WO2008111802A1 - Method of recovering valuable metals from the vrds spent catalyst - Google Patents
Method of recovering valuable metals from the vrds spent catalyst Download PDFInfo
- Publication number
- WO2008111802A1 WO2008111802A1 PCT/KR2008/001412 KR2008001412W WO2008111802A1 WO 2008111802 A1 WO2008111802 A1 WO 2008111802A1 KR 2008001412 W KR2008001412 W KR 2008001412W WO 2008111802 A1 WO2008111802 A1 WO 2008111802A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- oxide
- sodium
- water
- filtrate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title abstract description 13
- 239000002184 metal Substances 0.000 title abstract description 13
- 150000002739 metals Chemical class 0.000 title abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 14
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 7
- 230000023556 desulfurization Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 9
- 239000011733 molybdenum Substances 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000010413 mother solution Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017089 AlO(OH) Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum 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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- 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
- This invention relates to a method of recovering metals, such as vanadium, molybdenum, nickel(hereafter, referred to as "valuable matals”), from the catalysts spent in the 'Vacuum Residue Desulfurization'(VRDS) process for desulfurization of pertoleum.
- valuable matals metals, such as vanadium, molybdenum, nickel(hereafter, referred to as "valuable matals”
- the conventonal method comprises removing the soaked oil from the spent catalysts by heating the catalysts over the boiling point of oil and thus evaporating the soaked oil from the catalysts.
- the spent catalysts are roeated at 400 ⁇ 600°C in the furnace with air(oxyzen) supplied to oxidize sulfur and metals in the catalysts.
- the sulfur is oxidized into SO and further the metals, such as molybdenum, vanadium, nickel and cobalt are oxidized into MoO , V O , NiO, and CoO, respectively.
- the SO is induced into an absober(cap-type tower), and then absorbed in water solution of sodium hydoxide to be converted into solution of sodium sulfite(Na SO3).
- the solution of sodium sulfite is dained out from the absorber.
- the conventional process comprises inducing the oxidized waste catalysts with sodium carbonate(Na CO ) continuously and quantitatively into a rotary kiln, and maintaining the rotary kiln at a temperature of 600 0 C to melt the oxides of the metals with the sodium carbonate therein.
- aluminium may be obtained in a form of mixture such as water-insoluble sodium aluminate.
- Vanadium and molybdenum are obtained in the form of their sodium salts, such as water-soluble sodium vanadate(NaVO ) and sodium molybdate(Na MoO ).
- the conventional process further comprises milling the roasted product obtained in the preceeding process, agitating the milled roasted-product in the warm water at a temperature of 8O 0 C and then leaching the formed sodium salts for one hours, washing the leachates at one or twice, controlling the washing liquid at pH 8.0, and agitating the washing liquids with ammonium chloride(NH cl) mixed therein to precipitate crystals of amonium metavanadate (NH VO ).
- the volume of ammonium chloride is used more than thioretical volume. Further, after separaing the precipiates from the mother solution, pH of the mother solution is lowered at the range of pH 2-3. And then, solution of ammonium chloride is added to the mother solution lowered at pH 2-3 so as to remove sufate ion(SO ) therein, and thus calcium sulfate(CaSO is precipitated. After removing the precipitates of calcium sulfate and then increasing pH of the mother solution, solution of calcium chloride is added to the mother solution so as to precipiate calcium molybdate(CaMoO ). molybdenum oxides can be obtained by leaching and washing
- the conventional method has disadvantages as followings.
- the method requires expensive equipments, such as a rotary Kiln, for roasting at a high temperature(900°C). Because costs is very high, a recovery of nickel wolud not be performed.
- the waste catalysts contain aluminum oxide therein at a rate of 65 percentage, the aluminum oxide is discarded in a form of water- insoluble aluminum compound, thereby resulting in waste of resources.
- the present invention comprises pre- treating the waste catalysts for deoiling and desulfurization; forming sodium aluminate, sodium vanadate and sodium molybdate as water-soluble reactants, and nickel oxide, cobalt oxide as water-insoluble reactants by reacting the pre-treated waste crystals in solution of sodium hydroxide at a temperature of 135 ⁇ 160°C; and leaching the water-inslouble nickel oxide, cobalt oxide and impurities, thereby remaining the water-soluble sodium aluminate, sodium vanadate and sodium molybdate in the solution.
- the present invention further comprises heating the filtrate containing the sodium aluminate, sodium vanadate and sodium molybdate so as to increase a temperature of the filtrate over a temerature of 8O 0 C, and agitating the filtrate with adding hydrochloric acid or sulfhuric acid therein so as to maintain pH 9.5; forming aluminum oxide at the temperture over 11O 0 C with heat of the reaction; and recovering the aluminum oxide by leaching.
- the present invention comprises forming a solution containing sodium vanadate and sodium molybdate bt treating the waste catalysts; heating the solution with the solution maintained in pH 1.0—1.0; and precipitating molybdenum oxide and vanadium oxide in the solution by aeration thereof.
- the present invention further comprises adding ammonia water to the solution in which molybdenum oxide and vanadium oxide are precipitated and thus agitating the mixtured solution so as to precipitate amonium metavanadate with ammonium molybdate remaining in the solution; and recovering and separating the crystals of the precipitated amonium metavanadate from the solution.
