WO2005035804A9 - Recovery of precious metals from waste catalysts - Google Patents
Recovery of precious metals from waste catalystsInfo
- Publication number
- WO2005035804A9 WO2005035804A9 PCT/KR2004/000013 KR2004000013W WO2005035804A9 WO 2005035804 A9 WO2005035804 A9 WO 2005035804A9 KR 2004000013 W KR2004000013 W KR 2004000013W WO 2005035804 A9 WO2005035804 A9 WO 2005035804A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metals
- waste
- catalysts
- precious metals
- catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 239000010970 precious metal Substances 0.000 title claims abstract description 16
- 238000011084 recovery Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- -1 platinum series metals Chemical class 0.000 claims abstract description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010298 pulverizing process Methods 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 239000000969 carrier Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 38
- 229910052697 platinum Inorganic materials 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 238000005272 metallurgy Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
Definitions
- the present invention relates to a recovery method of platinum group metals (PGM) from waste catalyst, and in particular to an effective recovery method of platinum group metals from waste catalysts used for purifying a waste gas of an automobile.
- PGM platinum group metals
- Platinum group metals such as Pt, Pd, etc. have a very high dissolution temperature and a good corrosion resistance property with respect to chemical corrosion.
- the PGM has particular chemical characteristics such as a reduction catalyst operation etc.
- the annual production over the world of platinum group metals is about 200 tons wherein over 90% of the same are produced in the South Africa and the old Russian countries. Canada produces about 6%, and the South America countries, the US, Australia, and Japan respectively produce a small amount of the same.
- the platinum group metals are generally used for a catalyst for purifying a waste gas of an automobile and a catalyst for petroleum industry
- the platinum group metals have a high ionization electric potential, so that the dissolution of metal itself is difficult.
- an extraction and separation of the platinum group metal are difficult due to a catalyst carrier and other catalyst component and pollution.
- a wet metallurgy process, a dry metallurgy process and a wet and dry metallurgy process are used as a method for extracting metals in order to platinum group precious metals from a waste catalysts used for purifying a waste gas of an automobile.
- HCL hydrochloric acid or nitrohydrochloric acid
- the above method is simple and has been used for a long time.
- a lot of leaching agent may be disadvantageously used, and multiple processes are performed for leaching and thereby the entire processes is complicated.
- the surface of AI 2 O 3 /SiO 2 has a porous structure as shown in Figure 2.
- the entrances of the porous structure may be blocked due to aging, so that the yield of the dissolution process of platinum is decreased.
- the waste catalysts are pulverized so that the catalysts contained in the interior of the porous structure can be dissolved. Thereafter, organic material is removed, and a heat treatment is performed in order to reduce the oxidized catalyst, and then reduction is performed.
- rhodium reacts with alumina for thereby producing solid solution, so that yield is low.
- waste catalysts are dried with moisture of 1-5% and are pulverized with an average grain of 200 ⁇ m or less and are calcinated at a temperature of 50 ⁇ 850°C.
- the waste catalysts are reduced under an environment of H 2 /N 2 mixed gas at a mixture ratio of 1 :99 ⁇ 80:20.
- the amount of moisture is low, so that there is limit for fine-powdered catalysts.
- Disclosure of Invention Accordingly, it is an object of the present invention to provide an effective recovery method of platinum group metals, improving the problems of the wet method.
- reduction agents having moisture are added to waste catalysts and are pulverized with a grain size of 20 ⁇ m or less and platinum group metals are extracted by the wet method and filtered.
- the method according to the present invention is characterized in that a pulverizing process of waste catalysts is performed with adding reduction agents. Namely, the pulverizing process and reducing process are concurrently performed as compared to the conventional method.
- the waste catalysts are heated and first dried, and then are pulverized.
- the waste catalysts are pulverized using a certain reduction agent having moisture, for example, hydrazine hydrate, for thereby obtaining very fine grains, so that it is possible to increase dissolution level and yield.
- a certain reduction agent having moisture for example, hydrazine hydrate
- common reduction agent used in a common reduction process may be used.
