CN102586607B - Method for extracting platinum, rhodium and palladium from failed platinum alloy gauze - Google Patents
Method for extracting platinum, rhodium and palladium from failed platinum alloy gauze Download PDFInfo
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- CN102586607B CN102586607B CN2012100585872A CN201210058587A CN102586607B CN 102586607 B CN102586607 B CN 102586607B CN 2012100585872 A CN2012100585872 A CN 2012100585872A CN 201210058587 A CN201210058587 A CN 201210058587A CN 102586607 B CN102586607 B CN 102586607B
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Abstract
The invention relates to a method for extracting platinum, rhodium and palladium from a failed platinum alloy gauze, which comprises the following steps of: separating to extract precious metals such as the platinum, the rhodium and the palladium from the failed platinum alloy gauze; dissolving through hydrochloric acid and nitric acid; removing nitro group, transforming sodium and leaching; obtaining platinum, rhodium and palladium complexing solution; adopting an ammonium chloride precipitation method to separate the platinum; adopting a sodium nitrite complexometry to separate the palladium and the rhodium; adopting a six nitroso rhodium acid ammonium method to purify the rhodium; adopting a dichlorodiamminopalladium method to purify the palladium; carrying out reduction to obtain spongy platinum, spongy palladium and rhodium powder through adding hydrazine hydrate; vacuum drying and roasting; and purifying again. The extracting method has advanced and reasonable process, and accurate and detailed parameters; the purity of the extracted spongy platinum, spongy palladium and rhodium powder is great than 99.9 percent, and the quality is stable; and the method is a very ideal method for extracting the precious metals such as the platinum, the rhodium and the palladium from the failed platinum alloy gauze.
Description
Technical field
The present invention relates to a kind of method of from inefficacy platinum alloy net, extracting platinum, rhodium, palladium, belong to the technical field of precious metal recovery, purification recycling.
Background technology
Precious metal is the rare metal in the metallic substance, for example platinum, rhodium, palladium, gold etc., high temperature resistant, anti-oxidant, corrosion-resistant, active big, characteristics such as selectivity is high, good stability that precious metal mostly has, mostly has catalytic activity, the industrial catalyzer of doing of being everlasting uses, for example the catalyzer in nitric acid industry, petrochemical complex, waste-gas cleaning, fuel cell; The noble metal catalyst of industrial application mostly carries out katalysis with the form of platinum alloy net, and the platinum alloy host will form the ternary alloy catalyzer by 92.5% platinum, 3.5% rhodium, 4% palladium; The platinum alloy mesh catalyst in use, platinum, rhodium, palladium have consumption and loss in various degree, also having impurity deposits on the net at platinum alloy, catalytic effect is reduced significantly, such catalysis platinum guaze can not use, need to change or copy new net, because the field of industrial use catalysis platinum guaze is more, inefficacy platinum guaze storage is increasing, both can cause environmental pollution, can cause the waste of precious metal again, how reclaiming, utilize the precious metal in the inefficacy platinum alloy net has been the ten minutes important research project.
Because noble metal platinum, rhodium, palladium in the inefficacy platinum alloy net are a kind of rare metals, inertia own is stronger, separates, extracts very difficult, and poison gas is bigger in the sepn process, and extraction effect is not good.
Summary of the invention
Goal of the invention
The objective of the invention is the situation at background technology, adopt a kind of new processing method, from inefficacy platinum alloy net, separate, extract platinum, rhodium, palladium, extract platinum with the ammonium chloroplatinate precipitator method, extract palladium with the Sodium Nitrite complexometry, extract rhodium with six nitroso-group rhodiums acid ammonium method, to cut the waste, decontamination makes the precious metal in the inefficacy platinum alloy net obtain reclaiming and utilizing.
