts completely, takes out and cools in crucible;
In step (2), for subsequent use with the washing freshen of 80 DEG C;
In step (3), pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 80 DEG C, send iridium post;
In step (6), keep solution be 5mol/l hydrochloric acid, with account for liquor capacity 0.5% sulfuric acid;
Use calcium phosphate+ forage platinum, then go out platinum with the back extraction of 1.5mol/l sodium hydroxide solution, send platreating to purify;
In step (7), xanthate precipitator method separate palladium: solution control ph is 1.5, add 3 Bei Yellow medicines of theoretical amount under room temperature, the reaction times is 60min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine.
Embodiment 4
The separation method of the multiple precious metal of another kind of the present invention, comprises the steps:
(1) pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, loads that to be heated to temperature in crucible be 700 DEG C, and 2h, after material melts completely, takes out and cools in crucible;
(2) pre-treatment before distillation: by the water-soluble pulp of frit of cooling, pass into sulfurous gas, to neutral; For subsequent use with the washing freshen of 70 DEG C;
Fractionation by distillation osmium and ruthenium:
Above-mentioned slag is proceeded in reactor in batches and distills;
Do medium with sulfuric acid, sodium chlorate makees oxygenant, absorbs ruthenium with the ethanolic soln that the hydrochloric acid soln of 1:1 and mass concentration are 0.5%; With mass concentration be 30% hydrazine hydrate solution and mass concentration be 0.5% ethanolic soln absorb osmium;
Ruthenium absorption liquid send ruthenium post to continue to be processed into the finished product; Osmium absorption liquid send osmium post to continue to be processed into the finished product;
(3) pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 70 DEG C, send iridium post;
(4) iridium is carried:
Above-mentioned recrement, adopts mass ratio to be solid: liquid=1:5, adds 4N hydrochloric acid heating for dissolving; Described solid is recrement, and described liquid is 4N hydrochloric acid;
Dissolving with hydrochloric acid liquid filters, and liquid catches up with acid repeatedly, and filter residue reclaims and returns pyrogenic process;
In the hydrochloric acid soln (i.e. filtrate) of iridium, add oxygenant, make iridium change IV valency into, then add ammonium chloride, generate black ammonium iridichloride precipitation; Concentrated mother liquor also adds oxygenant until without ammonium iridichloride Precipitation;
Mass concentration be 15% ammonium chloride solution washing ammonium iridichloride, leave standstill, sedimentation, filtration.
Iridium salt is separated with mother liquor; Thick ammonium iridichloride send iridium purification post to continue to purify; Described oxygenant is hydrogen peroxide or nitric acid; Filter flask or filter vat is adopted to filter; Described oxygenant is hydrogen peroxide or nitric acid.Filter flask or filter vat is adopted to filter.
(5) heavy iridium mother liquor is used for reclaiming platinum, palladium, rhodium successively;
(6) carry the waste residue that iridium produces, with aqua regia dissolution, chloride precipitation method extracts platinum, obtains ammonium chloroplatinate and send platreating;
(7) xanthate precipitator method separate palladium: solution control ph is 0.5, add 1 Bei Yellow medicine of theoretical amount under room temperature, the reaction times is 30min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine;
(8) copper powder substitution method separate rhodium: solution being heated to temperature is 95 DEG C, adds copper powder, constantly stirs, until react completely, obtains thick rhodium powder and send rhodium refining purification.
Embodiment 5
Embodiment 5 is with the difference of embodiment 4: in step (1), and being heated to temperature in loading crucible is 750 DEG C, and 2.5h, after material melts completely, takes out and cools in crucible;
In step (2), for subsequent use with the washing freshen of 75 DEG C;
In step (3), vinasse is neutralized, for subsequent use with the washing freshen of 75 DEG C, send iridium post;
In step (7), xanthate precipitator method separate palladium: solution control ph is 1, add 2 Bei Yellow medicines of theoretical amount under room temperature, the reaction times is 50min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine.
