KR101727891B1 - Environment-Friendly Wet Process for Molybdenum Recovery From Spent Desulfurization Catalyst for Oil Refinery - Google Patents
Environment-Friendly Wet Process for Molybdenum Recovery From Spent Desulfurization Catalyst for Oil Refinery Download PDFInfo
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- KR101727891B1 KR101727891B1 KR1020160061939A KR20160061939A KR101727891B1 KR 101727891 B1 KR101727891 B1 KR 101727891B1 KR 1020160061939 A KR1020160061939 A KR 1020160061939A KR 20160061939 A KR20160061939 A KR 20160061939A KR 101727891 B1 KR101727891 B1 KR 101727891B1
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- molybdenum
- moo
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- 238000000034 method Methods 0.000 title claims abstract description 87
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 43
- 239000011733 molybdenum Substances 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 12
- 230000023556 desulfurization Effects 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000000909 electrodialysis Methods 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 12
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000005341 cation exchange Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000012467 final product Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 94
- 229910052759 nickel Inorganic materials 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229910017052 cobalt Inorganic materials 0.000 claims description 27
- 239000010941 cobalt Substances 0.000 claims description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- 239000002699 waste material Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000638 solvent extraction Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 150000002751 molybdenum Chemical class 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 2
- 238000001556 precipitation Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- -1 alumina (Al 2 O 3 ) Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002195 soluble material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Urology & Nephrology (AREA)
- Health & Medical Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
본 발명은 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정에 관한 것으로, 더욱 상세하게는 폐촉매에 존재하는 몰리브덴(Mo), 니켈(Ni), 코발트(Co), 철(Fe) 및 담체로 이용된 알루미나(Al2O3) 등을 무기산을 이용하여 몰리브덴(Mo)을 산화시킨 다음, 용해성 물질인 니켈(Ni), 코발트(Co), 철(Fe)은 용액 내에 이온상태로 용해시키고 황(S)을 회수하며, 이를 여과하여 고체성분에 알카리 용액을 첨가하여 몰리브덴(Mo) 성분을 용해시켜 합성공정을 통해 산화몰리브덴(MoO3)을 최종 회수함과 동시에 상기 금속성분을 분리할 수 있는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정에 관한 것이다.The present invention relates to an environmentally friendly wet process for recovering molybdenum from a refinery oil desulfurization catalyst, and more particularly, to a process for recovering molybdenum from a spent catalyst for recovering molybdenum, Molybdenum (Mo) is oxidized using inorganic acid such as alumina (Al 2 O 3 ), and then soluble materials such as nickel (Ni), cobalt (Co) and iron (Fe) (Mo) component is dissolved by adding an alkali solution to the solid component by filtration to finally recover the molybdenum oxide (MoO 3 ) through the synthesis step and to separate the metal component And an environmentally friendly wet process for recovering molybdenum from a refinery de-sulfurized spent catalyst.
일반적으로, 금속성분을 함유하는 폐액으로부터 선택적 금속을 회수하는 방법, 특히 철과 코발트, 니켈 등을 회수하는 방법에는 이온교환법, 용매추출법, 침전법 등이 있다.In general, a method of recovering a selective metal from a waste liquid containing a metal component, particularly, a method of recovering iron, cobalt, nickel, and the like, includes an ion exchange method, a solvent extraction method, and a precipitation method.
이온교환법은 이온교환막을 이용하여 산 또는 알칼리를 분리 농축하여 산과 알칼리를 분리 회수하는 기술로서, 역삼투막을 사용하여 수분을 제거함으로써 농축이 가능하며, 이러한 막분리법은 가열조작이 없기 때문에 에너지 절약형이다. 그러나 폐액 중에 다량의 염과 금속이온이 함유되어 있는 경우에는 이온교환이 비효율적이고 대용량의 이온교환기가 필요하게 되는 단점이 있다. 이온교환막에 의하여 폐산을 회수하는 방법은 고정되어 있는 이온교환막을 이용하여 농도차 만으로 유리산을 회수하는 확산투석법과 양이온 교환막과 음이온 교환막을 동시에 사용하고 양극의 전극으로부터 직류전원을 공급하여 분리를 촉진시키는 전기투석법이 있다.The ion exchange method is a technology for separate and recovering acid and alkali by separately separating acid or alkali using an ion exchange membrane. It is possible to concentrate by removing water using a reverse osmosis membrane. Such a membrane separation method is energy saving because there is no heating operation. However, when a large amount of salt and metal ions are contained in the waste solution, ion exchange is inefficient and a large-capacity ion exchanger is required. A method of recovering spent acid by ion exchange membrane is a diffusion dialysis method in which a free acid is recovered only by a concentration difference using a fixed ion exchange membrane, a cation exchange membrane and an anion exchange membrane are used at the same time, a DC power is supplied from an anode electrode, There is an electrodialysis method.