Technical scheme
The chemical substance material that the present invention uses is: inefficacy platinum alloy net, hydrochloric acid, nitric acid, sodium-chlor, sodium hydroxide, ammonium chloride, Sodium Nitrite, hydrazine hydrate, ammoniacal liquor, sodium sulphite, Silver Nitrate, deionized water, hydrogen, it is as follows that consumption is prepared in its combination: with gram, milliliter, centimetre
3Be measure unit
Inefficacy platinum alloy net: Pt Rh Pd 6000g ± 10g
Hydrochloric acid: HCl 80000ml ± 100ml
Nitric acid: HNO
320000ml ± 100ml
Sodium-chlor: NaCl 10000g ± 100g
Sodium hydroxide: NaOH 1000g ± 10g
Ammonium chloride: NH
4Cl 20000g ± 100g
Sodium Nitrite: NaNO
27000g ± 100g
Hydrazine hydrate: N
2H
4H
2O 15000ml ± 100ml
Ammoniacal liquor: NH
3H
2O 11000ml ± 100ml
Sodium sulphite: Na
2S 600g ± 10g
Silver Nitrate: AgNO
310g ± 1g
Deionized water: H
2O 200000ml ± 100ml
Hydrogen: H
210000cm
3± 100cm
3
Nitrogen: N
220000cm
3± 100cm
3
Extracting method is as follows:
(1) selected chemical substance material
To carry out selectedly to extracting chemical substance material that platinum, rhodium, palladium uses, and carry out quality purity, concentration control:
Inefficacy platinum alloy net: solid-state solid platinum 92.5%, rhodium 3.5%, palladium 4.0%
Hydrochloric acid: liquid strength of fluid 12mol/L
Nitric acid: liquid strength of fluid 14.5mol/L
Sodium-chlor: solid-state solid 99%
Sodium hydroxide: solid-state solid 99%
Ammonium chloride: solid-state solid 99.5%
Sodium Nitrite: solid-state solid 99%
Hydrazine hydrate: liquid strength of fluid 13.2mol/L
Ammoniacal liquor: liquid strength of fluid 14.5mol/L
Sodium sulphite: solid-state solid 99.5%
Silver Nitrate: solid-state solid 99.5%
Deionized water: liquid liquid 99.9%
Hydrogen: gaseous state gas 99%
Nitrogen: gaseous state gas 99%
(2) heating, dissolving inefficacy platinum alloy net
Shear fails platinum alloy net becomes the net sheet of 30 * 30mm, and net sheet inefficacy platinum alloy net 6000g is added in the earthenware porcelain receptacle, measures hydrochloric acid 3000ml, nitric acid 7500ml, deionized water 8000ml, adds in the earthenware porcelain receptacle, becomes mixed solution;
Opening electric heater makes mixed solution be warming up to 95 ℃ ± 2 ℃, stirs 20min with agitator, dissolves time 360min ± 10min under heated condition;
The dissolving back becomes: platinum alloy solution;
(3) except nitro, commentaries on classics sodium salt, suction filtration
1. continue to make solution evaporation concentrate time 200min ± 10min at 95 ℃ ± 2 ℃ heating platinum alloy solution; When solution concentration during to 13000ml, slowly add hydrochloric acid 2000ml, stir while adding, make it to discharge whole brown nitrogen dioxide gas;
2. continue when continuing to be concentrated into 10000ml, to add sodium-chlor 3900g, and stir at 95 ℃ ± 2 ℃ heating platinum alloy solution; When solution was pulpous state, the adding temperature was 95 ℃ ± 2 ℃ deionized water 50000ml, stirs 10min, becomes: platinum rhodium palladium complex solution;
3. suction filtration places B on the filter flask with platinum rhodium palladium complex solution, carries out suction filtration with millipore filtration, retains aqua regia insoluble slag on the filter membrane, reclaims in addition, and filtrate is evacuated in the filter flask, and filtrate is: platinum rhodium palladium complex solution;
(4) extraction, purification platinum, platinum separates with the palladium rhodium
1. measure platinum rhodium palladium complex solution 45000ml, place earthenware porcelain receptacle, stir 10min, add ammonium chloride 2500g then, continue to stir 5min, still aging 30min becomes: the ammonium chloroplatinate mixing solutions then;
2. suction filtration places B on the filter flask with the ammonium chloroplatinate mixing solutions, uses the millipore filtration suction filtration, retains product filter cake, i.e. ammonium chloroplatinate (NH on the filter membrane
4)
2PtCl
6
Washing, suction filtration, with the 0.4mol/L aqueous ammonium chloride solution 5000ml washing leaching cake of preparation in advance, suction filtration then, filtrate is evacuated in the filter flask, and filtrate is dark red palladium rhodium complex solution, retains stand-by;
Behind washing, the suction filtration: the ammonium chloroplatinate filter cake;
3. the platinum of purifying places the ceramic reduction cylinder with the ammonium chloroplatinate filter cake, adds deionized water 6000ml, is heated to 85 ℃ ± 2 ℃, stir 5min, add hydrazine hydrate 1800ml then, continue to stir 5min, reheat to 95 ℃ ± 2 ℃, make its boiling, time 20min becomes: the platinum mixed solution;
Suction filtration places B on the filter flask with the platinum mixed solution, carries out suction filtration with millipore filtration;
Washing, suction filtration, with 500ml deionized water wash filter cake, suction filtration then, filtrate is evacuated in the filter flask, retains the product filter cake on the filter membrane;
Vacuum-drying places quartz container with the product filter cake behind the washing suction filtration, and is dry in vacuum drying oven, 115 ℃ of drying temperatures, and vacuum tightness 18Pa, time of drying, 600min became after the drying: the platina powder;
High temperature sintering places sintering oven with the platina powder of drying, at 900 ℃ ± 5 ℃ following sintering 60min ± 5min, cools to 25 ℃ behind the sintering with the furnace, after the cooling spongy platinum;