- NaBH 4 also may be used.
- the extraction process of platinum group metals is achieved in such a manner that the pulverized and pre-processed waste catalyst powders are processed based on the common wet method using nitrohydrochloric acid.
- a method for recovering platinum from waste catalysts there are two methods. Namely, there are a method for melting platinum, and a method for melting carrier. In the method for melting carrier, sulfuric acid is generally used.
- Aqueous solution of aluminum sulfate, etc. is prepared, and platinum contained in residue is refined. Since a small amount of platinum is melted in the process in w hich t he c arrier i s d issolved, the p rocess i s c omplicated, and t he y ield i s decreased. Therefore, in the present invention, the method in which platinum is first melted is used.
- diluted nitrohydrochloric acid (hydrochloric acid 3 + nitric acid 1 + water 5) is used for a mild process. Solution is filtered, and carrier is filtered and washed. Ammonium chloride is added, and platinum is precipitated.
- Solubility of ammonium chloroplatinate with respect to water at 25°C is 7.7g/l. In addition, solubility is decreased based on an addition of ammonium chloride, and solubility in ammonium chloride of 15-20% is 0.023g/l.
- the solubility is determined based on the amount of ammonia in aqueous solution.
- FIG. 1 is a view illustrating the process of the present invention.
- the measurements of the amount of platinum group metals of the waste catalysts containing platinum group and the extraction ratio of the platinum group metals are performed based on a conventional method such as XRF, AAS, ICPS (Inductively Coupled Plasma emission Spectrometry).
- XRF XRF
- AAS atomic layer deposition
- ICPS Inductively Coupled Plasma emission Spectrometry
- the present invention is basically characterized in that a pulverizing method of waste catalysts for an effective extraction, a proper pulverizing average grain and proper pre-process method, and a method for an effective filtering of the precious metallic solution and the residue are properly implemented.
- Figure 1 is a flow chart of a process of the present invention
- Figure 2 is a view illustrating the shape of a surface of an alumina carrier before/after use.
- Acid nitrohydrochloric acid , temperature: 9O 0 C : Standard waste catalyst of 2,120ppm Pt used : Within error range of analyzer
- Waste catalyst carrying Pt/Rd/Rh which is used for purifying a waste gas of an automobile, is pulverized like the example 1.
- Diluted nitrohydrochloric acid (hydrochloric acid 3 + nitric acid 1 + water 5) is pumped to tank and heated to 40 ⁇ 50°C, and extraction is performed for 5 hours.
- the solution is filtered, and a carrier is separated and is washed.
- the filtered solution is concentrated.
- Ammonium chloride is added by a concentration of 17.7%, and the platinum is precipitated and filtered.
- Aluminum scraps are provided and filtered. An extraction ratio is measured, and a result of the measurement is shown in Table 3.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
This invention is related to the recovery method of precious metals from waste catalysts. More particularly, this invention is related to the recovery s method of platinum series metals from automobile waste catalysts or alumina waste catalysts containing the precious metals. The recovery method of precious metal from waste catalyst of the invention is comprised of following steps: adding the reduction agent containing moisture to waste catalyst and pulverizing the catalyst to have the grain size below 20 to microns; extracting the precious metals by wet process; and filtering the precious metals. After said pulverizing, the catalyst is solved by nitrohydrochloric acid, filtered and washed to remove carrier, and the acid solution is concentrated. After concentration step, ammonium chloride is added to the solution to precipitate is precious metal, and the precipitated metal is filtered. Aluminium scrap is added to the residue to precipitate precious metal, and the precipitated metal is filtered and recovered.
Description
RECOVERY OF PRECIOUS METALS FROM WASTE
CATALYSTS
Technical Field The present invention relates to a recovery method of platinum group metals (PGM) from waste catalyst, and in particular to an effective recovery method of platinum group metals from waste catalysts used for purifying a waste gas of an automobile.