- the present invention can increase yield of vanadium and molybdenum from the waste catalyst at lower temperature and further recover aluminum as well as nickel and coblat without additional processes. [16] Further, the present invention can recover valuable matals from the waste catalysts without discharging waste water containing ammonia nitrogen, thereby reducing costs for purifying waster water. [17] in addition, the present invention can reduce costs of maunfacturing beecause it does not require expensive equipments, such as a rotary Kiln, for roasting at a high temperature(900°C).
- Fig.l shows a flow diagram of the process according to the present invention.
- the waste catalysts used in the 'Vacuum Residue Desulfurization'(VRDS) process for desulfurization of pertoleum may be pre-treated by the known various methods.
- the pre-treatments of the waste catalysts such as oil-removing, sulphur- removing, and oxidization of metals, are accomplished by generally known processes.
- oils soaked in the waste catalysts are removed by heating the catalysts at a temperature over the boiling point of oil.
- the deoiled waste catalysts are maintaining at a temperature of 400 0 C with heating in the deoiling process. Before cooling, the waste catalysts are induced into the roasting furnace and roasted with the supplied oxygen at a temperature of 400 ⁇ 600°C.
- the metals, such as molybdenum, vanadium, nickel, cobalt, in the waste catalysts are oxidized and thus co verted into their oxides, such as MoO , V O , NiO, CoO, and also the sulphur is oxidized and converted into sulphuric acid gas(SO 2).
- waste catalysts are dissolved in solution of sodium hydroxide and then the solution is agitated, the non-reactants including NiO, Fe2O3 are leached and thus separated from the solution.
- 80PBW(Parts By Weight) of and 80PBW of sodium hydroxide are poured and then mixed in a reactor equipped with an agitator.
- the sodium hydroxide is dissolved with heat of dissolution.
- the solution is heated pres- surelessly until the temperature of the solution reached at 135-16O 0 C by adding 100 80PBW of the oxidized waste catalysts therein.
- CoO would not be dissolved and thus remain in the solution. 400PBW of water is added so as to prevent reprecipitation of reactants by dilution of the solution. Then, the residues including NiO are leached from the solution. Nickel can be simply recovered from the residues.
- the filtrate contains sodium aluminate(NaAl(OH) ). To separate the sodium aluminate from the filtrate, the filtrate
- the reactant, Al(OH) can not be separted by leaching. Accordingly, a rotary kiln should be required for recovery of aluminum in the condition of the reaction ®.
- the reactant, AlO(OH) by the reaction ⁇ may remain but may also be leached. Therefore, the condition of reaction temperatures in the reaction ⁇ is accepatable. When the reaction proceeds at a temperature over 8O 0 C, the temperature get increased over 11O 0 C by the heat of reaction.
- the above process of recovering aluminum is required to be proceeded at a temperature over 11O 0 C because the reactant, Al(OH) is not produced at the temperature.
- the temperature of the reaction is not liminted by the upper limit but preferably maintained at a temperature of 100 0 C.
- the filtrate is agitated below pH 1 at 85- 100 0 C and further aetated therein continuously or periodically.
- mixtures of molybdenum oxide and vanadium oxide are precipitated in the solution.
- the precipitated molybdenum oxide and vanadium oxide may be obtained by leaching.
- acid solution should be used to maintain the solution below pH 2, preferably below pH 1 at a temperature of 8O 0 C.
- This temperature of reaction is dominantly lower than that of the conventional procsess, whcih makes heating equipments of high price to be useless.
- the present invention may further comprise adding ammonia water to the solution in which molybdenum oxide(MoO ) and vanadium oxide(V O ) are precipitated, agitating the mixtured solution and thus precipitating amonium metavanadate(NH VO ) and ammonium molybdate((NH )2MoO4) by using diiference of solubilty thereof; and recovering and separating the crystals of the precipitated amonium metavanadate and ammonium molybdate from the solution.
- molybdenum oxide(MoO ) and vanadium oxide(V O ) are furhter added to the mother solution with amonium water.
- molybdenum oxide(MoO ) and vanadium oxide(V O ) are dissolved in the mother solution by re-heating, and then amonium metavanadate is obtained by cooling the mother solution.
- ammonium molybdate and amonium metavanadate of high purity are obtained by minimizing dissoved amonium metavanadate.
- the specific weight of mother solution may vary as quantity of water or molybdenum in the waste catalyst. When the specific weight is below 2.5, the mother solution may be reused as reaction solution. When the specific weight is over 2.5, the mother solution becomes ammonium molybdate with 0.0% vanadium by cooling and then removing amonium metavanadate therefrom.
- Molybdenum oxide and/or vanadium oxide may be obtained by pyrolizing at least one of the amonium metavanadate and ammonium molybdate. Amonia gas generated in the process is converted into amonia water and then reused as a form of amonia water in the process. [54]
- the present invention can increase yield of vanadium and molybdenum from the waste catalyst at lower temperature and further recover aluminum as well as nickel and coblat without additional processes. [56] Further, the present invention can reduce costs of maunfacturing beecause it does not require expensive equipments, such as a rotary Kiln, for roasting at a high temperature(900°C). [57] Additionally, the present invention can recover valuable matals from the waste catalysts without discharging waste water containing ammonia nitrogen, thereby reducing costs for purifying waster water.
