CN1043250C - Method for recovering platinum and aluminum from waste aluminum-based catalyst and digestion furnace - Google Patents
Method for recovering platinum and aluminum from waste aluminum-based catalyst and digestion furnace Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 64
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000029087 digestion Effects 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 239000011449 brick Substances 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002419 base digestion Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- 235000011127 sodium aluminium sulphate Nutrition 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000003350 kerosene Substances 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 26
- 239000002893 slag Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000003311 flocculating effect Effects 0.000 claims description 3
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 239000012527 feed solution Substances 0.000 claims description 2
- 238000010285 flame spraying Methods 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims 4
- 239000002585 base Substances 0.000 claims 1
- 125000006850 spacer group Chemical group 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 3
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 230000006378 damage Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 229910000510 noble metal Inorganic materials 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- 239000002912 waste gas Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
Abstract
A method and a digester for recovering platinum and aluminum from a waste aluminum-based catalyst. The method comprises the steps of alkali digestion, water leaching dealuminization, chlorination and platinum dissolution of an aqueous solution, flocculation of silica gel by animal glue, destruction of animal glue by dilute sulfuric acid, replacement of zinc (or iron) to obtain crude platinum, refining of the crude platinum to obtain pure platinum, and preparation of sodium alum or other aluminum salts by water leaching dealuminization. The digestion furnace is composed of a furnace bottom, a refractory brick furnace building wall, a lining heat preservation layer, a furnace top, a heat source and a temperature thermocouple, is in a cuboid shape, adopts a movable top structure, and uses a kerosene blowtorch as the heat source.
Description
A method and a digester for recovering platinum and aluminum from a waste aluminum-based catalyst. The present invention belongs to noble metal metallurgy.
Noble metal catalysts are widely used in the petrochemical industry and consist of a substrate and a noble metal active part. After long-term use, the active component in the catalyst is expensiveMetals are contaminated with various impurities and lose their activity, and become spent catalysts. Noble metals are widely used, but the resources are limited, so the noble metals are expensive, and the waste materials containing the noble metals naturally become very important secondary resources. The method for recovering noble metal from the spent catalyst includes a noble metal selective dissolution method, a soluble carrier dissolution method, a dry volatilization method, a plasma smelting method, a copper smelting trapping method and the like. Patent ZL91104386.1 "method for recovering platinum from waste catalyst" (application date: 91.06.24) adopts a method of selective dissolution of noble metal to treat T-12 waste platinum catalyst, and provides a simple method with high platinum recovery rate and high purity, but the application is limited to a catalyst with insoluble matrix, and the matrix is not recovered and utilized. The 1-5 aluminum-based platinum catalyst is Al2O3The pellet catalyst as matrix consists of Al as main component%2O396Pt 0.36-0.37SiO21.67Fe 0.37Mn 0.11Pb trace Ni, 1.5-2mm pellet diameter, all calcined at 1150 deg.C, and Al matrix2O3The crystal form of (A) has been changed from r-type to a-type, wherein the powder accounts for about 30-40%, and most of platinum is distributed in Al in a micro-fine particle state2O3The middle or edge area of the matrix is coated by the matrix, belongs to a material difficult to process, and is processed by a method of selective dissolution of noble metal, so that the recovery rate of platinum is not high.
The object of the present invention is to provide a catalyst derived from Al2O3Recovery of platinum for any crystalline form of the spent aluminum-based catalystHigh efficiency, high purity, simple and easy operation, and can comprehensively recover aluminum, and special equipment for effectively implementing the method.