Background Art
Platinum group metals (PGM) such as Pt, Pd, etc. have a very high dissolution temperature and a good corrosion resistance property with respect to chemical corrosion. In addition, the PGM has particular chemical characteristics such as a reduction catalyst operation etc. The annual production over the world of platinum group metals is about 200 tons wherein over 90% of the same are produced in the South Africa and the old Russian countries. Canada produces about 6%, and the South America countries, the US, Australia, and Japan respectively produce a small amount of the same. The platinum group metals are generally used for a catalyst for purifying a waste gas of an automobile and a catalyst for petroleum industry
As the time is passed, the performance of the catalysts is decreased, and finally, they are wasted. In particular, platinum group metals are expensive and totally imported from other countries. Therefore, recycling the platinum group metals is economically advantageous, and the resource may be effectively used.
When recovering precious metals carried in the carrier of the catalyst, it is performed based on several methods. There are technical advantages and
disadvantages in each method. In particular, the platinum group metals have a high ionization electric potential, so that the dissolution of metal itself is difficult. In addition, an extraction and separation of the platinum group metal are difficult due to a catalyst carrier and other catalyst component and pollution. A wet metallurgy process, a dry metallurgy process and a wet and dry metallurgy process are used as a method for extracting metals in order to platinum group precious metals from a waste catalysts used for purifying a waste gas of an automobile.
In the wet metallurgy process, platinum group elements such as platinum in waste catalysts are dissolved using hydrochloric acid or nitrohydrochloric acid (HCL: HNO3 = 3:1 ) and recovered in a form of chloride after waste catalysts are pulverized.
The above method is simple and has been used for a long time. In the case that the above leaching agent is used, a lot of leaching agent may be disadvantageously used, and multiple processes are performed for leaching and thereby the entire processes is complicated.
In order to maximize the surface area, the surface of AI2O3/SiO2 has a porous structure as shown in Figure 2. However, in the case of waste catalysts, the entrances of the porous structure may be blocked due to aging, so that the yield of the dissolution process of platinum is decreased.
Therefore, in a p re-process of the wet metallurgy process, the waste catalysts are pulverized so that the catalysts contained in the interior of the porous structure can be dissolved. Thereafter, organic material is removed, and a heat treatment is performed in order to reduce the oxidized catalyst, and then reduction is performed. However, in the case that reduction is performed after calcinations, rhodium reacts with alumina for thereby producing solid solution, so that yield is low.
In addition, in the case that reduction and calcinations are performed at
the same time, a very expensive apparatus and operation cost are needed. In order to overcome the above disadvantages, in the Japanese patent No. 1559593, catalysts are pulverized and reduced, omitting a calcinations process. Platinum group metals are dissolved using inorganic acid for thereby first recovering of platinum group metals. Next, a corresponding catalyst is calcinated at over 11000C to transform the carrier to α-alumina. The platinum group metals remaining in a corresponding carrier are dissolved using inorganic acid for thereby second recovering of platinum group metals. In the above method, the calcinations are performed at an intermediate stage of processes, so that the process is complicated, and energy consumption is increased.
In the Korean patent No. 367708, in the wet process, waste catalysts are dried with moisture of 1-5% and are pulverized with an average grain of 200μm or less and are calcinated at a temperature of 50~850°C. The waste catalysts are reduced under an environment of H2/N2 mixed gas at a mixture ratio of 1 :99~80:20. However, in the above method, the amount of moisture is low, so that there is limit for fine-powdered catalysts. There is a problem for increasing the yield because the dissolution of platinum is low.
Disclosure of Invention Accordingly, it is an object of the present invention to provide an effective recovery method of platinum group metals, improving the problems of the wet method.
It is another object of the present invention to provide a recovery method of platinum group metals from a waste catalyst used for purifying a waste gas of an automobile or various waste catalysts carrying precious metals. In the above method, reduction agents having moisture are added to waste catalysts and are pulverized with a grain size of 20μm or less and platinum group metals are extracted by the wet method and filtered.