용매추출법은 용매의 선택적인 추출능력을 이용하여 폐액으로부터 금속을 추출하는 방법으로, 용매의 조성을 조절하여 여러 금속의 혼합액으로부터 비교적 순수하게 금속성분을 회수할 수 있다는 장점이 있는데 반해, 추출이 지속됨에 따라 용매의 오염에 따른 추출성능의 저하 및 추출설비의 규모가 크다는 단점이 있다. 한편, 광물로부터 금속소재의 제조는 침출, 분리, 정제, 환원 등 일련의 공정을 거쳐 이루어지는데, 최근 광물 품위의 저하 및 고순도 금속소재에 대한 수요가 증대됨에 따라 보다 효율적인 분리정제기술의 개발이 요구되고 있으며, 특히 환경과 에너지에 대한 관심이 높아지면서 환경 친화적이고 저에너지형 분리정제기술에 대한 관심이 고조되고 있다.The solvent extraction method is a method of extracting metal from a waste solution by using a selective extraction ability of a solvent. It is advantageous that a metal component can be recovered relatively purely from a mixed solution of various metals by controlling the composition of a solvent, The extraction performance is deteriorated due to the contamination of the solvent and the scale of the extraction equipment is large. On the other hand, the production of metal materials from minerals takes place through a series of processes such as leaching, separation, purification, and reduction. Recently, as the demand for high purity metal materials has increased, the development of more efficient separation and purification technology As the interest in environment and energy has increased, interest in environmentally friendly low-energy separation and purification technology is increasing.
침전법은 금속과 화합물을 형성하는 침전제를 가하여 금속을 선택적으로 침전시켜 분리하는 정제기술로서, 수용액 내에서 불용성인 염으로 전환시켜 침전시킨 후에 여과과정을 거쳐 얻어내는 방법으로 비교적 설비의 규모가 작고 공정 또한 비교적 간단하므로 현재까지 소규모 단위공장에서 가장 널리 사용되고 있는 방법이지만, 공침에 의한 불순물의 혼입으로 고순도의 제품으로 회수하기가 어렵기 때문에 일정 수준 이상의 순도를 갖는 금속을 얻기 위해서는 화학침전을 여러 차례 반복해야 하는 치명적인 단점이 있다.The precipitation method is a purification technique in which a precipitant that forms a compound with a metal is added to precipitate a metal by selective precipitation. The precipitate is converted into an insoluble salt in an aqueous solution, precipitated, and then filtered to obtain a relatively small scale Since the process is relatively simple, it is the most widely used method in a small-scale unit factory. However, since it is difficult to recover as a high-purity product due to incorporation of impurities by coprecipitation, in order to obtain a metal having a certain degree of purity, There are fatal disadvantages that must be repeated.
상기와 같이 폐액으로부터 금속성분을 회수하는 종래의 방법을 보면, 대한민국 등록특허 제10-0277503호에서는 일반적으로 석유탈황 폐촉매를 고온 소다배소하면 불용성 알루미늄 니켈 화합물이 생성되어 니켈성분을 분리, 회수할 수 없기 때문에, 석유탈황(Vacuum Residue Desulfurization, VRDS) 폐촉매를 저온산화배소 및 황산암모늄을 침출한 용액 중에서 니켈성분을 NiSO4 형태로 분리, 회수하고 상기의 니켈성분을 회수한 폐촉매 잔사를 다시 고온 산화배소, 수침출 및 침전시켜 V2O5와 CaMoO4 형태로 분리, 회수하는 방법을 제시하고 있다.According to the conventional method for recovering the metal component from the waste liquid as described above, Korean Patent No. 10-0277503 discloses that when the petroleum desulfurization spent catalyst is generally roasted at high temperature, an insoluble aluminum nickel compound is produced and the nickel component is separated and recovered Therefore, the nickel component is separated and recovered in the form of NiSO 4 in a solution of low temperature oxidation rosin and ammonium sulfate leached out from the waste catalyst of Vacuum Residue Desulfurization (VRDS), and the spent catalyst residue obtained by recovering the nickel component is re- And then separated and recovered in the form of V 2 O 5 and CaMoO 4 by high temperature oxidation roasting, water leaching and precipitation.