(5) palladium separates with rhodium
1. platinum is placed the ceramic reduction cylinder with dark red palladium rhodium complex solution after the palladium rhodium separates, heat temperature raising to 55 ℃ ± 2 ℃ stirs 5min, add hydrazine hydrate 1800ml then, continue to stir 5min, reheat to 95 ℃ ± 2 ℃, make its boiling 10min, become: palladium rhodium powder mixing solutions;
2. suction filtration places B on the filter flask with palladium rhodium powder mixing solutions, uses the millipore filtration suction filtration, gets the product filter cake;
Washing, suction filtration, with 500ml deionized water wash filter cake, suction filtration is retained the product filter cake on the filter membrane then, i.e. palladium rhodium powder, waste liquid is evacuated in the filter flask;
3. palladium rhodium powder is placed earthenware porcelain receptacle, add hydrochloric acid 2000ml, nitric acid 1000ml is warming up to 95 ℃ ± 2 ℃, stirs 10min, adds sodium-chlor 130g then, and restir 10min becomes: sodium type palladium rhodium solution;
4. sodium type palladium rhodium solution is added in the beaker, the 2.5mol/L aqueous sodium hydroxide solution 10ml that add deionized water 25000ml, prepares in advance places on the electric heater then, is heated to 95 ℃ ± 2 ℃, make its boiling, add the 7.2mol/L sodium nitrite in aqueous solution 1800ml of preparation in advance again, continue ebuillition of heated, and stir 60min ± 5min, making the pH value is 7, be light yellow mixing solutions, stop heating then, make it naturally cool to 25 ℃;
5. suction filtration places the B of filter flask with light yellow mixing solutions, carries out suction filtration with millipore filtration, gets the product filter cake;
Washing, suction filtration, with 500ml deionized water wash filter cake, suction filtration then, the filter cake on the filter membrane is iron, aluminium, calcium, zinc impurity, discards, filtrate is palladium rhodium complex liquid, retains;
6. palladium rhodium complex liquid is added in the beaker, be cooled to 18 ℃, add ammonium chloride 500g ± 10g then, stir 5min, still aging 60min ± 5min;
7. suction filtration places B on the filter flask with still aging palladium rhodium complex liquid, carries out suction filtration with millipore filtration, and the filter cake on the filter membrane is six nitroso-group rhodiums acid ammonium, i.e. (NH
4)
3Rh (NO
2)
6, to retain, filtrate is the palladium complex liquid, collects;
(6) purification palladium
1. the palladium complex liquid is placed beaker, place then on the electric heater, be heated to 95 ℃ ± 2 ℃, when making it be concentrated to 1/3 amount, add hydrochloric acid 1000ml, stir and remove nitro, until no brown NO
2Till gas discharges;
Continuation concentrates 95 ℃ ± 2 ℃ heating, when being pulpous state, adds deionized water 2500ml, and stirs 5min, stops heating then, makes it be cooled to 25 ℃;
Add ammoniacal liquor 1000ml, and stir, be heated to 95 ℃ ± 2 ℃ subsequently, make its boiling, add ammoniacal liquor regulator solution pH=8.5～9.0, and constant, stop heating then, make it be cooled to 25 ℃, become the palladium mixed solution;
2. suction filtration places B on the filter flask with the palladium mixed solution, carries out suction filtration with millipore filtration, and the filter cake on the filter membrane is impurity, discards, and filtrate is the palladium complex liquid, and collects;
The palladium complex liquid is placed beaker, add the 1mol/L hydrochloric acid soln 1500ml of preparation in advance then, and stir, regulate pH=1～0.5, leave standstill 20min, the inferior palladium precipitation of yellow dichloro two amminos occurs, become: the inferior palladium mixed solution of dichloro two amminos, and collect;
3. suction filtration places B on the filter flask with the inferior palladium mixed solution of dichloro two amminos, use the millipore filtration suction filtration, retains the product filter cake on the filter membrane, i.e. dichloro two amminos Asia palladium;
Washing, suction filtration, with the 1mol/L aqueous hydrochloric acid 500ml washing leaching cake of preparing in advance, making filtrate is clear liquor, suction filtration then;
4. the heavy palladium of secondary, the inferior palladium of product filter cake dichloro two amminos is placed beaker, add deionized water 2000ml, ammoniacal liquor 1000ml, place then to be heated to 95 ℃ ± 2 ℃ on the electricradiator, make its boiling, stir 5min, make its dissolving, regulate pH=9, add the 1mol/L aqueous hydrochloric acid 1000ml of preparation in advance then, stir 5min, regulate pH=1, the inferior palladium secondary sedimentation of dichloro two amminos; Stop heating then, be cooled to 25 ℃, become: the inferior palladium mixed solution of dichloro two amminos;
Suction filtration places B on the filter flask with the inferior palladium mixed solution of dichloro two amminos of secondary sedimentation, use the millipore filtration suction filtration, retention product filter cake on the filter membrane, and filtrate is evacuated in the filter flask;
5. the inferior palladium of product filter cake dichloro two amminos is placed beaker, add deionized water 2000ml, be heated to 65 ℃ ± 2 ℃, add hydrazine hydrate 55ml then, and stir, continue to be heated to 95 ℃ ± 2 ℃, make its boiling, time 10min becomes: palladium powder solution;