The method provided by the invention comprises the steps of alkali digestion, water leaching and dealuminization, aqueous solution chlorination and platinum dissolution, animal glue flocculation silica gel, dilute sulfate nitrate animal glue, zinc replacement (or iron replacement) to obtain crude platinum, refining the crude platinum to obtain pure platinum, and water leaching and dealuminization of aluminum liquid to prepare sodium alum Na2AL2(SO4)4·24H2O]The method comprises the following specific steps: (1) mixing the waste catalyst with sodium hydroxide in the weight ratio of waste catalyst to sodium hydroxide of 1: 1-3, preferably 1: 1-1.2, performing alkali digestion reaction in a digestion furnace designed and manufactured at the temperature of 500-850 ℃, preferably 600-800 ℃, so that the alumina with any crystal form in the matrix reacts with the sodium hydroxide to produce water-soluble aluminum salt: ， (ii) a (2) Leaching the alkaline digestion slag by water, wherein the ratio of the weight gram of the alkaline digestion slag to the volume milliliter of water is 1: 5-12, preferably 1: 5-10, the temperature is the boiling temperature of water, the time is 5-30 minutes, the aluminum removal rate is more than or equal to 98 percent, and the platinum content of a water leaching aluminum removal liquid is less than 0.0005 gram/liter; (3) dissolving water-immersed slag in 3-6mol/LHCl medium at 80-85 deg.C for 1 time at a ratio of weight gram of slag to volume milliliter of HCl solution of about 1: 4, wherein platinum is activated by alkali digestion, most of the platinum can be dissolved in HCl for 1-2 hours, after extracting supernatant, adding sodium chlorate oxidant into the residual slag under the conditions of HCl medium with the same concentration, dosage ratio and temperature, wherein the addition amount of the sodium chlorate oxidant is 10% of the weight of the residual slag, and the time is 1-2 hours, and dissolving the sodium chlorate oxidant once again; (4) mixing the two platinum solutions, adding 5-10% gelatin solution (volume ratio) = 1: 10000-25: 1000) into platinum solution at room temperature, stirring slowly to flocculate silica gel, filtering to remove silica gel and platinum-dissolving residue, and adding into solution2-3% concentrated sulfuric acid at 90-100 deg.C, and breaking animal glue for 20-30 min; (5) gradually adding zinc powder (or iron powder) into the solution obtained in the step (4) at normal temperature for replacement to obtain crude platinum precipitate, filtering, dissolving the crude platinum once again by a aqua regia dissolving method or a sodium chlorate oxidation aqueous solution chlorination method, hydrolyzing by sodium bromate, hydrolyzing by a carrier, precipitating platinum by ammonium chloride, and calcining to obtain pure sponge platinum powder refined by a traditional refining method; (6) adding sulfuric acid into the water leaching dealumination solution for reaction, evaporating the obtained solution to obtain sodium alum [ Na]2AL2(SO4)4·24H2O]And (4) crystallizing.
In order to realize high implementation efficiency of the method, the alkali digestion furnace is designed and manufactured, and is now described with reference to the attached drawings, wherein fig. 1 is a schematic view of a digestion furnace (I), a1 is a front view, b1 is a side view, C1 is a top view, 1, a furnace top steel frame, 2, a furnace top heat-insulating brick, 3, a hanging ring, 4, a furnace wall, 5, an inner lining heat-insulating layer, 6, a heat source fire spraying hole, 7 and a thermocouple. FIG. 2 is a schematic view of the charging of a digester (I), A is a schematic view of the charging of a bottom tray, B2-5 layers of trays are schematic views of the charging of the digester, C is a schematic view of arrangement of refractory brick pads of a hearth, 8 is a refractory brick pad, 9 is a flame path of the hearth, FIG. 3 is a schematic view of the charging and the charging of a digester (II),
a2 is a front view, b2 is a side view, C2 is a top view,
(1) (2), (3), (4), (5), (6), (7) show the same as in FIG. 1,
(10) is a fire-resisting brick.