또한, 대한민국 등록특허 제10-0978999호에서는 바나듐 몰리브덴 및 니켈이 함유된 탈황 폐촉매를 종래의 킬른을 통한 고온 소다배소공정을 거치지 않고, 상압 및 고온가압 알카리 침출을 통해 바나듐 및 몰리브덴 성분을 가용화하여 각각 90% 이상 침출할 수 있으며, 침출액을 용매 TIOA로 용매추출 후 수산화나트륨으로 역추출하여 각각 암모늄바나데이트 및 몰리브덴산으로 선택적 침전시켜 필터링하여 세척하고 하소공정을 거쳐 V2O5, MoO3로 제조한다. 또 폐촉매 잔사에 잔류하는 니켈 성분은 배소를 하지 않은 영향으로 불용성물질인 니켈알루미나 산화물이 형성되지 않음으로 염산 또는 황산으로 약 95% 침출할 수 있으며, 암모니아로 산에 침출된 알루미늄 및 철을 제거한다. 또 침출된 니켈은 용매 LiX84i에 추출한 후에 염산으로 역추출하여 미량 금속을 분리하고, 탄산나트륨으로 탄산화반응시켜 침전된 탄산니켈 케이크를 필터링하여 세척, 하소하여 분쇄공정을 통해 고순도 산화니켈을 제조함으로써 배소시 발생하는 폐가스를 사전에 차단하여 대기 오염을 줄이고 가스발생에 따른 후단 포집설비를 대폭 줄일 수 있다고 하나, 상기와 같은 공정들은 아직까지 상용화되지 못하고 있는 실정이다.Korean Patent No. 10-0978999 discloses a method of solubilizing vanadium and molybdenum components through atmospheric pressure and hot pressurized alkali leaching without using a conventional high temperature soda roasting process through a kiln in a desulfurized spent catalyst containing vanadium molybdenum and nickel It can be leached by more than 90%. The leachate is extracted with solvent TIOA and then back extracted with sodium hydroxide. The precipitate is selectively filtered with ammonium vanadate and molybdic acid, filtered, cleaned, and treated with V 2 O 5 and MoO 3 . In addition, the nickel component remaining in the spent catalyst residue does not form nickel insoluble nickel alumina oxide due to the non-roasting effect, so it can leach out about 95% with hydrochloric acid or sulfuric acid and remove aluminum and iron leached into the acid with ammonia do. In addition, the leached nickel is extracted into the solvent LiX84i and then back extracted with hydrochloric acid to separate the trace metals. The precipitated nickel carbonate cake is subjected to a carbonation reaction with sodium carbonate, and the precipitated nickel carbonate cake is filtered, washed and calcined to produce high- It is possible to reduce the air pollution by cutting off the generated offgas in advance and drastically reduce the post-end collection facility due to the generation of gas. However, the above-mentioned processes have not been commercialized yet.
그리고 대한민국 등록특허 제10-1360292호에는 호열성 균주를 이용하여 석유 정제공정에서 발생하는 폐촉매를 생물학적으로 침출(bioleaching)시켜 니켈(Al), 알루미늄(Al), 철(Fe), 바나듐(V) 및 몰리브데늄(Mo)을 회수할 수 있는 방법을 제공하고 있고, 유가금속 침출반응시 반응시간을 단축하고 폐촉매의 분쇄처리 비용을 절감할 수 있으나, 이는 사용되는 미생물의 내구성 및 회수효율 등의 문제점이 있는 것으로 파악된다.Korean Patent No. 10-1360292 discloses a method of bioleaching a waste catalyst generated in a petroleum refining process by using a thermophilic strain to remove nickel, aluminum (Al), iron (Fe), vanadium (V ) And molybdenum (Mo) can be recovered. It is possible to reduce the reaction time and the pulverization treatment cost of the waste catalyst in the leaching of the metal-rich metal. However, the durability and the recovery efficiency And so on.