Embodiment 6
Embodiment 6 is with the difference of embodiment 4: in step (1), pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, being heated to temperature in loading crucible is 800 DEG C, and 3h, after material melts completely, takes out and cools in crucible;
In step (2), for subsequent use with the washing freshen of 80 DEG C;
In step (3), vinasse is neutralized, for subsequent use with the washing freshen of 80 DEG C, send iridium post;
In step (7), solution control ph is 1.5, and add 3 Bei Yellow medicines of theoretical amount under room temperature, the reaction times is 60min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The method personnel of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, specification sheets and equivalent thereof.
Claims (4)
1. the separation method of one kind of multiple precious metals, is characterized in that comprising the steps:
(1) pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, load in crucible be heated to temperature be 700-800 DEG C, 2-3h after material melts completely, take out in crucible and cool;
(2) pre-treatment before distillation: by the water-soluble pulp of frit of cooling, pass into sulfurous gas, to neutral; For subsequent use with the washing freshen of 70-80 DEG C;
Fractionation by distillation osmium and ruthenium: above-mentioned slag is proceeded in reactor in batches and distills;
Do medium with sulfuric acid, sodium chlorate makees oxygenant, absorbs ruthenium with the ethanolic soln that the hydrochloric acid soln of 1:1 and mass concentration are 0.5%; With mass concentration be 30% hydrazine hydrate solution and mass concentration be 0.5% ethanolic soln absorb osmium;
Ruthenium absorption liquid send ruthenium post to continue to be processed into the finished product; Osmium absorption liquid send osmium post to continue to be processed into the finished product;
(3) pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 70-80 DEG C, send iridium post;
(4) carry iridium: above-mentioned recrement, employing mass ratio is solid: liquid=1:5, adds 4N hydrochloric acid heating for dissolving;
Described solid is recrement, and described liquid is 4N hydrochloric acid;
Filtered by dissolving with hydrochloric acid liquid, dissolving with hydrochloric acid liquid catches up with acid repeatedly, and filter residue reclaims and returns pyrogenic process;
To the hydrochloric acid soln of iridium, namely add oxygenant in filtrate, make iridium change IV valency into, then add ammonium chloride, generate black ammonium iridichloride precipitation;
Concentrated mother liquor also adds oxygenant until without ammonium iridichloride Precipitation;
With the ammonium chloride solution repetitive scrubbing ammonium iridichloride that mass concentration is 15%, filter after standing sedimentation; Iridium salt is separated with mother liquor; Thick ammonium iridichloride send iridium purification post to continue to purify;
(5) heavy iridium mother liquor is used for reclaiming platinum, palladium, rhodium successively;
(6) Solvent Extraction Separation of Platinum: adopt tributyl phosphate Extraction of Platinum from heavy iridium mother liquor;
Keep solution be 3-5mol/l hydrochloric acid, with account for liquor capacity 0.5% sulfuric acid;
Use calcium phosphate+ forage platinum, then go out platinum with the back extraction of 0.5-1.5mol/l sodium hydroxide solution, send platreating to purify;
(7) xanthate precipitator method separate palladium: solution control ph is 0.5-1.5, add the 1-3 Bei Yellow medicine of theoretical amount under room temperature, the reaction times is 30-60min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine;
(8) copper powder substitution method separate rhodium: solution being heated to temperature is 95 DEG C, adds copper powder, constantly stirs, until react completely, obtains thick rhodium powder and send rhodium refining purification.