6. suction filtration places B on the filter flask with palladium powder solution, uses the millipore filtration suction filtration, retains the product filter cake on the filter membrane;
Washing, suction filtration, with 1500ml deionized water wash filter cake, suction filtration is retained the product filter cake on the filter membrane then, and filtrate is evacuated in the filter flask;
7. vacuum-drying places quartz crucible with the product filter cake, places vacuum drying oven dry then, 120 ℃ of drying temperatures, and vacuum tightness 15Pa, time of drying, 600min became thick palladium powder after the drying;
8. roasting places stoving oven with dried thick palladium powder, uses earlier nitrogen flooding removing and harmful gas, nitrogen input speed 40cm
3/ min feeds the hydrogen firing reduction, hydrogen input speed 40cm then
3/ min at 800 ℃ ± 5 ℃ following roasting 60min ± 5min, stops heating then, cools to 25 ℃ with the furnace, and the cooling back is the silver gray palladium sponge;
(7) purification rhodium
1. the filter cake six nitroso-group rhodiums acid ammonium with step (5)-7. obtain places beaker, adds hydrochloric acid 2000ml, places then to be heated to 95 ℃ ± 2 ℃ on the electricradiator, and stirs, and becomes solution; When solution concentration during to 1000ml, add hydrochloric acid 500ml again, continue to stir, to remove nitro, until no brown NO
2Till gas discharges;
2. continue 95 ℃ ± 2 ℃ of heating, make its boiling, when solution concentration during to 800ml ± 50ml, add sodium-chlor 80g, and stir, when heating is concentrated into pulpous state, add deionized water 6000ml, become chlordene rhodium acid sodium solution; Add the 2.5mol/L aqueous sodium hydroxide solution 50ml of preparation in advance then, stirring and adjusting pH=1.5; Add the 7.2mol/L sodium nitrite in aqueous solution 1000ml of preparation in advance again, continue ebuillition of heated 60min; Stop heating then, naturally cool to 25 ℃;
3. suction filtration places the B of filter flask with cooled solution, uses the millipore filtration suction filtration, retains filter cake on the filter membrane, reclaims in addition, and filtrate is extracted in the filter flask, and collects, i.e. the rhodium complex liquid;
4. the rhodium complex liquid is collected in the beaker, adds the 0.6mol/L sodium sulfide solution 240ml of preparation in advance, and stir, then still aging 720min; Carry out suction filtration then, to remove a small amount of palladium, filtrate is the rhodium complex liquid;
5. the rhodium complex liquid is placed beaker, place then to be heated to 95 ℃ ± 2 ℃ on the electricradiator, make its boiling, add the 7.2mol/L sodium nitrite in aqueous solution 60ml of preparation in advance then, and stir, continue to boil 60min; Stop heating then, naturally cool to 25 ℃;
6. suction filtration, with rhodium complex liquid millipore filtration suction filtration, filtrate is chlordene rhodium acid sodium solution; If filtrate is yellow, add the 0.6mol/L sodium sulfide solution 10ml of preparation in advance again, leave standstill 10min, clarify until filtrate;
7. clear liquor is cooled to 18 ℃, adds ammonium chloride 200g, and stir, leave standstill 60min again, make six nitroso-group rhodiums acid ammonia precipitation, use the millipore filtration suction filtration then, get six nitroso-group rhodiums acid ammonia filter cake;
8. six nitroso-group rhodiums acid ammonia filter cake is placed beaker, add hydrochloric acid 2000ml, be heated to 95 ℃ ± 2 ℃, make its dissolving, remove nitro, continue to add hydrochloric acid 1000ml, until no brown NO
2Till gas is emitted;
9. continue to be heated to 95 ℃ ± 2 ℃, when being concentrated into 600ml ± 50ml, add sodium-chlor 110g, and stir, when solution evaporation during to pulpous state, add deionized water 1000ml, to remove hydrochloric acid, add deionized water 2800ml subsequently again, with regulator solution concentration;
10. suction filtration with solution millipore filtration suction filtration, is retained chlordene rhodium acid sodium filtrate;
Be heated to 95 ℃ ± 2 ℃ then, and stir, drip hydrazine hydrate 600ml then, make solution become white, the rhodium powder sinks, and continues to boil 20min, stops heating then, makes it naturally cool to 25 ℃;
Washing, suction filtration, with 1000ml deionized water wash filter cake, suction filtration then, washing, suction filtration repeat 5 times; Get product filter cake, i.e. rhodium powder filter cake behind washing, the suction filtration;
(8) detect, chemically examine, analyze, characterize
Spongy platinum, palladium sponge, the pattern of rhodium powder, color and luster, composition, purity, the physical and chemical performance that extracts detected, analyzes, characterizes;
Carry out constituent content analysis with Atomic Absorption Spectroscopy AAS;
Carry out morphology analysis with scanning electronic microscope;
Conclusion: spongy platinum is that grey black look solid, purity are 99.99%; Palladium sponge is the silver gray solid, and purity is 99.95%; The rhodium powder is the canescence powder, and purity is 99.9%;
(9) store
Spongy platinum, palladium sponge, rhodium powder to preparation are stored in respectively in the brown transparent Glass Containers, and airtight lucifuge is stored in cool place, dry clean environment, 20 ℃ ± 2 ℃ of moistureproof, sun-proof, acid-proof alkali salt erosion, storing temps, relative humidity≤10%.