그 외에도 수산화 금속으로의 침전법이 있는데, 침전경향은 Fe+3 > Al+3 > Cr+2 > Zn+2 > Ni+2 > Fe+2 > Co+2 > Mn+2 > Mg+2 > Ca+2 등의 순으로 낮은 pH값에도 침전이 잘 발생되지만, Ni+2, Fe+2, Co+2 등은 침전경향이 너무 유사하여 선택성이 매우 낮아지게 된다.In addition, there is a precipitation of a metal hydroxide, precipitation trend Fe +3> Al +3> Cr +2 > Zn +2> Ni +2> Fe +2> Co +2> Mn +2> Mg +2> Ca + 2, and so on. However, Ni +2 , Fe +2 , Co + 2 and so on have very low selectivity due to the similar tendency of precipitation.
현재까지 다성분계 금속혼합용액에서 금속을 선택적으로 분리 회수하는 방법에는 Hydroxide 침전법, Sulfide 침전법, 용매추출법 등이 대표적인데, 용매추출법에도 용매의 종류에 따라 세분화되며, 이온교환수지법, 카르복실산 추출법, 아민수지법 등을 큰 범위에서의 용매추출법에 포함시키기도 한다. 이러한 방법들은 회수율이 좋으면 공침발생으로 순도가 낮은 단점이 있으며, 순도는 높지만 반응속도가 느리고 장치비가 많이 소요되는 여러 가지 문제점을 갖고 있다.Until now, typical methods for selectively separating and recovering metals from multi-component metal mixed solutions include hydroxide precipitation method, sulfide precipitation method, solvent extraction method, etc. In the solvent extraction method, it is subdivided according to the kind of solvent, and ion exchange resin method, Acid extraction method, and amine resin method may be included in the solvent extraction method in a large range. These methods have disadvantages in that the purity is low due to the occurrence of coprecipitation when the recovery rate is good, and there are various problems that the purity is high but the reaction rate is slow and the apparatus cost is high.
한편, 본 발명은 기존의 용매추출법과 침전법을 개선하기 위해 폐촉매에 존재하는 몰리브덴(Mo), 니켈(Ni), 코발트(Co), 철(Fe) 및 담체로 이용된 알루미나(Al2O3) 등을 무기산을 이용하여 몰리브덴(Mo)을 산화시키고, 용해성 물질인 니켈(Ni), 코발트(Co), 철(Fe)은 용액 내에 이온상태로 용해시킨 다음, 몰리브덴(Mo) 성분을 알카리 용액에 용해시키고 양이온 교환막이 설치된 전기투석시스템을 이용함으로써 몰리브덴(Mo) 성분뿐만 아니라 다른 금속성분들도 모두 회수하기 위한 복합기술이며, 사용된 산과 알카리를 회수하여 재사용함으로써 환경에 친화적인 습식공정기술을 개발하였다.In order to improve the conventional solvent extraction method and precipitation method, the present invention provides a method of recovering alumina (Al 2 O), which is used as a carrier, on a molybdenum (Mo), nickel (Ni), cobalt 3 ) and the like are dissolved in an ionic state by dissolving molybdenum (Mo) using an inorganic acid and soluble materials such as nickel (Ni), cobalt (Co) and iron (Fe) It is a complex technology for recovering not only molybdenum (Mo) component but also other metallic components by dissolving in solution and using electrodialysis system equipped with cation exchange membrane. By recovering and reusing acid and alkali used, environmentally friendly wet process technology Respectively.