Abstract
The present invention discloses method of recovering valuable metals, such as vanadium, molybdenum, nickel from the catalysts spent in the VRDS process for desulfurization of pertoleum. The method comprises leaching water-insoluble reactants after reacting the pre-treated waste crystals in solution of sodium hydroxide, maintaining the filtrate at pH 9.5 by adding sulfhuric acid or hydrochloric acid and then heating the filtrate, removing aluminium oxide from the soltuion, aerating the filtrate continously or priodically and agitating the filtrate below pH 1 at 80-100 °C, thereby precipitating molybdenum oxide and vanadium oxide, and leaching and washing the precipitated molybdenum oxide and vanadium oxide.
Description
Description
METHOD OF RECOVERING VALUABLE METALS FROM THE
VRDS SPENT CATALYST
Technical Field
[1] This invention relates to a method of recovering metals, such as vanadium, molybdenum, nickel(hereafter, referred to as "valuable matals"), from the catalysts spent in the 'Vacuum Residue Desulfurization'(VRDS) process for desulfurization of pertoleum. Background Art
[2] There is known a conventional method for recovering the valuable metals from the spent catalysts in the VRDS.
[3] The conventonal method comprises removing the soaked oil from the spent catalysts by heating the catalysts over the boiling point of oil and thus evaporating the soaked oil from the catalysts. The spent catalysts are roeated at 400~600°C in the furnace with air(oxyzen) supplied to oxidize sulfur and metals in the catalysts. In the roasting process, the sulfur is oxidized into SO and further the metals, such as molybdenum, vanadium, nickel and cobalt are oxidized into MoO , V O , NiO, and CoO, respectively. The SO is induced into an absober(cap-type tower), and then absorbed in water solution of sodium hydoxide to be converted into solution of sodium sulfite(Na SO3). The solution of sodium sulfite is dained out from the absorber.
[4] In recovery of nickel and cobalt, the oxides of nickel and cobalt are milled, and then nickel and cobalt are extracted from the miled oxides of the metals in ammonia solution. As the extracted nickel and cobalt contains water soaked therein during the previous extraction process, an addional process of drying the soaked nickel and cobalt is required. This makes the whole processes for recovery of metals complex. Further, ammonium salts of nickel and cobalt are formed in the extraction process and thus make separation of the metals incomplete. Because of the above-mentioned disadvantages, a process for roasting proceeds without recovering nickel and cobalt.
[5] The conventional process comprises inducing the oxidized waste catalysts with sodium carbonate(Na CO ) continuously and quantitatively into a rotary kiln, and maintaining the rotary kiln at a temperature of 6000C to melt the oxides of the metals with the sodium carbonate therein. In this process, aluminium may be obtained in a form of mixture such as water-insoluble sodium aluminate. Vanadium and molybdenum are obtained in the form of their sodium salts, such as water-soluble sodium vanadate(NaVO ) and sodium molybdate(Na MoO ).
3 2 4
[6] The conventional process further comprises milling the roasted product obtained in
the preceeding process, agitating the milled roasted-product in the warm water at a temperature of 8O0C and then leaching the formed sodium salts for one hours, washing the leachates at one or twice, controlling the washing liquid at pH 8.0, and agitating the washing liquids with ammonium chloride(NH cl) mixed therein to precipitate crystals of amonium metavanadate (NH VO ).
4 3
[7] In this process, the volume of ammonium chloride is used more than thioretical volume. Further, after separaing the precipiates from the mother solution, pH of the mother solution is lowered at the range of pH 2-3. And then, solution of ammonium chloride is added to the mother solution lowered at pH 2-3 so as to remove sufate ion(SO ) therein, and thus calcium sulfate(CaSO is precipitated. After removing the precipitates of calcium sulfate and then increasing pH of the mother solution, solution of calcium chloride is added to the mother solution so as to precipiate calcium molybdate(CaMoO ). molybdenum oxides can be obtained by leaching and washing
4 the precipiated calcium molybdate, and then decompounding the precipiated calcium molybdate with hydrochloric acid. Disclosure of Invention Technical Problem
[8] The conventional method has disadvantages as followings. The method requires expensive equipments, such as a rotary Kiln, for roasting at a high temperature(900°C). Because costs is very high, a recovery of nickel wolud not be performed. Though the waste catalysts contain aluminum oxide therein at a rate of 65 percentage, the aluminum oxide is discarded in a form of water- insoluble aluminum compound, thereby resulting in waste of resources. Technical Solution
[9] It is an object of the present invention to provide methods of recovering valuable matals from the waste catalysts used in the VRDS, which can increase high yield of vanadium and molybdenum from the waste catalyst at lower temperature and further recover aluminum as well as nickel and coblat without additional processes.
[10] It is further object of the present invention to provide methods of recovering valuable matals from the waste catalysts without discharging waste water containing ammonia nitrogen, thereby reducing costs for purifying waster water.
[11] In order to solve the above disadvantages, the present invention comprises pre- treating the waste catalysts for deoiling and desulfurization; forming sodium aluminate, sodium vanadate and sodium molybdate as water-soluble reactants, and nickel oxide, cobalt oxide as water-insoluble reactants by reacting the pre-treated waste crystals in solution of sodium hydroxide at a temperature of 135~160°C; and leaching the water-inslouble nickel oxide, cobalt oxide and impurities, thereby remaining the
water-soluble sodium aluminate, sodium vanadate and sodium molybdate in the solution.