2. the separation method of one kind of multiple precious metals, is characterized in that comprising the steps:
(1) pyrogenic process: be that the ratio of 1:3 mixes with mass ratio by material and sodium peroxide, load in crucible be heated to temperature be 700-800 DEG C, 2-3h after material melts completely, take out in crucible and cool;
(2) pre-treatment before distillation: by the water-soluble pulp of frit of cooling, pass into sulfurous gas, to neutral; For subsequent use with the washing freshen of 70-80 DEG C;
Fractionation by distillation osmium and ruthenium: above-mentioned slag is proceeded in reactor in batches and distills;
Do medium with sulfuric acid, sodium chlorate makees oxygenant, absorbs ruthenium with the ethanolic soln that the hydrochloric acid soln of 1:1 and mass concentration are 0.5%; With mass concentration be 30% hydrazine hydrate solution and mass concentration be 0.5% ethanolic soln absorb osmium;
Ruthenium absorption liquid send ruthenium post to continue to be processed into the finished product; Osmium absorption liquid send osmium post to continue to be processed into the finished product;
(3) pre-treatment before carrying iridium: vinasse is neutralized, for subsequent use with the washing freshen of 70-80 DEG C, send iridium post;
(4) carry iridium: above-mentioned recrement, employing mass ratio is solid: liquid=1:5, adds 4N hydrochloric acid heating for dissolving;
Described solid is recrement, and described liquid is 4N hydrochloric acid; Filtered by dissolving with hydrochloric acid liquid, dissolving with hydrochloric acid liquid catches up with acid repeatedly, and filter residue reclaims and returns pyrogenic process; To the hydrochloric acid soln of iridium, namely add oxygenant in filtrate, make iridium change IV valency into, then add ammonium chloride, generate black ammonium iridichloride precipitation; Concentrated mother liquor also adds oxygenant until without ammonium iridichloride Precipitation;
With the ammonium chloride solution repetitive scrubbing ammonium iridichloride that mass concentration is 15%, filter after standing sedimentation; Iridium salt is separated with mother liquor; Thick ammonium iridichloride send iridium purification post to continue to purify;
(5) heavy iridium mother liquor is used for reclaiming platinum, palladium, rhodium successively;
(6) carry the waste residue that iridium produces, with aqua regia dissolution, chloride precipitation method extracts platinum, obtains ammonium chloroplatinate and send platreating;
(7) xanthate precipitator method separate palladium: solution control ph is 0.5-1.5, add the 1-3 Bei Yellow medicine of theoretical amount under room temperature, the reaction times is 30-60min, obtains ethyl oxydithiocarbonic acid palladium; Palladium is sent to refine;
(8) copper powder substitution method separate rhodium: solution being heated to temperature is 95 DEG C, adds copper powder, constantly stirs, until react completely, obtains thick rhodium powder and send rhodium refining purification.
3. the separation method of multiple precious metal according to claim 1 and 2, is characterized in that: in step (4), and described oxygenant is hydrogen peroxide or nitric acid.
4. the separation method of multiple precious metal according to claim 1 and 2, is characterized in that: in step (4), adopts filter flask or filter vat to filter.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105300961A (en) * | 2015-10-16 | 2016-02-03 | 贵研检测科技（云南）有限公司 | Separation and enrichment determination method for Ir, Rh, Pt, Pd and Au in secondary resource material |
| CN106698530A (en) * | 2017-02-28 | 2017-05-24 | 南京东锐铂业有限公司 | Production process of potassium osmate |
| CN107502739A (en) * | 2017-08-03 | 2017-12-22 | 泸西县扩铂贵金属有限公司 | A kind of method extracted osmium, iridium, ruthenium and be directly processed into corresponding compound |
| CN108660323A (en) * | 2018-06-20 | 2018-10-16 | 南京东锐铂业有限公司 | The new method of osmium powder purification |
| CN113049572A (en) * | 2021-04-02 | 2021-06-29 | 山东省计量科学研究院 | Method for accurately measuring gold content in gold ornament containing osmium iridium ruthenium alloy |