본 발명의 목적은 기존의 용매추출법과 침전법을 개선하기 위한 것으로, 폐촉매에 존재하는 몰리브덴(Mo), 니켈(Ni), 코발트(Co), 철(Fe) 및 담체로 이용된 알루미나(Al2O3) 등을 무기산을 이용하여 몰리브덴(Mo)을 산화시키고, 용해성 물질인 니켈(Ni), 코발트(Co), 철(Fe)은 용액 내에 이온상태로 용해시킨 다음, 몰리브덴(Mo) 성분을 알카리 용액에 용해시키고 양이온 교환막이 설치된 전기투석시스템을 이용함으로써 몰리브덴(Mo) 성분뿐만 아니라 다른 금속성분들도 모두 회수하기 위한 복합기술이며, 이에 사용된 산과 알카리를 회수하여 재사용할 수 있는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정을 제공하는 것이다.It is an object of the present invention to improve the conventional solvent extraction method and precipitation method and to provide a method of recovering molybdenum (Mo), nickel (Ni), cobalt (Co), iron (Fe) 2 O 3) such as to using a mineral acid to oxidize the molybdenum (Mo), soluble material is nickel (Ni), cobalt (Co), iron (Fe) is dissolved in ion state in a solution, molybdenum (Mo) component Is a complex technology for recovering not only molybdenum (Mo) components but also other metallic components by using an electrodialysis system having a cation exchange membrane and dissolving them in an alkali solution, and recovering the acid and alkali used therefrom, And an environmentally friendly wet process for recovering molybdenum from the catalyst.
본 발명에 의한 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정은, 양극전해조와 음극전해조 사이에 양이온 교환막이 설치된 전기투석시스템을 이용하여 정유 탈황 폐촉매로부터 몰리브덴 회수방법에 있어서, 폐촉매 슬러리 속의 황화몰리브덴(MoS2)을 질산(HNO3)을 이용하여 전환반응을 수행하면, 몰리브덴(Mo) 성분은 산화몰리브덴(MoO3) 형태의 고형분으로 존재하고, 금속성분인 니켈(Ni), 코발트(Co), 철(Fe), 알루미나(Al2O3)는 질산(HNO3)에 용해되어 다성분계 금속용액을 형성하는 제1 단계; 상기 산화몰리브덴(MoO3) 형태의 고형분을 알카리 용액에 용해시킨 몰리브덴염(Na2MoO4)을 양극전해조에 투입하고 전기를 공급하면, 양극전해조에는 알카리 이온이 양이온 교환막을 통해 음극전해조로 이동하여 몰리브덴산(H2MoO4)이 생성되고, 음극전해조에는 알카리 용액이 생성되는 제2 단계; 상기 몰리브덴산(H2MoO4)을 여과하여 생성된 고형물은 건조하여 최종제품인 산화몰리브덴(MoO3)으로 회수하는 제3 단계로 이루어지는 것을 특징으로 한다.The eco-wet process for recovering molybdenum from the refined oil desulfurization catalyst according to the present invention is characterized in that in the molybdenum recovery method from the purified oil desulfurization spent catalyst using an electrodialysis system in which a cation exchange membrane is provided between the anode electrolyzer and the cathode electrolyzer, When molybdenum sulfide (MoS 2 ) is converted into nitric acid (HNO 3 ), the molybdenum (Mo) component is present as a solid component in the form of molybdenum oxide (MoO 3 ), and the metal components nickel (Ni), cobalt Co), iron (Fe), alumina (Al 2 O 3) is a first step of forming the metal component is dissolved in a solution of nitric acid (HNO 3); When molybdenum salt (Na 2 MoO 4 ) obtained by dissolving the solid component in the form of molybdenum oxide (MoO 3 ) in an alkali solution is supplied to the anode electrolytic cell and electricity is supplied, the alkaline ion moves to the anode electrolytic bath through the cation- A second step in which molybdic acid (H 2 MoO 4 ) is generated and an alkali solution is produced in the cathode electrolyzer; And a third step of filtering the molybdic acid (H 2 MoO 4 ) and drying the resulting solid to recover molybdenum oxide (MoO 3 ) as a final product.