[12] The present invention further comprises heating the filtrate containing the sodium aluminate, sodium vanadate and sodium molybdate so as to increase a temperature of the filtrate over a temerature of 8O0C, and agitating the filtrate with adding hydrochloric acid or sulfhuric acid therein so as to maintain pH 9.5; forming aluminum oxide at the temperture over 11O0C with heat of the reaction; and recovering the aluminum oxide by leaching.
[13] Furthermore, the present invention comprises forming a solution containing sodium vanadate and sodium molybdate bt treating the waste catalysts; heating the solution with the solution maintained in pH 1.0—1.0; and precipitating molybdenum oxide and vanadium oxide in the solution by aeration thereof.
[14] The present invention further comprises adding ammonia water to the solution in which molybdenum oxide and vanadium oxide are precipitated and thus agitating the mixtured solution so as to precipitate amonium metavanadate with ammonium molybdate remaining in the solution; and recovering and separating the crystals of the precipitated amonium metavanadate from the solution.
Advantageous Effects
[15] The present invention can increase yield of vanadium and molybdenum from the waste catalyst at lower temperature and further recover aluminum as well as nickel and coblat without additional processes. [16] Further,the present invention can recover valuable matals from the waste catalysts without discharging waste water containing ammonia nitrogen, thereby reducing costs for purifying waster water. [17] in addition, the present invention can reduce costs of maunfacturing beecause it does not require expensive equipments, such as a rotary Kiln, for roasting at a high temperature(900°C).
Brief Description of the Drawings [18] Fig.l shows a flow diagram of the process according to the present invention.
Best Mode for Carrying Out the Invention
[19] The present invention is desribed in detail with reference to the attached drawing.
[20] The waste catalysts used in the 'Vacuum Residue Desulfurization'(VRDS) process for desulfurization of pertoleum may be pre-treated by the known various methods.
That is, the pre-treatments of the waste catalysts, such as oil-removing, sulphur- removing, and oxidization of metals, are accomplished by generally known processes.
For example, oils soaked in the waste catalysts are removed by heating the catalysts at a temperature over the boiling point of oil.
[21] The deoiled waste catalysts are maintaining at a temperature of 4000C with heating in the deoiling process. Before cooling, the waste catalysts are induced into the roasting furnace and roasted with the supplied oxygen at a temperature of 400~600°C.
[22] In the roasting process, the metals, such as molybdenum, vanadium, nickel, cobalt, in the waste catalysts are oxidized and thus co verted into their oxides, such as MoO , V O , NiO, CoO, and also the sulphur is oxidized and converted into sulphuric acid gas(SO 2).
[23] The sulphuric acid gas is absorbed in solution of sodium hydroxide(NaOH) and converted into sodium sulfite(Na SO ), which is drained out.
[24] The waste catalysts are dissolved in solution of sodium hydroxide and then the solution is agitated, the non-reactants including NiO, Fe2O3 are leached and thus separated from the solution.
[25] Preferably, 80PBW(Parts By Weight) of and 80PBW of sodium hydroxide are poured and then mixed in a reactor equipped with an agitator. In this process, the sodium hydroxide is dissolved with heat of dissolution. The solution is heated pres- surelessly until the temperature of the solution reached at 135-16O0C by adding 100 80PBW of the oxidized waste catalysts therein.
[26] To react the waste catalysts in the solution at 16O0C for 2-3 hours, NiO, FeO and
CoO would not be dissolved and thus remain in the solution. 400PBW of water is added so as to prevent reprecipitation of reactants by dilution of the solution. Then, the residues including NiO are leached from the solution. Nickel can be simply recovered from the residues.
[27] Then, aluminum is recovered from the filtrate. The filtrate contains sodium aluminate(NaAl(OH) ). To separate the sodium aluminate from the filtrate, the filtrate
4 is stirred with an agitator and heated at a temperature of 85~90°Cand then sulfhuric acid or hydrochloric acid(20~30%) is added into the filtrate. The addition of the acid to the solution should be controlled to be maintained at pH 9.5. In this process, aluminum oxide(Al O ) is poducted and thus leached from the solution. The aluminum oxide is washed with water until vanadium is not detected in the water. The water in the aluminum oxide is dried with suction of a vacuum pump.
[28] The above processes for recovering aluminum may be applied to the recovery of vanadium in the same manner. In the process of recovering vanadium, aluminum oxide is replaced with sodium aluminate and sodium tungstate exist in a form of water solution.
[29] In the reaction of filtrate with HCl solution, the reaction temperature and the basicity or acidity are very critical.
[30] The beolw reaction formulars show various products of aluminum oxide according to gradients of temperature at pH 9.5-14.
[31]
[32] NaAl(OH) +HCl=Al(OH) +NaCl+ H2O (0°C~normal temperature) ®
[33] NaAl(OH) +HCl=A10(0H)+NaCl+2H20 (8O0C ~ 950C) ©
[34] 2NaAl(OH) 4 +2HCl=Al 2 O 3 +2NaCl+5H2O(100°C~ 12O0C) ®
[35] In the reaction ®, the reactant, Al(OH) can not be separted by leaching. Accordingly, a rotary kiln should be required for recovery of aluminum in the condition of the reaction ®.