| CN114737063A (en) * | 2022-03-22 | 2022-07-12 | 咸阳欧冶科技有限公司 | Platinum alloy purification process |
| CN115536082A (en) * | 2022-11-04 | 2022-12-30 | 郴州高鑫材料有限公司 | Method for preparing rhodium trichloride and ammonium chloroiridate from rhodium-iridium/silica gel adsorbent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428445A (en) * | 2001-12-22 | 2003-07-09 | 中南大学 | Method for extracting osmium, iridium and ruthenium |
| JP2005097695A (en) * | 2003-09-26 | 2005-04-14 | Sumitomo Metal Mining Co Ltd | Mutual separation method for platinum group element |
| CA2636927A1 (en) * | 2006-01-13 | 2007-07-19 | Asaka Riken Co., Ltd. | Method for separation and recovery of noble metals |
| CN101985696A (en) * | 2010-12-01 | 2011-03-16 | 金川集团有限公司 | Method for extracting iridium from iridium containing materials |
| CN101985699A (en) * | 2010-12-01 | 2011-03-16 | 金川集团有限公司 | Method for extracting osmium from osmium-containing material |
| US7935173B1 (en) * | 2010-07-23 | 2011-05-03 | Metals Recovery Technology Inc. | Process for recovery of precious metals |
| CN103014322A (en) * | 2013-01-07 | 2013-04-03 | 郴州高鑫铂业有限公司 | Method for efficiently separating and purifying rhodium and ruthenium |
| CN103320620A (en) * | 2013-07-01 | 2013-09-25 | 金川集团股份有限公司 | Method for efficiently enriching gold and platinum group metals from complex low-grade rhodium iridium residues |
-
2014
- 2014-09-11 CN CN201410461779.7A patent/CN104232920B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428445A (en) * | 2001-12-22 | 2003-07-09 | 中南大学 | Method for extracting osmium, iridium and ruthenium |
| JP2005097695A (en) * | 2003-09-26 | 2005-04-14 | Sumitomo Metal Mining Co Ltd | Mutual separation method for platinum group element |
| CA2636927A1 (en) * | 2006-01-13 | 2007-07-19 | Asaka Riken Co., Ltd. | Method for separation and recovery of noble metals |
| US7935173B1 (en) * | 2010-07-23 | 2011-05-03 | Metals Recovery Technology Inc. | Process for recovery of precious metals |
| CN101985696A (en) * | 2010-12-01 | 2011-03-16 | 金川集团有限公司 | Method for extracting iridium from iridium containing materials |
| CN101985699A (en) * | 2010-12-01 | 2011-03-16 | 金川集团有限公司 | Method for extracting osmium from osmium-containing material |
| CN103014322A (en) * | 2013-01-07 | 2013-04-03 | 郴州高鑫铂业有限公司 | Method for efficiently separating and purifying rhodium and ruthenium |
| CN103320620A (en) * | 2013-07-01 | 2013-09-25 | 金川集团股份有限公司 | Method for efficiently enriching gold and platinum group metals from complex low-grade rhodium iridium residues |
Non-Patent Citations (1)
| Title |
|---|
| 刘时杰: "铂族金属提取冶金技术发展及展望", 《有色冶炼》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105300961A (en) * | 2015-10-16 | 2016-02-03 | 贵研检测科技（云南）有限公司 | Separation and enrichment determination method for Ir, Rh, Pt, Pd and Au in secondary resource material |
| CN106698530A (en) * | 2017-02-28 | 2017-05-24 | 南京东锐铂业有限公司 | Production process of potassium osmate |
| CN107502739A (en) * | 2017-08-03 | 2017-12-22 | 泸西县扩铂贵金属有限公司 | A kind of method extracted osmium, iridium, ruthenium and be directly processed into corresponding compound |
| CN107502739B (en) * | 2017-08-03 | 2019-04-05 | 泸西县扩铂贵金属有限公司 | A method of it extracting osmium, iridium, ruthenium and is directly processed into corresponding compound |
| CN108660323A (en) * | 2018-06-20 | 2018-10-16 | 南京东锐铂业有限公司 | The new method of osmium powder purification |
| CN113049572A (en) * | 2021-04-02 | 2021-06-29 | 山东省计量科学研究院 | Method for accurately measuring gold content in gold ornament containing osmium iridium ruthenium alloy |
| CN113049572B (en) * | 2021-04-02 | 2023-02-28 | 山东省计量科学研究院 | Method for accurately measuring gold content in gold jewelry containing osmium-iridium-ruthenium alloy |
| CN114737063A (en) * | 2022-03-22 | 2022-07-12 | 咸阳欧冶科技有限公司 | Platinum alloy purification process |
| CN115536082A (en) * | 2022-11-04 | 2022-12-30 | 郴州高鑫材料有限公司 | Method for preparing rhodium trichloride and ammonium chloroiridate from rhodium-iridium/silica gel adsorbent |
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