또한, 상기 제1 단계에서의 황화몰리브덴(MoS2) 전환반응에서 발생하는 황산(H2SO4)은 소석회(Ca(OH)2)를 투입하여 황산석고(CaSO4)로 침전 수거하며, 이때 발생되는 NO기체는 공기 또는 산소를 투입하고 산화시켜 질산(HNO3)으로 전환시킨 후, 황화몰리브덴(MoS2) 전환반응에 재사용한다. 상기 제2 단계에서의 음극전해조에 생성된 알카리 용액은 폐촉매 슬러리에 포함된 산화몰리브덴(MoO3)을 용해하는 용해공정에 재사용하며, 상기 알카리 용액은 수산화나트륨(NaOH)을 사용하는 것이 바람직하다.In addition, sulfuric acid (H 2 SO 4 ) generated in the molybdenum sulfide (MoS 2 ) conversion reaction in the first step is precipitated with sulfuric acid gypsum (CaSO 4 ) by adding calcium hydroxide (Ca (OH) 2 ) The generated NO gas is converted into nitric acid (HNO 3 ) by introducing air or oxygen and oxidizing it, and then reused for conversion of molybdenum sulfide (MoS 2 ). The alkali solution generated in the anode electrolytic cell in the second step is reused in a dissolving step of dissolving molybdenum oxide (MoO 3 ) contained in the waste catalyst slurry, and the alkaline solution is preferably sodium hydroxide (NaOH) .
그리고 상기 제1 단계에서의 황화몰리브덴(MoS2) 전환반응에서 질산(HNO3)에 용해된 금속성분인 니켈(Ni), 코발트(Co), 철(Fe)은 용매추출법 또는 전기투석시스템을 통해 분리하는 것을 특징으로 하고 있다.In the first step, nickel (Ni), cobalt (Co), and iron (Fe), which are dissolved in nitric acid (HNO 3 ) in the molybdenum sulfide (MoS 2 ) conversion reaction, are separated by a solvent extraction method or an electrodialysis system And separates them.
본 발명의 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정은 로타리 킬른이나 다단 배소로를 사용한 건식배소방식을 사용하지 않고 무기산(HNO3)을 이용하여 황화합물(MoS2) 형태로 있는 존재하는 몰리브덴(Mo)을 산화몰리브덴(MoO3)으로 전환함에 따라 폐촉매와 공기를 고온에서 배소하기 위한 에너지는 물론 배소공정에서 발생하는 배기가스 처리를 위한 환경설비 비용이 절감되며, 또한 본 발명은 황화몰리브덴(MoS2) 전환반응에서 발생하는 황산(H2SO4)에 소석회(Ca(OH)2)를 투입하여 황산석고(CaSO4)로 침전 수거함으로써 환경에 유해한 황(S) 함량을 엄격하게 관리할 수 있고, 이때 발생되는 NO기체는 공기 또는 산소를 투입하고 산화시켜 질산(HNO3)으로 전환시킨 후, 황화몰리브덴(MoS2) 전환반응에 재사용함으로써 배출기체를 최소화할 수 있는 효과가 있다.Eco-friendly wet process for molybdenum is recovered from refinery desulfurization waste catalyst of the present invention rotary kiln or without the use of dry roasting method using a multi-stage roasting inorganic sulfur compounds using (HNO 3) (MoS 2) the presence of molybdenum, which in the form (Mo) is converted to molybdenum oxide (MoO 3 ), the energy for roasting the waste catalyst and air at a high temperature as well as the environmental facility cost for treating the exhaust gas generated in the roasting process is reduced. Ca (OH) 2 ) is added to the sulfuric acid (H 2 SO 4 ) generated in the conversion reaction (MoS 2 ) and precipitated with sulfuric acid gypsum (CaSO 4 ) to strictly control the sulfur content The NO gas is converted into nitric acid (HNO 3 ) by oxidizing and oxidizing air or oxygen, and then reused in the conversion reaction of molybdenum sulfide (MoS 2 ) There is an effect that can be changed.
이에 따라, 본 발명은 고순도의 몰리브덴(Mo) 성분을 선택적으로 회수하는 것이 가능하고 회수율이 높을 뿐만 아니라 니켈(Ni), 코발트(Co), 철(Fe)과 같은 금속성분들도 복합적으로 분리 회수할 수 있으며, 또한 양이온 교환막이 설치된 전기투석시스템을 이용함으로써 몰리브덴(Mo) 성분뿐만 아니라 이에 사용된 알카리 용액을 회수하여 재사용할 수 있어 환경에 매우 친화적인 장점이 있다.Accordingly, the present invention is capable of selectively recovering a high-purity molybdenum (Mo) component and not only has a high recovery rate, but also collects and collects metallic components such as nickel (Ni), cobalt (Co), and iron In addition, by using an electrodialysis system having a cation exchange membrane, molybdenum (Mo) components as well as alkaline solutions used therein can be recovered and reused, which is advantageous to the environment.