[36] In the reaction ©, the reactant, AlO(OH) by the reaction © may remain but may also be leached. Therefore, the condition of reaction temperatures in the reaction © is accepatable. When the reaction proceeds at a temperature over 8O0C, the temperature get increased over 11O0C by the heat of reaction.
[37] Accordingly, the above process of recovering aluminum is required to be proceeded at a temperature over 11O0C because the reactant, Al(OH) is not produced at the temperature. The temperature of the reaction is not liminted by the upper limit but preferably maintained at a temperature of 1000C.
[38] As the filtrate is maintained at 12O0C by applying pressure, solution of HCl is added to the filtrate of pH 9-14. Then, sole Al O may be obtained by removing sodium oxide(Na O) from the filtrate. There remain sodium vanadate(NaVO ) and sodium molybdate(Na MoO ) in the filtrate from which A12O3 is removed. Preferably, the filtrate is agitated below pH l(pH -1.0) at 850C until the reaction is completed.
[39]
[40] As shown in the following reaction formulas land π, the filtrate is agitated below pH 1 at 85- 1000C and further aetated therein continuously or periodically. As a result of the process, mixtures of molybdenum oxide and vanadium oxide are precipitated in the solution. The precipitated molybdenum oxide and vanadium oxide may be obtained by leaching.
[41] reaction formula I:
[42]
Na - - 0 - V yj v ϊr.
Na - - 0 - V
2NaCl
[43] [44] reaction formula II
Na - O O H - O 0 Dehydration 0 0 - H
// by aeration
Mo 2HCl Mo Mo + H - 0 -H pHl ~ 2 ^ // X-
Na - O O H - O 0 0 ! 0 - - H
2NaCl
[46] [47] While the filtration is aerated by blowing air, reaction of hydration occurs and thus the metal oxides are precipitated in the solution of reaction. The aeration allows hydration to accur at a lower temperature ,thereby allowing additonal heating to be eliminated. In this reaction, molybdenum oxide and vanadium oxide are precipitated as amorphous crystal and thus may be obtained by leaching and washing.
[48] In the above process, acid solution should be used to maintain the solution below pH 2, preferably below pH 1 at a temperature of 8O0C. This temperature of reaction is dominantly lower than that of the conventional procsess, whcih makes heating equipments of high price to be useless.
[49] The present invention may further comprise adding ammonia water to the solution in which molybdenum oxide(MoO ) and vanadium oxide(V O ) are precipitated, agitating the mixtured solution and thus precipitating amonium metavanadate(NH VO ) and ammonium molybdate((NH )2MoO4) by using diiference of solubilty thereof; and recovering and separating the crystals of the precipitated amonium metavanadate and ammonium molybdate from the solution.
[50] After sepating ammonium molybdate from the mother solution, molybdenum oxide(MoO ) and vanadium oxide(V O ) are furhter added to the mother solution with amonium water. Thus, molybdenum oxide(MoO ) and vanadium oxide(V O ) are dissolved in the mother solution by re-heating, and then amonium metavanadate is obtained by cooling the mother solution. These processes are repeated until the specific weight of the mother solution reaches to 2.5.
[51] Through the processes, ammonium molybdate and amonium metavanadate of high purity are obtained by minimizing dissoved amonium metavanadate. [52] After the process, the specific weight of mother solution may vary as quantity of water or molybdenum in the waste catalyst. When the specific weight is below 2.5, the mother solution may be reused as reaction solution. When the specific weight is over 2.5, the mother solution becomes ammonium molybdate with 0.0% vanadium by cooling and then removing amonium metavanadate therefrom.
[53] Molybdenum oxide and/or vanadium oxide may be obtained by pyrolizing at least one of the amonium metavanadate and ammonium molybdate. Amonia gas generated
in the process is converted into amonia water and then reused as a form of amonia water in the process. [54]
Industrial Applicability
[55] The present invention can increase yield of vanadium and molybdenum from the waste catalyst at lower temperature and further recover aluminum as well as nickel and coblat without additional processes. [56] Further, the present invention can reduce costs of maunfacturing beecause it does not require expensive equipments, such as a rotary Kiln, for roasting at a high temperature(900°C). [57] Additionally, the present invention can recover valuable matals from the waste catalysts without discharging waste water containing ammonia nitrogen, thereby reducing costs for purifying waster water.
Claims
[1] A method of recovering valuable matals from the waste catalysts in VRDS, comprising: pre-treating the waste catalysts for deoiling and desulfurization; forming sodium aluminate, sodium vanadate and sodium molybdate as water- soluble reactants, and nickel oxide, cobalt oxide as water-insoluble reactants by reacting the pre-treated waste crystals in solution of sodium hydroxide at a temperature of 135~160°C; and leaching the water-inslouble nickel oxide, cobalt oxide and impurities, thereby remaining the water-soluble sodium aluminate, sodium vanadate and sodium molybdate in the solution.
[2] A method according to claim 1, further comprising heating the filtrate containing the sodium aluminate, sodium vanadate and sodium molybdate so as to increase a temperature of the filtrate over a temerature of 8O0C, and agitating the filtrate with adding hydrochloric acid or sulfhuric acid therein so as to maintain pH 9.5; forming aluminum oxide at the temperture over 11O0C with heat of the reaction; and recovering the aluminum oxide by leaching.