The designed and manufactured digestion furnace consists of furnace bottoms (8,9), a furnace wall (4), an inner lining heat-insulating layer (5), furnace tops (1,2,3), a heat source (6) and a thermocouple (7), and is in a cuboid shape, and is characterized in that the furnace bottom is provided with a cross-shaped flame channel (9), furnace bottom refractory brick cushion blocks (8) are laid above the channel, and the cushion blocks are arranged above and around the flame channel and are spaced from each other; the furnace wall (4) is built by refractory bricks, and a light insulating brick layer (5) is built in the furnace wall; the furnace top is movable and is formed by alternately stacking a steel frame (1) with a lifting ring (3) and 2 or 3 layers of light heat-insulating bricks in the steel frame; kerosene blowtorch is used as heat source, and the lower part of the furnace is simultaneously sprayed into the furnace from the four-side flame spraying holes (6), and the flame flowing direction is adjusted by the fire blocking bricks (10) and the material tray for fire isolation and the coordination with the flame channel at the bottom of the furnace. The digestion furnace with the structure has high heating speed, good heat preservation performance and energy consumption saving; the movable furnace top structure is convenient for hoisting and placing, is convenient for charging and discharging, ensures that the furnace top has uniform air permeability and enough heat preservation, is favorable for volatilization of combustion waste gas and water vapor of reaction products and flame diffusion, can ensure that the upper area of the furnace reaches the temperature required by reaction, and can also be provided with a material drying steel disc above the furnace top to bake wet materials by utilizing waste heat; the material in the furnace can fill the whole furnace chamber, so the processing capacity of the equipment is high; the size of the furnace body can be adjusted according to the production scale, the adaptability is strong, the material tray can be made of materials such as burning-resistant cast iron, steel plates, stainless steel plates and the like, and can bear the corrosion of caustic alkali at the temperature of 800 ℃; the operation atmosphere is good, and a separate ventilation and dust collection system is not required to be established.
The invention has the advantages that: 1. the recovery rate of platinum is more than or equal to 97 percent, the purity is as high as 99.95 to 99.99 percent, and the platinum can be directly used for preparing a new catalyst; 2. The method is simple and easy toimplement, 3, the aluminum energy can be comprehensively recovered, 4, the digestion furnace has reasonable structure, stable and reliable operation, low energy consumption and no environmental pollution.
Examples
Two kinds of digestion furnaces are built by using refractory bricks, light insulating bricks, steel, a blast lamp and a thermocouple according to the structural design in the specification:
the effective size of the furnace of the digestion furnace (I) is 1400 multiplied by 1100 multiplied by 1000mm, each furnace can be provided with 104 small material trays with the size of 290 multiplied by 220 multiplied by 140mm, the material is charged with 800 multiplied by 880Kg, 8 kerosene blowlamps are used for blasting fire, the heating and digestion time is 6 to 7 hours per furnace, the coal oil consumption is 70Kg per furnace, the primary water leaching and dealuminization rate is 88 to 92 percent, the noble metal platinum is enriched by 8.3 to 12.5 times, and the platinum content of the water leaching dealuminization liquid is less than 0.0005 g/l (the same below). The effective size of the furnace of the digestion furnace (II) is 1100 multiplied by 900mm, each furnace is provided with 6 large charging trays with the size of 900 multiplied by 430 multiplied by 420mm, the furnace is charged with 400 plus materials/furnace, 4 blowlamps are used for blasting fire, the heating and digestion time is 3 to 3.5 hours/furnace, the coal consumption oil is 25 Kg/furnace, the cumulative dealuminization rate of the secondary digestion water is 98 to 98.5 percent, and the platinum enrichment is 50 to 66.6 times.