도 1은 본 발명에 의한 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정을 나타내는 구성도이다.FIG. 1 is a schematic view showing an environmentally friendly wet process for recovering molybdenum from an essential oil desulfurization catalyst according to the present invention.
본 발명은 양극전해조와 음극전해조 사이에 양이온 교환막이 설치된 전기투석시스템을 이용하여 정유 탈황 폐촉매로부터 몰리브덴 회수방법에 있어서, 폐촉매 슬러리 속의 황화몰리브덴(MoS2)을 질산(HNO3)을 이용하여 전환반응을 수행하면, 몰리브덴(Mo) 성분은 산화몰리브덴(MoO3) 형태의 고형분으로 존재하고, 금속성분인 니켈(Ni), 코발트(Co), 철(Fe), 알루미나(Al2O3)는 질산(HNO3)에 용해되어 다성분계 금속용액을 형성하는 제1 단계; 상기 산화몰리브덴(MoO3) 형태의 고형분을 알카리 용액에 용해시킨 몰리브덴염(Na2MoO4)을 양극전해조에 투입하고 전기를 공급하면, 양극전해조에는 알카리 이온이 양이온 교환막을 통해 음극전해조로 이동하여 몰리브덴산(H2MoO4)이 생성되고, 음극전해조에는 알카리 용액이 생성되는 제2 단계; 상기 몰리브덴산(H2MoO4)을 여과하여 생성된 고형물은 건조하여 최종 제품인 산화몰리브덴(MoO3)으로 회수하는 제3 단계로 이루어진다.The present invention relates to a method for recovering molybdenum from an essential desulfurization spent catalyst by using an electrodialysis system in which a cation exchange membrane is provided between a cathode electrolytic cell and a cathode electrolytic bath, characterized in that molybdenum sulfide (MoS 2 ) in the waste catalyst slurry is nitric acid (HNO 3 ) When the conversion reaction is carried out, the molybdenum (Mo) component is present as a solid content in the form of molybdenum oxide (MoO 3 ), and the metal components of nickel (Ni), cobalt (Co), iron (Fe), alumina (Al 2 O 3 ) A first step of dissolving in a nitric acid (HNO 3 ) to form a multi-component metal solution; When molybdenum salt (Na 2 MoO 4 ) obtained by dissolving the solid component in the form of molybdenum oxide (MoO 3 ) in an alkali solution is supplied to the anode electrolytic cell and electricity is supplied, the alkaline ion moves to the anode electrolytic bath through the cation- A second step in which molybdic acid (H 2 MoO 4 ) is generated and an alkali solution is produced in the cathode electrolyzer; The molybdic acid (H 2 MoO 4 ) is filtered and the resulting solid is dried and recovered as molybdenum oxide (MoO 3 ) as a final product.
이하에서는 도면을 참조하여 본 발명의 각 단계별 공정을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 예시하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, the process of each step of the present invention will be described in detail with reference to the drawings, which is intended to be illustrative of the invention so that those skilled in the art can easily carry out the invention, Quot; and " the "
도 1에 도시된 바와 같이, 본 발명에 의한 제1 단계공정은 폐촉매 슬러리 속의 황화몰리브덴(MoS2)을 질산(HNO3)을 이용하여 전환반응을 수행하면, 몰리브덴(Mo) 성분은 산화몰리브덴(MoO3) 형태의 고형분으로 존재하고, 금속성분인 니켈(Ni), 코발트(Co), 철(Fe), 알루미나(Al2O3)는 질산(HNO3)에 용해되어 다성분계 금속용액을 형성하게 된다.As shown in FIG. 1, in the first step of the present invention, when molybdenum sulfide (MoS 2 ) in the waste catalyst slurry is subjected to a conversion reaction using nitric acid (HNO 3 ), the molybdenum (Mo) (MoO 3) present in the form of a solid content, and the metal components of nickel (Ni), cobalt (Co), iron (Fe), alumina (Al 2 O 3) is dissolved in nitric acid (HNO 3) is a component metal solution Respectively.