[3] A method of recovering valuable matals from the waste catalysts in VRDS, comprising: forming a solution containing sodium vanadate and sodium molybdate bt treating the waste catalysts; heating the solution with the solution maintained in pH 1.0—1.0; and precipitating molybdenum oxide and vanadium oxide in the solution by aeration thereof.
[4] A method according to claim 3 further comprising adding ammonia water to the solution in which molybdenum oxide and vanadium oxide are precipitated and thus agitating the mixtured solution so as to precipitate amonium metavanadate with ammonium molybdate remaining in the solution; and recovering and separating the crystals of the precipitated amonium metavanadate from the solution.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/530,743 US20100111787A1 (en) | 2007-03-13 | 2008-03-13 | Method of recovering valuable metals from the vrds spent catalyst |
| JP2009553521A JP2010521286A (en) | 2007-03-13 | 2008-03-13 | Method for recovering valuable metals from petroleum desulfurization catalysts |
| EP08723449A EP2125136A4 (en) | 2007-03-13 | 2008-03-13 | Method of recovering valuable metals from the vrds spent catalyst |
| CA 2679442 CA2679442A1 (en) | 2007-03-13 | 2008-03-13 | Method of recovering valuable metals from the vrds spent catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20070025283A KR20070043736A (en) | 2007-03-13 | 2007-03-13 | A recovering method of 98% of precious metals including vanadium and molybdenum from discarded desulfurization catalyst used in oil via lower temperature roaster |
| KR10-2007-0025283 | 2007-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008111802A1 true WO2008111802A1 (en) | 2008-09-18 |
Family
ID=38178057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2008/001412 WO2008111802A1 (en) | 2007-03-13 | 2008-03-13 | Method of recovering valuable metals from the vrds spent catalyst |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20100111787A1 (en) |
| EP (1) | EP2125136A4 (en) |
| JP (1) | JP2010521286A (en) |
| KR (2) | KR20070043736A (en) |
| CN (1) | CN101631598A (en) |
| CA (1) | CA2679442A1 (en) |
| WO (1) | WO2008111802A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967007A (en) * | 2010-11-23 | 2011-02-09 | 云南临沧鑫圆锗业股份有限公司 | Process method for improving chlorination distillation recovery rate of coarse germanium dioxide |
| EP2465605A3 (en) * | 2010-12-20 | 2014-04-30 | Sachtleben Chemie GmbH | Titania-supported hydrotreating catalysts |
| CN114635032A (en) * | 2022-02-24 | 2022-06-17 | 湖南长宏新能源材料有限责任公司 | Comprehensive recycling method for waste catalyst |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101487549B1 (en) * | 2008-04-30 | 2015-01-29 | 주식회사 코캣 | A Separation and Recovery Process of Metals from Petroleum Desulfurization Waste Catalyst |
| KR101041378B1 (en) * | 2009-08-28 | 2011-06-15 | 한국지질자원연구원 | Recovery method of valuable metals and sulfur from spent petroleum catalyst |
| KR101101755B1 (en) * | 2009-09-16 | 2012-01-05 | 주식회사 리싸이텍코리아 | Method for recycling waste cemented carbide sludge |
| EP2404649A1 (en) * | 2010-07-06 | 2012-01-11 | Total Raffinage Marketing | Flakes management in hydrocarbon processing units |
| NL2005158C2 (en) | 2010-07-26 | 2012-01-30 | Greenshores Patent B V | Process for isolating vanadium from a solid composition. |
| CN102950010B (en) * | 2011-08-31 | 2015-05-20 | 中国石油化工股份有限公司 | Method for utilizing molybdenum in waste cobalt-molybdenum-system sulfur-tolerant shift catalyst |
| CN103521046B (en) * | 2012-07-04 | 2015-12-09 | 北京三聚环保新材料股份有限公司 | A kind of method preparing ambient temperature desulfuration agent with copper zinc dead catalyst |
| CN103058286A (en) * | 2013-01-08 | 2013-04-24 | 苏州科技学院 | Synthetic method of novel meso-porous metal oxide material |
| TWI465579B (en) | 2013-03-25 | 2014-12-21 | ping tao Wu | Method for recycling metal in waste catalyst comprised of aluminum |
| CN104232902A (en) * | 2014-09-03 | 2014-12-24 | 陈敏 | Method for recycling tungsten, molybdenum, aluminum and cobalt from waste catalyst through wet process |
| CN104384167B (en) * | 2014-09-09 | 2018-12-25 | 华电高科环保技术有限公司 | A kind of comprehensive reutilization method of discarded titanium-based vanadium system SCR catalyst |
| CN105457973B (en) * | 2015-12-23 | 2017-07-14 | 中国石油大学(北京) | The method and processing system handled chlorine aluminium acidic ionic liquids dead catalyst |
| CN110387471B (en) * | 2018-04-23 | 2021-12-17 | 中国石油化工股份有限公司 | Deep nickel removing method for waste catalytic cracking catalyst, silicon-aluminum material obtained by deep nickel removing method and application of silicon-aluminum material |
| CN110387470B (en) * | 2018-04-23 | 2022-01-04 | 中国石油化工股份有限公司 | Treatment method of waste catalytic cracking catalyst, silicon-aluminum material obtained by treatment method and application of silicon-aluminum material |