Example 1 pellet-shaped spent aluminum-based platinum catalyst 1000g, content of a-Al2O396.5 percent and Pt 3650g/t, (1) carrying out alkaline digestion reaction for 1.5 hours under the conditions that the temperature is 700 ℃, and the weight ratio of the waste catalyst to the sodium hydroxide is not less than 1: 1; (2) leaching alkali to eliminate slag with water in the weight ratio of slag to water volume of 1 to 5 at boiling temperature for 6 min and aluminum eliminating rate of 98%; (3) placing the water leaching slag in a 6N HCl medium, wherein the ratio of the weight gram of the slag to the volume milliliter of the HCl solution is 1: 4, and adding sodium chlorate with the weight of 10 percent of the slag as an oxidant to chloridize and dissolve platinum; (4) gradually adding zinc powder into the platinum solution at normal temperature to replace crude platinum, filtering the crude platinum powder, dissolving the crude platinum powder for 1 time by the method (3), hydrolyzing the platinum solution obtained in the step (5) and the step (4) by sodium bromate, hydrolyzing a carrier, hydrolyzing ammonium chloride to precipitate platinum, and calcining by the traditional refining method to obtain 3.563g of spongy platinum, wherein the purity is 99.95 percent, and the recovery rate is 97.6 percent; (6) water immersion aluminium removing liquidAdding industrial sulfuric acid to react, evaporating the solution to obtain sodium alum crystals Na2AL2(SO4)4·24H2O]And recovering the aluminum.
Example 2 pellet-shaped waste aluminum-based platinum catalyst 10g containing r-Al2O396.5%, Pt4000g/t (1) alkali digested for 1 hour at 800 ℃ with spent catalyst sodium hydroxide = 1: 2.82; (2) the conditions of water leaching dealumination are the same as example 1, the aluminum removal rate is 98.50%, platinum concentrate is produced, the grade is 26.6%, the weight is 0.15g, the platinum is enriched by 66.5 times, and the recovery rate is more than 99%.
EXAMPLE 3 pellet-shaped spent aluminum-based platinum catalyst 902.2g, containing 2Al2O396.5percent of Pt897g/t, (1) carrying out alkali digestion for 2 hours under the conditions of waste material and sodium hydroxide = 1: 1 and the temperature of 600 ℃, and (2) carrying out water leaching dealumination under the same conditions as example 1, wherein the aluminum removal rate is 98 percent, a platinum concentrate is produced, the grade is 5.93 percent, the weight is 13.659, the platinum enrichment is 66 times, and the recovery rate is more than 99 percent.
Example 4 pellet-shaped spent alumina-based platinum catalyst 300Kg containing a-Al2O396.5% and 0.36% of Pt0, and (1) mixing the waste catalyst with sodium hydroxide, wherein the ratio of waste to sodium hydroxide is = 1: 1.2, reacting for 6 hours in a designed and manufactured alkali digestion furnace (I) at the temperature of 800 ℃, and (2) leaching alkali digestion slag by water, wherein the ratio of the weight kilogram of the slag to the volume liter of the water is 1: 10, and the temperature is as follows: boiling water at the temperature of 30 minutes, wherein the leaching rate of aluminum is 92 percent, the leaching solution contains less than 0.0005 g/L of platinum, (3) leaching slag with water is 24Kg (containing Pt4.48 percent), platinum is dissolved once at the leakage rate of 85 ℃ (platinum is activated by alkaline digestion and HCl is soluble) under the condition that 3molHCl medium and the ratio of the weight kilogram of slag to the volume liter of hydrochloric acid is 1: 4), extracting supernatant, dissolving the slag with dilute aqua regia (concentrated nitric acid: concentrated hydrochloric acid = 1: 3, and adding water for diluting 1 time), nitrotizing the aqua regia dissolving solution, converting the aqua regia dissolving solution into hydrochloric acid medium, mixing with the 1 st HCl dissolving solution, adding 5 percent animal glue solution at normal temperature, wherein the glue solution to the feed solution (volume ratio) = 25: 1000, stirring, filtering after flocculating silica gel, washing slag, and obtaining 18Kg (containing Pt 0.116 percent) of platinum residue, and the platinum rate is 98.07 percent; returning the platinum-dissolved residue to the digestion process to recover platinum again.