Beneficial effect
The present invention compares with background technology has tangible advance, it is separation and Extraction noble metal platinum from inefficacy platinum alloy net, rhodium, palladium, by hydrochloric acid+nitric acid dissolve, except nitro, change the sodium type, suction filtration, get platinum rhodium palladium ternary complex solution, adopt chloride precipitation method Separation of Pt, with Sodium Nitrite complexing seperation palladium, rhodium is with six nitroso-group rhodiums acid ammonium method purification rhodium, the inferior palladium method of dichloro two amminos purification palladium, add hydrazine hydrate reduction and get spongy platinum, palladium sponge and rhodium powder are through vacuum-drying, roasting is purified, and this extracting method technology is rationally advanced, parameter is accurately full and accurate, the spongy platinum that extracts, the purity of palladium sponge and rhodium powder＞99.9%, steady quality is very good to extract platinum from inefficacy platinum alloy net, rhodium, the method of palladium.
Description of drawings
Fig. 1 is the heating of inefficacy platinum alloy net, dissolved state figure
Fig. 2 is the spongy platinum shape appearance figure
Fig. 3 is the palladium sponge shape appearance figure
Fig. 4 is rhodium powder shape appearance figure
Shown in the figure, list of numerals is as follows:
1, electrically heated oscillating agitator, 2, display screen, 3, pilot lamp, 4, power switch, 5, the electrically heated modulator, 6, vibration stirs modulator, 7, earthenware porcelain receptacle, 8, inefficacy platinum alloy net, 9, hydrochloric acid+salpeter solution, 10, container cover, 11, the air outlet.
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
Fig. 1 is the heating of inefficacy platinum alloy net, dissolved state figure, and it is correct that want each position, according to quantity proportioning, operation according to the order of sequence.
Extracting the value of platinum, rhodium, palladium use chemical substance, is to determine by the scope of predetermined set, with gram, milliliter, millimeter
3Be measure unit, when industrialization is extracted, with kilogram, liter, rice
3Be measure unit.
The heating of inefficacy platinum alloy net, dissolving are carried out in earthenware porcelain receptacle, inefficacy platinum alloy net 8 is placed in the earthenware porcelain receptacle 7, add hydrochloric acid+salpeter solution 9 then, hydrochloric acid+salpeter solution 9 will flood inefficacy platinum alloy net 8, earthenware porcelain receptacle 7 tops are container cover 10, and container cover 10 is provided with air outlet 11; Earthenware porcelain receptacle 7 places on the electrically heated concussion agitator 1, electrically heated concussion agitator 1 is provided with display screen 2, pilot lamp 3, power switch 4, electrically heated modulator 5, concussion stirring modulator 6, the Heating temperature of hydrochloric acid+salpeter solution 9 is by 5 regulation and control of electrically heated modulator, and the concussion in the earthenware porcelain receptacle 7 is stirred by concussion and stirred modulator 6 regulation and control.
Shown in Figure 2, be the spongy platinum shape appearance figure, among the figure as can be known: spongy platinum is the grey black look, and is glossy, is irregular loose heaped-up.
Shown in Figure 3, be the palladium sponge shape appearance figure, among the figure as can be known: palladium sponge is silver gray, and is glossy, is irregular loose heaped-up.
Shown in Figure 4, be rhodium powder shape appearance figure, among the figure as can be known: the rhodium powder is the grey powder, is the dense accumulation shape.
Claims (2)
1. method of from inefficacy platinum alloy net, extracting platinum, rhodium, palladium, it is characterized in that: the chemical substance material of use is: inefficacy platinum alloy net, hydrochloric acid, nitric acid, sodium-chlor, sodium hydroxide, ammonium chloride, Sodium Nitrite, hydrazine hydrate, ammoniacal liquor, sodium sulphite, deionized water, hydrogen, it is as follows that consumption is prepared in its combination: with gram, milliliter, centimetre
3Be measure unit
Extracting method is as follows:
(1) selected chemical substance material
To carry out selectedly to extracting chemical substance material that platinum, rhodium, palladium uses, and carry out quality purity, concentration control:
Inefficacy platinum alloy net: solid-state solid platinum 92.5%, rhodium 3.5%, palladium 4.0%
Hydrochloric acid: liquid strength of fluid 12mol/L
Nitric acid: liquid strength of fluid 14.5mol/L
Sodium-chlor: solid-state solid 99%
Sodium hydroxide: solid-state solid 99%
Ammonium chloride: solid-state solid 99.5%
Sodium Nitrite: solid-state solid 99%
Hydrazine hydrate: liquid strength of fluid 13.2mol/L
Ammoniacal liquor: liquid strength of fluid 14.5mol/L
Sodium sulphite: solid-state solid 99.5%
Deionized water: liquid liquid 99.9%
Hydrogen: gaseous state gas 99%
Nitrogen: gaseous state gas 99%
(2) heating, dissolving inefficacy platinum alloy net
Shear fails platinum alloy net becomes the net sheet of 30 * 30mm, and net sheet inefficacy platinum alloy net 6000g is added in the earthenware porcelain receptacle, measures hydrochloric acid 3000ml, nitric acid 7500ml, deionized water 8000ml, adds in the earthenware porcelain receptacle, becomes mixed solution;