The method according to the present invention is characterized in that a pulverizing process of waste catalysts is performed with adding reduction agents. Namely, the pulverizing process and reducing process are concurrently performed as compared to the conventional method. In the conventional method, the waste catalysts are heated and first dried, and then are pulverized. In the present invention, the waste catalysts are pulverized using a certain reduction agent having moisture, for example, hydrazine hydrate, for thereby obtaining very fine grains, so that it is possible to increase dissolution level and yield. In the present invention, common reduction agent used in a common reduction process may be used. For example, NaBH4 also may be used.
In the method according to the present invention, it is possible to simplify the pre-process.
In the present invention, the extraction process of platinum group metals is achieved in such a manner that the pulverized and pre-processed waste catalyst powders are processed based on the common wet method using nitrohydrochloric acid. As a method for recovering platinum from waste catalysts, there are two methods. Namely, there are a method for melting platinum, and a method for melting carrier. In the method for melting carrier, sulfuric acid is generally used.
Aqueous solution of aluminum sulfate, etc. is prepared, and platinum contained in residue is refined. Since a small amount of platinum is melted in the process in w hich t he c arrier i s d issolved, the p rocess i s c omplicated, and t he y ield i s decreased. Therefore, in the present invention, the method in which platinum is first melted is used. In the above methods, there are a method of using nitrohydrochloric acid (hydrochloric acid + nitric acid + water), a method of using hydrochloric acid + chlorine gas, and a method of using hydrochloric acid + hydrogen peroxide. In the present invention, diluted nitrohydrochloric acid
(hydrochloric acid 3 + nitric acid 1 + water 5) is used for a mild process. Solution is filtered, and carrier is filtered and washed. Ammonium chloride is added, and platinum is precipitated.
Precipitation reaction of platinum is as follows.
H2PtCI6 -> 2NH4CI -> (NH4) 2PtCI2 + 2HCI
Solubility of ammonium chloroplatinate with respect to water at 25°C is 7.7g/l. In addition, solubility is decreased based on an addition of ammonium chloride, and solubility in ammonium chloride of 15-20% is 0.023g/l.
The solubility is determined based on the amount of ammonia in aqueous solution.
Therefore, a large amount of ammonia chloride is needed. In the present invention, heat generated in the following precipitation process by aluminum is used for concentrating of acid solution using heat exchanger, so that it is possible to perform precipitation by providing a small amount of ammonia chloride to the concentrated liquid without additional energy. Platinum recovered through the precipitation is above 95%. Platinum is recovered by adding aluminum scrap to filtered liquid. The precipitation by aluminum is a most common method of extracting platinum from leaching solution. In the above method, about 100% yield of precious metals is obtained without any loss. The above method is implemented based on the following formula.
2Al + 6HCI -> 2AICI3 + 3H2.
In the above reaction, additional aluminum is needed for a heat
generating reaction. At this time, it is preferable that aluminum is provided in a ball form because ball has large surface area with respect to the volume. The diameter of a luminum b all i s p referably 3 mm. The heat g enerated d uring t he heat generating reaction is used through the heat exchanger for a concentration of acid solution having dissolved platinum. Figure 1 is a view illustrating the process of the present invention.
The measurements of the amount of platinum group metals of the waste catalysts containing platinum group and the extraction ratio of the platinum group metals are performed based on a conventional method such as XRF, AAS, ICPS (Inductively Coupled Plasma emission Spectrometry). The above method may be preferably selected by a person skilled in the art.
The present invention is basically characterized in that a pulverizing method of waste catalysts for an effective extraction, a proper pulverizing average grain and proper pre-process method, and a method for an effective filtering of the precious metallic solution and the residue are properly implemented.
Brief Description of Drawings
The present invention will become better understood with reference to the accompanying drawings and examples, which are given only by way of illustration and thus the present invention is not to be construed as being limited thereto.
Figure 1 is a flow chart of a process of the present invention; and Figure 2 is a view illustrating the shape of a surface of an alumina carrier before/after use.
Best Mode for Carrying Out the Invention
[Comparison example 1]
Waste catalyst carrying Pt/Rd/Rh, which is used for purifying a waste gas of an automobile, is dried in such a manner that amount of moisture is 5% or less, and the waste catalysts are pulverized using a ball mill through a dry milling method. A result of the acid dissolution is shown in Table 1.