The method is not more suitable for recovering platinum and aluminum by using the aluminum-based platinum-containing catalyst, but also suitable for recovering noble metal and aluminum by using the aluminum-based platinum-containing catalyst, palladium-containing catalyst and rhodium-containing catalyst.
Claims (3)
1. A process for recovering Pt and Al from waste Al-base catalyst includes alkali digestion, water immersion for dealuminization, dissolving Pt in aqueous solution by chlorination, flocculating silica gel with animal glue, breaking animal glue by diluted sulfuric acid, zinc displacement (or iron displacement) to obtain coarse Pt, refining to obtain pure Pt, water immersion for dealuminization to prepare Na alum2AL2(SO4)4·24H2O]The method comprises the following steps: 1.1 alkaline digestion conditions were: mixing the waste catalyst with alkali, wherein the alkali is sodium hydroxide, the dosage of the alkali is the waste catalyst and the sodium hydroxide (weight ratio) = 1: 1-3, the temperature is 500-;
1.2 the water immersion dealumination conditions are as follows: leaching aluminum salt from the alkaline digestion residue with water to remove aluminum, wherein the ratio of the weight gram of the alkaline digestion residue to the volume milliliter of the water is 1: 5-12, the temperature is the boiling temperature of the water, and the time is 5-30 minutes;
1.3 the conditions for dissolving platinum by water solution chlorination are as follows: dissolving the water leached aluminum-removed slag in 3-6mol/LHCl medium at 80-85 deg.C for 1 time for 1-2 hours in a ratio of weight gram of slag to volume milliliter of HCl solution of about 1: 4, extracting supernatant, adding sodium chlorate oxidant into the residue under the conditions of HCl medium with the same concentration, dosage ratio and temperature, wherein the addition is 10% of the weight of the residue, and dissolving for 1 time for 1-2 hours;
1.4 flocculating the silica gel with the conditions for destroying the gelatin by dilute sulfuric acid are as follows: at normal temperature, adding 5-10% animal glue solution into platinum solution, wherein the volume ratio of glue solution to feed solution is = 1: 10000-25: 1000, slowly stirring to flocculate silica gel, filtering, adding 2-3% concentrated sulfuric acid into the solution, and keeping the temperature at 90-100 ℃ for 20-30 minutes;
1.5 zinc displacement or iron displacement to obtain crude platinum → the refining method of the crude platinum is as follows: adding zinc powder (or iron powder) into the solution obtained in step 1.4 at normal temperature, gradually replacing to obtain crude platinum precipitate, dissolving the crude platinum after filtering by aqua regia or sodium chlorate oxidation aqueous solution chlorination method, hydrolyzing with sodium bromate, hydrolyzing the carrier, precipitating platinum with ammonium chloride, and calcining to obtain pure sponge platinum powder refined platinum by traditional refining method;
1.6 the method for preparing the sodium alum by leaching the molten aluminum by water comprises the following steps: adding sulfuric acid into the water leaching dealumination solution for reaction, evaporating the obtained solution to obtain sodium alum [ Na]2AL2(SO4)4·24H2O]And (4) crystallizing.
2. The method for recovering platinum and aluminum from a waste aluminum-based catalyst according to claim 1, wherein:
2.1 the alkaline digestion conditions are: mixing the waste catalyst and sodium hydroxide, wherein the dosage of the waste catalyst and the sodium hydroxide is (weight ratio) = 1: 1-1.2, the temperature is 600-;
2.2 the water leaching dealumination conditions are as follows: the alkaline digestion residue is subjected to dealuminization by leaching aluminum salt with water, wherein the dosage of the aluminum salt is that the ratio of the weight gram of the alkaline digestion residue to the volume milliliter of water is 1: 5-10, the temperature is the boiling temperature of the water, and the time is 5-30 minutes.