Opening electric heater makes mixed solution be warming up to 95 ℃ ± 2 ℃, stirs 20min with agitator, dissolves time 360min ± 10min under heated condition;
The dissolving back becomes: platinum alloy solution;
(3) except nitro, commentaries on classics sodium salt, suction filtration
1. continue to make solution evaporation concentrate time 200min ± 10min at 95 ℃ ± 2 ℃ heating platinum alloy solution; When solution concentration during to 13000ml, slowly add hydrochloric acid 2000ml, stir while adding, make it to discharge whole brown nitrogen dioxide gas;
2. continue when continuing to be concentrated into 10000ml, to add sodium-chlor 3900g, and stir at 95 ℃ ± 2 ℃ heating platinum alloy solution; When solution was pulpous state, the adding temperature was 95 ℃ ± 2 ℃ deionized water 50000ml, stirs 10min, becomes: platinum rhodium palladium complex solution;
3. suction filtration places B on the filter flask with platinum rhodium palladium complex solution, carries out suction filtration with millipore filtration, retains aqua regia insoluble slag on the filter membrane, reclaims in addition, and filtrate is evacuated in the filter flask, and filtrate is: platinum rhodium palladium complex solution;
(4) extraction, purification platinum, platinum separates with the palladium rhodium
1. measure platinum rhodium palladium complex solution 45000ml, place earthenware porcelain receptacle, stir 10min, add ammonium chloride 2500g then, continue to stir 5min, still aging 30min becomes: the ammonium chloroplatinate mixing solutions then;
2. suction filtration places B on the filter flask with the ammonium chloroplatinate mixing solutions, uses the millipore filtration suction filtration, retains product filter cake, i.e. ammonium chloroplatinate (NH on the filter membrane
4)
2PtCl
6
Washing, suction filtration, with the 0.4mol/L aqueous ammonium chloride solution 5000ml washing leaching cake of preparation in advance, suction filtration then, filtrate is evacuated in the filter flask, and filtrate is dark red palladium rhodium complex solution, retains stand-by;
Behind washing, the suction filtration: the ammonium chloroplatinate filter cake;
3. the platinum of purifying places the ceramic reduction cylinder with the ammonium chloroplatinate filter cake, adds deionized water 6000ml, is heated to 85 ℃ ± 2 ℃, stir 5min, add hydrazine hydrate 1800ml then, continue to stir 5min, reheat to 95 ℃ ± 2 ℃, make its boiling, time 20min becomes: the platinum mixed solution;
Suction filtration places B on the filter flask with the platinum mixed solution, carries out suction filtration with millipore filtration;
Washing, suction filtration, with 500ml deionized water wash filter cake, suction filtration then, filtrate is evacuated in the filter flask, retains the product filter cake on the filter membrane;
Vacuum-drying places quartz container with the product filter cake behind the washing suction filtration, and is dry in vacuum drying oven, 115 ℃ of drying temperatures, and vacuum tightness 18Pa, time of drying, 600min became after the drying: the platina powder;
High temperature sintering places sintering oven with the platina powder of drying, at 900 ℃ ± 5 ℃ following sintering 60min ± 5min, cools to 25 ℃ behind the sintering with the furnace, after the cooling spongy platinum;
(5) palladium separates with rhodium
1. platinum is placed the ceramic reduction cylinder with dark red palladium rhodium complex solution after the palladium rhodium separates, heat temperature raising to 55 ℃ ± 2 ℃ stirs 5min, add hydrazine hydrate 1800ml then, continue to stir 5min, reheat to 95 ℃ ± 2 ℃, make its boiling 10min, become: palladium rhodium powder mixing solutions;
2. suction filtration places B on the filter flask with palladium rhodium powder mixing solutions, uses the millipore filtration suction filtration, gets the product filter cake;
Washing, suction filtration, with 500ml deionized water wash filter cake, suction filtration is retained the product filter cake on the filter membrane then, i.e. palladium rhodium powder, waste liquid is evacuated in the filter flask;
3. palladium rhodium powder is placed earthenware porcelain receptacle, add hydrochloric acid 2000ml, nitric acid 1000ml is warming up to 95 ℃ ± 2 ℃, stirs 10min, adds sodium-chlor 130g then, and restir 10min becomes: sodium type palladium rhodium solution;
4. sodium type palladium rhodium solution is added in the beaker, the 2.5mol/L aqueous sodium hydroxide solution 10ml that add deionized water 25000ml, prepares in advance places on the electric heater then, is heated to 95 ℃ ± 2 ℃, make its boiling, add the 7.2mol/L sodium nitrite in aqueous solution 1800ml of preparation in advance again, continue ebuillition of heated, and stir 60min ± 5min, making the pH value is 7, be light yellow mixing solutions, stop heating then, make it naturally cool to 25 ℃;
5. suction filtration places the B of filter flask with light yellow mixing solutions, carries out suction filtration with millipore filtration, gets the product filter cake;
Washing, suction filtration, with 500ml deionized water wash filter cake, suction filtration then, the filter cake on the filter membrane is iron, aluminium, calcium, zinc impurity, discards, filtrate is palladium rhodium complex liquid, retains;