[Table 1] Experiment of pulverizing in ball mill and dissolution
[Example 1]
Hydrazine hydrate of 5weight% of the amount of waste catalyst is added, and waste catalysts are pulverized using ball mill based on a wet milling method. Table 2 shows a result of the acid dissolution.
[Table 2] Experiment of pulverizing in ball mill and dissolution
Acid: nitrohydrochloric acid , temperature: 9O0C : Standard waste catalyst of 2,120ppm Pt used : Within error range of analyzer
[Example 2] Waste catalyst carrying Pt/Rd/Rh, which is used for purifying a waste gas of an automobile, is pulverized like the example 1. Diluted nitrohydrochloric acid (hydrochloric acid 3 + nitric acid 1 + water 5) is pumped to tank and heated
to 40~50°C, and extraction is performed for 5 hours. The solution is filtered, and a carrier is separated and is washed. The filtered solution is concentrated. Ammonium chloride is added by a concentration of 17.7%, and the platinum is precipitated and filtered. Aluminum scraps are provided and filtered. An extraction ratio is measured, and a result of the measurement is shown in Table 3.
[Table 3]
Industrial Applicability
As described above, it is possible to effectively recover platinum group metals by a recovery method according to the present invention, and the process is simplified.
Claims
1. A recovery m ethod of p latinum g roup m etals o r p recious metals from waste catalysts comprised of following steps : adding a reduction agent containing moisture to the waste catalysts; pulverizing the waste catalysts to have the grain size below 20microns; extracting metals by wet process; and filtering to recover platinum group metals or precious metals.
2. The method of claim 1 , wherein the method is comprised of following steps: dissolving the catalysts by nitrohydrochloric after pulverizing; filtering and washing to remove the carriers; concentrating the acid solution; adding ammonium chloride solution to precipitate precious metals; filtering the precipitated metals; adding aluminium scrap to the residue to precipitate precious metals; and filtering and recovering the precipitated metals.
3. The method of either claim 1 or claim 2, wherein said reduction agent is hydrazine.
4. The method of claim 2, wherein said concentration of the acid solution is performed using heat of exothermic reaction by addition of aluminum scraps.
5. The method of claim 2, wherein said ammonium chloride is added for thereby having the concentration of 15-20%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0071266 | 2003-10-14 | ||
| KR20030071266A KR100563384B1 (en) | 2003-10-14 | 2003-10-14 | Recovery of precious metals from waste catalysts |
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| Publication Number | Publication Date |
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| WO2005035804A1 WO2005035804A1 (en) | 2005-04-21 |
| WO2005035804A9 true WO2005035804A9 (en) | 2006-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2004/000013 WO2005035804A1 (en) | 2003-10-14 | 2004-01-07 | Recovery of precious metals from waste catalysts |
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| Country | Link |
|---|---|
| KR (1) | KR100563384B1 (en) |
| CN (1) | CN100419101C (en) |
| WO (1) | WO2005035804A1 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100758877B1 (en) | 2006-04-26 | 2007-09-14 | 한국지질자원연구원 | Refining method of high purity platinum from platinum scrap |
| KR100858551B1 (en) * | 2006-11-13 | 2008-09-25 | 진인수 | A method of extraction of platinum group metals from the spent catalysts by electrochemical processes |
| KR100884368B1 (en) | 2007-05-14 | 2009-02-18 | 진인수 | The preparing method of yellow rhodium sulfate III solution |
| HU0900034D0 (en) | 2009-01-23 | 2009-03-30 | Dobos Gabor Dr | Process for recovering precious metals from waste catalyst |