3. A digester for carrying out the method according to claim 1, consisting of a bottom (8,9), walls (4), an insulating layer (5) for the lining, a top (1,2,3), a heat source (6) and a thermocouple (7) for measuring temperature, which is-cuboid, characterized in that the bottom has a cross-shaped flame channel (9), over which are laid bottom refractory brick spacers (8) arranged with a spacing between them, above and around the flame channel; the furnace wall is built by refractory bricks, and a light insulating brick layer is built in the furnace wall; the furnace top is movable and is formed by stacking a steel frame (1) with a hanging ring (3) and 2 or 3 layers of light heat-insulating bricks (2) in the steel frame in a crossed manner; kerosene blowtorch is used as heat source (6), and the lower part of the furnace is simultaneously sprayed into the furnace from the four-side flame spraying holes, and flame flowing direction is adjusted by the fire blocking bricks (10) and the material tray fire isolation and the coordination with the flame channel at the bottom of the furnace.
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| CN95109350A CN1043250C (en) | 1995-08-23 | 1995-08-23 | Method for recovering platinum and aluminum from waste aluminum-based catalyst and digestion furnace |
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| CN95109350A CN1043250C (en) | 1995-08-23 | 1995-08-23 | Method for recovering platinum and aluminum from waste aluminum-based catalyst and digestion furnace |
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| CN1143682A CN1143682A (en) | 1997-02-26 |
| CN1043250C true CN1043250C (en) | 1999-05-05 |
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| CN95109350A Expired - Fee Related CN1043250C (en) | 1995-08-23 | 1995-08-23 | Method for recovering platinum and aluminum from waste aluminum-based catalyst and digestion furnace |
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| CN103194606B (en) * | 2013-03-28 | 2014-06-04 | 贵研资源（易门）有限公司 | Method for concentrating platinum group metals from alumina-based waste catalyst |
| CN103361499A (en) * | 2013-07-23 | 2013-10-23 | 昆明贵金属研究所 | Method for recovering rare earth elements from spent automobile catalyst |
| CN103398865B (en) * | 2013-07-24 | 2015-11-18 | 贵研资源（易门）有限公司 | The sampling of platinum group metal high-area carbon spent catalyst and method for making sample |
| CN104694768B (en) * | 2013-12-05 | 2016-09-07 | 陈怡雯 | Method from aluminium slag reducing metal aluminium |
| CN104342558A (en) * | 2014-05-12 | 2015-02-11 | 上海派特贵金属环保科技有限公司 | A method for recycling palladium from a spent precious metal catalyst |
| CN104060095A (en) * | 2014-06-17 | 2014-09-24 | 励福实业（江门）贵金属有限公司 | Method of recovering palladium from palladium-loading aluminum oxide waste catalyst |
| CN107841628A (en) * | 2017-10-31 | 2018-03-27 | 昆明理工大学 | A kind of microwave treatment platinum dead catalyst separation aluminium and the method for being enriched with platinum |
| CN108929958B (en) * | 2018-07-27 | 2020-11-10 | 江苏北矿金属循环利用科技有限公司 | Method for enriching platinum from oxidized leached sediment of silicon-aluminum-based platinum-containing dead catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2671104A1 (en) * | 1990-12-28 | 1992-07-03 | Inst Francais Du Petrole | Process for antipollution treatment of a deactivated catalyst containing at least one noble metal and total recovery of the said metal and of the support alumina |
| CN1067926A (en) * | 1991-06-24 | 1993-01-13 | 中国有色金属工业总公司昆明贵金属研究所 | Method for recovering platinum from waste catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2671104A1 (en) * | 1990-12-28 | 1992-07-03 | Inst Francais Du Petrole | Process for antipollution treatment of a deactivated catalyst containing at least one noble metal and total recovery of the said metal and of the support alumina |
| CN1067926A (en) * | 1991-06-24 | 1993-01-13 | 中国有色金属工业总公司昆明贵金属研究所 | Method for recovering platinum from waste catalyst |
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