| CN110527834A (en) * | 2018-05-23 | 2019-12-03 | 国家能源投资集团有限责任公司 | The method for handling waste flue gas denitration catalyst |
| CN110195161B (en) * | 2019-06-10 | 2021-02-12 | 江西理工大学 | Method for recovering Al and Co from waste aluminum-based catalyst sodium-modification roasting water-immersed slag |
| KR102319523B1 (en) * | 2019-11-29 | 2021-10-29 | 주식회사 모노리스 | Separation and recovery of valuable metals from desulfurized waste catalyst |
| CN111573733A (en) * | 2020-05-14 | 2020-08-25 | 大连众智创新催化剂有限公司 | Method for recycling waste catalyst |
| CN111690812B (en) * | 2020-06-15 | 2022-06-07 | 南方科技大学 | Recovery method of waste ternary lithium battery |
| CN114075623B (en) * | 2020-08-12 | 2023-03-31 | 中国科学院过程工程研究所 | Resource utilization method for two-stage extraction of vanadium-containing waste petroleum catalyst |
| CN114075625A (en) * | 2020-08-18 | 2022-02-22 | 刘虎 | Method for recovering valuable metals in carbon black |
| CN114480857A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method for recovering valuable metals in gasified ash |
| CN112408482A (en) * | 2020-10-28 | 2021-02-26 | 沈阳化工大学 | Comprehensive utilization method of alkali-soluble mother liquor of molybdenum-modified aluminum-nickel amorphous alloy catalyst |
| CN112410562A (en) * | 2020-10-30 | 2021-02-26 | 岳阳鼎格云天环保科技有限公司 | Treatment process of vanadium-titanium denitration waste catalyst |
| CN112301227A (en) * | 2020-10-30 | 2021-02-02 | 岳阳鼎格云天环保科技有限公司 | Recycling method of hydrogenation type waste catalyst |
| CN113430383B (en) * | 2021-06-29 | 2022-09-16 | 中国科学院过程工程研究所 | Method for extracting vanadium, nickel and molybdenum by leaching waste catalyst with ammonium sulfate solution |
| CN113981207A (en) * | 2021-10-11 | 2022-01-28 | 北京工业大学 | Method for leaching tungsten and molybdenum and application |
| CN114438332A (en) * | 2022-01-25 | 2022-05-06 | 中南大学 | Treatment method and application of waste hydrogenation catalyst |
| CN115401060B (en) * | 2022-08-24 | 2023-11-14 | 浙江红狮环保股份有限公司 | Method for removing chlorine content from organic hazardous waste |
| CN117660767A (en) * | 2024-01-31 | 2024-03-08 | 中国科学院过程工程研究所 | Method for recycling sodium vanadate from nickel-aluminum slag by adopting multi-section microbubbles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156375A (en) * | 1991-12-05 | 1993-06-22 | Taiyo Koukou Kk | Method for leaching valuable metal from waste catalyst |
| US20040213717A1 (en) * | 2003-04-25 | 2004-10-28 | Toshiaki Akahoshi | Process for separating and recovering valuable metals |
| JP2005262181A (en) * | 2004-03-22 | 2005-09-29 | Nippon Catalyst Cycle Kk | Method for separating phosphorus-containing substance from used catalyst |
| JP2006328440A (en) * | 2005-05-23 | 2006-12-07 | Sumitomo Metal Mining Co Ltd | Method for recovering nickel from spent catalyst |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS549995B2 (en) * | 1973-11-06 | 1979-04-28 | ||
| JPS5521088B2 (en) * | 1975-01-25 | 1980-06-07 | ||
| JPS5319118A (en) * | 1976-08-06 | 1978-02-22 | Baba Risaachi Inst Kk | Extraction of v and mo from oxidizing roasted ores containing same components |
| US4670229A (en) * | 1986-05-09 | 1987-06-02 | Amax Inc. | Cyclic process for recovering metal values and alumina from spent catalysts |
| US4666685A (en) * | 1986-05-09 | 1987-05-19 | Amax Inc. | Selective extraction of molybdenum and vanadium from spent catalysts by oxidative leaching with sodium aluminate and caustic |
| FR2668938B1 (en) * | 1990-11-12 | 1995-03-17 | Inst Francais Du Petrole | NOVEL PROCESS FOR ANTI-POLLUTION TREATMENT OF A REFINING CATALYST IN THE USED CONDITION AND TOTAL RECOVERY OF THE DIFFERENT METAL CONSTITUENTS OF SAID CATALYST. |
| FR2687170B1 (en) * | 1992-02-07 | 1994-09-30 | Eurecat Europ Retrait Catalys | RECOVERY OF MOLYBDENE AND VANADIUM FROM USED CATALYSTS. |
| JP3887511B2 (en) * | 1999-05-19 | 2007-02-28 | 三菱レイヨン株式会社 | Catalyst production method |
| JP3835148B2 (en) * | 2000-09-25 | 2006-10-18 | 住友金属鉱山株式会社 | Mo and V separation and recovery method |
| KR100674438B1 (en) | 2005-12-09 | 2007-01-25 | 서안켐텍 주식회사 | A process for separating vanadium and molybdenum from desulfurization waste catalyst |
-
2007
- 2007-03-13 KR KR20070025283A patent/KR20070043736A/en not_active Application Discontinuation
-
2008
- 2008-03-13 WO PCT/KR2008/001412 patent/WO2008111802A1/en active Application Filing
- 2008-03-13 CN CN200880008311A patent/CN101631598A/en active Pending
- 2008-03-13 CA CA 2679442 patent/CA2679442A1/en not_active Abandoned
- 2008-03-13 EP EP08723449A patent/EP2125136A4/en not_active Withdrawn
- 2008-03-13 US US12/530,743 patent/US20100111787A1/en not_active Abandoned
- 2008-03-13 KR KR20080023169A patent/KR101008496B1/en not_active IP Right Cessation