6. palladium rhodium complex liquid is added in the beaker, be cooled to 18 ℃, add ammonium chloride 500g ± 10g then, stir 5min, still aging 60min ± 5min;
7. suction filtration places B on the filter flask with still aging palladium rhodium complex liquid, carries out suction filtration with millipore filtration, and the filter cake on the filter membrane is six nitroso-group rhodiums acid ammonium, i.e. (NH
4)
3Rh (NO
2)
6, to retain, filtrate is the palladium complex liquid, collects;
(6) purification palladium
1. the palladium complex liquid is placed beaker, place then on the electric heater, be heated to 95 ℃ ± 2 ℃, when making it be concentrated to 1/3 amount, add hydrochloric acid 1000ml, stir and remove nitro, until no brown NO
2Till gas discharges;
Continuation concentrates 95 ℃ ± 2 ℃ heating, when being pulpous state, adds deionized water 2500ml, and stirs 5min, stops heating then, makes it be cooled to 25 ℃;
Add ammoniacal liquor 1000ml, and stir, be heated to 95 ℃ ± 2 ℃ subsequently, make its boiling, add ammoniacal liquor regulator solution pH=8.5～9.0, and constant, stop heating then, make it be cooled to 25 ℃, become the palladium mixed solution;
2. suction filtration places B on the filter flask with the palladium mixed solution, carries out suction filtration with millipore filtration, and the filter cake on the filter membrane is impurity, discards, and filtrate is the palladium complex liquid, and collects;
The palladium complex liquid is placed beaker, add the 1mol/L hydrochloric acid soln 1500ml of preparation in advance then, and stir, regulate pH=1～0.5, leave standstill 20min, the inferior palladium precipitation of yellow dichloro two amminos occurs, become: the inferior palladium mixed solution of dichloro two amminos, and collect;
3. suction filtration places B on the filter flask with the inferior palladium mixed solution of dichloro two amminos, use the millipore filtration suction filtration, retains the product filter cake on the filter membrane, i.e. dichloro two amminos Asia palladium;
Washing, suction filtration, with the 1mol/L aqueous hydrochloric acid 500ml washing leaching cake of preparing in advance, making filtrate is clear liquor, suction filtration then;
4. the heavy palladium of secondary, the inferior palladium of product filter cake dichloro two amminos is placed beaker, add deionized water 2000ml, ammoniacal liquor 1000ml, place then to be heated to 95 ℃ ± 2 ℃ on the electricradiator, make its boiling, stir 5min, make its dissolving, regulate pH=9, add the 1mol/L aqueous hydrochloric acid 1000ml of preparation in advance then, stir 5min, regulate pH=1, the inferior palladium secondary sedimentation of dichloro two amminos; Stop heating then, be cooled to 25 ℃, become: the inferior palladium mixed solution of dichloro two amminos;
Suction filtration places B on the filter flask with the inferior palladium mixed solution of dichloro two amminos of secondary sedimentation, use the millipore filtration suction filtration, retention product filter cake on the filter membrane, and filtrate is evacuated in the filter flask;
5. the inferior palladium of product filter cake dichloro two amminos is placed beaker, add deionized water 2000ml, be heated to 65 ℃ ± 2 ℃, add hydrazine hydrate 55ml then, and stir, continue to be heated to 95 ℃ ± 2 ℃, make its boiling, time 10min becomes: palladium powder solution;
6. suction filtration places B on the filter flask with palladium powder solution, uses the millipore filtration suction filtration, retains the product filter cake on the filter membrane;
Washing, suction filtration, with 1500ml deionized water wash filter cake, suction filtration is retained the product filter cake on the filter membrane then, and filtrate is evacuated in the filter flask;
7. vacuum-drying places quartz crucible with the product filter cake, places vacuum drying oven dry then, 120 ℃ of drying temperatures, and vacuum tightness 15Pa, time of drying, 600min became thick palladium powder after the drying;
8. roasting places stoving oven with dried thick palladium powder, uses earlier nitrogen flooding removing and harmful gas, nitrogen input speed 40cm
3/ min feeds the hydrogen firing reduction, hydrogen input speed 40cm then
3/ min at 800 ℃ ± 5 ℃ following roasting 60min ± 5min, stops heating then, cools to 25 ℃ with the furnace, and the cooling back is the silver gray palladium sponge;
(7) purification rhodium
1. the filter cake six nitroso-group rhodiums acid ammonium with step (5)-7. obtain places beaker, adds hydrochloric acid 2000ml, places then to be heated to 95 ℃ ± 2 ℃ on the electricradiator, and stirs, and becomes solution; When solution concentration during to 1000ml, add hydrochloric acid 500ml again, continue to stir, to remove nitro, until no brown NO
2Till gas discharges;
2. continue 95 ℃ ± 2 ℃ of heating, make its boiling, when solution concentration during to 800ml ± 50ml, add sodium-chlor 80g, and stir, when heating is concentrated into pulpous state, add deionized water 6000ml, become chlordene rhodium acid sodium solution; Add the 2.5mol/L aqueous sodium hydroxide solution 50ml of preparation in advance then, stirring and adjusting pH=1.5; Add the 7.2mol/L sodium nitrite in aqueous solution 1000ml of preparation in advance again, continue ebuillition of heated 60min; Stop heating then, naturally cool to 25 ℃;