| CN101519725B (en) * | 2009-04-09 | 2010-10-13 | 昆明贵金属研究所 | Method for extracting precious metal from auto-exhaust catalyst by hydrometallurgy and pyrometallurgy complex process |
| KR101134178B1 (en) * | 2009-11-18 | 2012-04-09 | 한국지질자원연구원 | Concentrating Process for Recovering Valuable Metals from Spent Automotive Catalysts |
| US7935173B1 (en) | 2010-07-23 | 2011-05-03 | Metals Recovery Technology Inc. | Process for recovery of precious metals |
| CN103184345A (en) * | 2013-03-26 | 2013-07-03 | 昆明贵金属研究所 | Method for removing iron and enriching platinum group metals from smelted iron trapping material |
| CN103276215B (en) * | 2013-06-03 | 2014-08-20 | 贵研资源（易门）有限公司 | Method for recovering noble metal from waste catalyst |
| CN103526033A (en) * | 2013-10-21 | 2014-01-22 | 昆明贵研催化剂有限责任公司 | Method for dissolving platinum group metals in automobile spent catalyst enrichment |
| CN103667706B (en) * | 2013-11-29 | 2016-04-20 | 重庆材料研究院有限公司 | The separating and purifying method of gold in a kind of plation waste material |
| CN104263945A (en) * | 2014-10-08 | 2015-01-07 | 昆明贵金属研究所 | Method for recovering platinum metal from waste catalyst |
| CN104480312B (en) * | 2014-11-23 | 2016-07-20 | 北京科技大学 | A kind of method that auto-exhaust catalyst noble metal reclaims |
| CN104988314A (en) * | 2015-05-11 | 2015-10-21 | 昆明贵金属研究所 | Method of recovering platinum group metals based on copper capture |
| CN108557875B (en) * | 2018-02-13 | 2020-05-08 | 洛阳理工学院 | Hydrothermal treatment method for waste SCR catalyst |
| CN108707754A (en) * | 2018-08-07 | 2018-10-26 | 陈子清 | The method and device of noble metal in a kind of recycling catalyst |
| CN110186731A (en) * | 2019-06-17 | 2019-08-30 | 成都光明光电股份有限公司 | The measurement method of platinum content in platinum material |
| CN110724828A (en) * | 2019-10-23 | 2020-01-24 | 金川集团股份有限公司 | Method for dissolving precious metal in waste catalyst |
| WO2021083758A1 (en) * | 2019-10-28 | 2021-05-06 | Syddansk Universitet | A method of recovering iridium |
| CN110904337B (en) * | 2019-12-10 | 2021-05-28 | 新疆有色金属研究所 | Preparation method of high-purity sponge palladium |
| CN110923472A (en) * | 2019-12-13 | 2020-03-27 | 南方科技大学 | Recovery process for recovering aluminum oxide powder from heat-conducting silica gel waste |
| CN113564379A (en) * | 2021-07-26 | 2021-10-29 | 福建有道贵金属材料科技有限公司 | Method for recovering precious metal from spent automobile catalyst |
| CN115055181A (en) * | 2022-07-06 | 2022-09-16 | 四川大学 | Method for preparing high-performance CO catalyst by recycling waste noble metal catalyst |
| KR102498447B1 (en) * | 2022-09-22 | 2023-02-10 | 노상균 | Method for extracting palladium from palladium-containing stainless steel |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08325649A (en) * | 1995-05-30 | 1996-12-10 | Hyuga Seirensho:Kk | Method for concentrating platinum-group metal from spent catalyst containing the metal |
| JP3079034B2 (en) * | 1996-05-27 | 2000-08-21 | 日鉱金属株式会社 | How to recover platinum |
| KR100367708B1 (en) * | 2000-05-29 | 2003-01-10 | 희성엥겔하드주식회사 | Recovery method of platinum group metals from spent catalyst |
| CN1385545A (en) * | 2002-05-24 | 2002-12-18 | 张方宇 | Method for recovering platinum, palladium and rhodium from waste catalyst in car tail gas |
-
2003
- 2003-10-14 KR KR20030071266A patent/KR100563384B1/en not_active IP Right Cessation
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- 2004-01-07 WO PCT/KR2004/000013 patent/WO2005035804A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100563384B1 (en) | 2006-03-27 |
| WO2005035804A1 (en) | 2005-04-21 |
| KR20050035976A (en) | 2005-04-20 |
| CN1997761A (en) | 2007-07-11 |
| CN100419101C (en) | 2008-09-17 |
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