- 2008-03-13 JP JP2009553521A patent/JP2010521286A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156375A (en) * | 1991-12-05 | 1993-06-22 | Taiyo Koukou Kk | Method for leaching valuable metal from waste catalyst |
| US20040213717A1 (en) * | 2003-04-25 | 2004-10-28 | Toshiaki Akahoshi | Process for separating and recovering valuable metals |
| JP2005262181A (en) * | 2004-03-22 | 2005-09-29 | Nippon Catalyst Cycle Kk | Method for separating phosphorus-containing substance from used catalyst |
| JP2006328440A (en) * | 2005-05-23 | 2006-12-07 | Sumitomo Metal Mining Co Ltd | Method for recovering nickel from spent catalyst |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP2125136A4 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967007A (en) * | 2010-11-23 | 2011-02-09 | 云南临沧鑫圆锗业股份有限公司 | Process method for improving chlorination distillation recovery rate of coarse germanium dioxide |
| EP2465605A3 (en) * | 2010-12-20 | 2014-04-30 | Sachtleben Chemie GmbH | Titania-supported hydrotreating catalysts |
| US9719031B2 (en) | 2010-12-20 | 2017-08-01 | Sachleben Chemie GmbH | Titania-supported hydrotreating catalysts |
| CN114635032A (en) * | 2022-02-24 | 2022-06-17 | 湖南长宏新能源材料有限责任公司 | Comprehensive recycling method for waste catalyst |
| CN114635032B (en) * | 2022-02-24 | 2024-01-30 | 湖南长宏新能源材料有限责任公司 | Comprehensive recycling method of waste catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2125136A1 (en) | 2009-12-02 |
| KR101008496B1 (en) | 2011-01-14 |
| CN101631598A (en) | 2010-01-20 |
| CA2679442A1 (en) | 2008-09-18 |
| EP2125136A4 (en) | 2011-11-09 |
| JP2010521286A (en) | 2010-06-24 |
| KR20080032057A (en) | 2008-04-14 |
| KR20070043736A (en) | 2007-04-25 |
| US20100111787A1 (en) | 2010-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2125136A1 (en) | Method of recovering valuable metals from the vrds spent catalyst | |
| JP6025868B2 (en) | Process to treat red mud | |
| EP1080239B1 (en) | Process to recover molybdenum and vanadium metals from spent catalyst by alkaline leaching | |
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| CN104263946A (en) | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst | |
| EP0771881A1 (en) | An integrated process for the recovery of metals and fused alumina from spent catalysts | |
| CN104152704A (en) | Method for separating and recovering vanadium and chromium from vanadium-chromium slag | |
| KR20040019292A (en) | Production of Pure Molybdenum Oxide from Low Grade Molybdenite Concentrates | |
| US4150976A (en) | Method for the recovery of metallic copper | |
| CN108588446B (en) | Method for extracting molybdenum and rhenium from rhenium-containing molybdenum concentrate | |
| CN105567964A (en) | Method for selectively reducing, separating and recycling vanadium and chrome from solution containing vanadium and chrome | |
| AU2021204219B2 (en) | Recovery of Metals from Pyrite | |
| CN114606387A (en) | Wet-process and pyrogenic-process combined comprehensive recovery method for arsenic-alkali residue | |
| WO2021056110A1 (en) | Process for the recovery of vanadium oxides from various materials | |
| CA1214382A (en) | Method for regenerating pickling acids | |
| KR101487549B1 (en) | A Separation and Recovery Process of Metals from Petroleum Desulfurization Waste Catalyst | |
| JPH078808A (en) | Method for environmental pollution preventing treatment of catalyst for purification under used condition and method for recovery of metal | |
| CN113293297B (en) | Multi-element recycling of residual oil hydrogenation waste catalyst | |
| US4474735A (en) | Process for the recovery of valuable metals from spent crude-oil sulfur-extraction catalysts | |
| CN109402411B (en) | Method for comprehensively recovering valuable metals from zinc smelting slag | |
| WO2009012544A2 (en) | Process to produce molybdenum compounds, from spent molybdenum catalyzers, industrial residues and metal alloys | |
| KR100277503B1 (en) | Separation and recovery of nickel, vanadium and molybdenum from petroleum desulfurization spent catalyst | |
| CN109338108A (en) | A kind of wet-treating tungsten product molybdenum removal slag and the process for recycling molybdenum, copper, tungsten, sulphur | |
| JP6852695B2 (en) | Scandium recovery method | |
| CN110042248A (en) | The method for preparing ferric vandate as raw material using dephosphorization mud |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 200880008311.5 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08723449 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2679442 Country of ref document: CA |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 5229/CHENP/2009 Country of ref document: IN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2009553521 Country of ref document: JP |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2008723449 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 12530743 Country of ref document: US |