3. suction filtration places the B of filter flask with cooled solution, uses the millipore filtration suction filtration, retains filter cake on the filter membrane, reclaims in addition, and filtrate is extracted in the filter flask, and collects, i.e. the rhodium complex liquid;
4. the rhodium complex liquid is collected in the beaker, adds the 0.6mol/L sodium sulfide solution 240ml of preparation in advance, and stir, then still aging 720min; Carry out suction filtration then, to remove a small amount of palladium, filtrate is the rhodium complex liquid;
5. the rhodium complex liquid is placed beaker, place then to be heated to 95 ℃ ± 2 ℃ on the electricradiator, make its boiling, add the 7.2mol/L sodium nitrite in aqueous solution 60ml of preparation in advance then, and stir, continue to boil 60min; Stop heating then, naturally cool to 25 ℃;
6. suction filtration, with rhodium complex liquid millipore filtration suction filtration, filtrate is chlordene rhodium acid sodium solution; If filtrate is yellow, add the 0.6mol/L sodium sulfide solution 10ml of preparation in advance again, leave standstill 10min, clarify until filtrate;
7. clear liquor is cooled to 18 ℃, adds ammonium chloride 200g, and stir, leave standstill 60min again, make six nitroso-group rhodiums acid ammonia precipitation, use the millipore filtration suction filtration then, get six nitroso-group rhodiums acid ammonia filter cake;
8. six nitroso-group rhodiums acid ammonia filter cake is placed beaker, add hydrochloric acid 2000ml, be heated to 95 ℃ ± 2 ℃, make its dissolving, remove nitro, continue to add hydrochloric acid 1000ml, until no brown NO
2Till gas is emitted;
9. continue to be heated to 95 ℃ ± 2 ℃, when being concentrated into 600ml ± 50ml, add sodium-chlor 110g, and stir, when solution evaporation during to pulpous state, add deionized water 1000ml, to remove hydrochloric acid, add deionized water 2800ml subsequently again, with regulator solution concentration;
10. suction filtration with solution millipore filtration suction filtration, is retained chlordene rhodium acid sodium filtrate;
Chlordene rhodium acid sodium filtrate is placed the reduction cylinder, add the 2.5mol/L aqueous sodium hydroxide solution 2ml of preparation in advance, make pH value of solution=2;
Be heated to 95 ℃ ± 2 ℃ then, and stir, drip hydrazine hydrate 600ml then, make solution become white, the rhodium powder sinks, and continues to boil 20min, stops heating then, makes it naturally cool to 25 ℃;
Washing, suction filtration, with 1000ml deionized water wash filter cake, suction filtration then, washing, suction filtration repeat 5 times; Get product filter cake, i.e. rhodium powder filter cake behind washing, the suction filtration;
(8) detect, chemically examine, analyze, characterize
Spongy platinum, palladium sponge, the pattern of rhodium powder, color and luster, composition, purity, the physical and chemical performance that extracts detected, analyzes, characterizes;
Carry out constituent content analysis with Atomic Absorption Spectroscopy AAS;
Carry out morphology analysis with scanning electronic microscope;
Conclusion: spongy platinum is that grey black look solid, purity are 99.99%; Palladium sponge is the silver gray solid, and purity is 99.95%; The rhodium powder is the canescence powder, and purity is 99.9%;
(9) store
Spongy platinum, palladium sponge, rhodium powder to preparation are stored in respectively in the brown transparent Glass Containers, and airtight lucifuge is stored in cool place, dry clean environment, 20 ℃ ± 2 ℃ of moistureproof, sun-proof, acid-proof alkali salt erosion, storing temps, relative humidity≤10%.
2. a kind of method of from inefficacy platinum alloy net, extracting platinum, rhodium, palladium according to claim 1, it is characterized in that: the heating of inefficacy platinum alloy net, dissolving are carried out in earthenware porcelain receptacle, inefficacy platinum alloy net (8) is placed in the earthenware porcelain receptacle (7), add hydrochloric acid+salpeter solution (9) then, hydrochloric acid+salpeter solution (9) will flood inefficacy platinum alloy net (8), earthenware porcelain receptacle (7) top is container cover (10), and container cover (10) is provided with air outlet (11); Earthenware porcelain receptacle (7) places on the electrically heated concussion agitator (1), electrically heated concussion agitator (1) is provided with display screen (2), pilot lamp (3), power switch (4), electrically heated modulator (5), modulator (6) is stirred in concussion, and the Heating temperature of hydrochloric acid+salpeter solution (9) is by electrically heated modulator (5) regulation and control, and the concussion in the earthenware porcelain receptacle (7) is stirred by concussion and stirred modulator (6) regulation and control.
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Effective date of registration: 20200108 Address after: No. a416, floor 4, business incubation building a, customs clearance service center, Wusu Comprehensive Bonded Zone, Taiyuan comprehensive reform demonstration zone, Taiyuan City, Shanxi Province Patentee after: Taiyuan Rui Lin Precious Metals Recycling Co., Ltd. Address before: 4, No. 1, unit 29, fertilizer District, Jinyuan District, Shanxi, Taiyuan 030021 Patentee before: Zhang Guixiang |