상기 제1 단계공정은 본 발명이 저에너지 및 원가절감 공정임을 단적으로 보여주는데, 기존의 공정은 황화몰리브덴(MoS2)을 산화몰리브덴(MoO3)으로 산화시키기 위해 건식배소공정으로 로터리킬른 등을 이용하여 550 ~ 700 정도의 영역에서 공정을 수행하는 것이 보통인데, 산소 공급원으로 공기를 이용하기 때문에 공기 승온에 따른 에너지 소비가 과다하게 요구되고 배소공정에서 발생하는 배기가스처리를 위해 많은 환경설비가 소요된다.In the first step, the present invention shows that the present invention is a low energy and cost saving process. In the conventional process, a dry roasting process is used to oxidize molybdenum sulfide (MoS 2 ) to molybdenum oxide (MoO 3 ) To 700 ° C. Since air is used as an oxygen supply source, energy consumption due to an increase in air temperature is excessively required, and a lot of environmental facilities are required to process the exhaust gas generated in the roasting process.
한편, 본 발명에서는 황화몰리브덴(MoS2) 전환반응에서 발생하는 황산(H2SO4)에 소석회(Ca(OH)2)를 투입하여 황산석고(CaSO4)로 침전 수거함으로써 환경에 유해한 황(S) 함량을 엄격하게 관리할 수 있고, 이 황(S) 성분을 제거하는 이유는 상업용 산화몰리브덴 제조에서 황(S) 함량이 엄격히 관리되고 있기 때문이다. In the present invention, calcium hydroxide (Ca (OH) 2 ) is added to sulfuric acid (H 2 SO 4 ) generated in the molybdenum sulfide (MoS 2 ) conversion reaction and precipitated with sulfuric acid gypsum (CaSO 4 ) S) content can be strictly controlled, and the reason why the sulfur (S) component is removed is that the sulfur (S) content is strictly controlled in the production of commercial molybdenum oxide.
그리고 상기 황화몰리브덴(MoS2) 전환반응에서 발생되는 NO기체는 공기 또는 산소를 투입하고 산화시켜 질산(HNO3)으로 전환시킨 후, 황화몰리브덴(MoS2) 전환반응에 재사용하는 것이 바람직한데, 상기 질소산화물 기체를 질산으로 전환시킴으로써 배출가스를 최소화할 수 있어 소규모 설비로 친환경 시스템을 형성할 수 있기 때문에 배출가스 총량이 기존 공정의 1,000분의 1가량으로 줄어들게 되는 효과를 나타낼 수 있다.And together the molybdenum sulfide (MoS 2) NO gas generated in the conversion reaction is preferred to inject air or oxygen and then was converted to nitric acid (HNO 3) oxidation, reuse the molybdenum sulfide (MoS 2) conversion reaction, the By converting the nitrogen oxide gas into nitric acid, the exhaust gas can be minimized and an eco-friendly system can be formed with a small-scale facility, so that the total amount of exhaust gas can be reduced to about one thousandth of that of the conventional process.
참고로, 상기 제1 단계공정에서 발생되는 NO기체가 질산(HNO3)으로 생성되는 반응은 아래 식(1)과 같이 진행되며, 몰리브덴(Mo) 1mol 당 습식배소공정에 4.5mol의 산소가 필요하고 6mol의 NO가 발생하게 된다.For reference, the reaction of the NO gas generated in the first step process with nitric acid (HNO 3 ) proceeds as shown in the following formula (1), and 4.5 mol of oxygen is required for the wet roasting process per mol of molybdenum (Mo) And 6 mol of NO is generated.
6NO + 4.5O2 + 3H2O → 6HNO3 ----- (1)6NO + 4.5O 2 + 3H 2 O? 6HNO 3 ----- (1)
또한, 제1 단계공정에서의 황화몰리브덴(MoS2) 전환반응에서 질산(HNO3)에 용해된 금속성분인 니켈(Ni), 코발트(Co), 철(Fe)은 기존의 용매추출법 또는 본 발명자가 개발한 전기투석시스템을 통해 분리하여 회수하게 되는바, 전기투석시스템에서의 1차 전기석출공정은 양극전해조에 물을 투입하고 음극전해조에는 철(Fe), 코발트(Co), 니켈(Ni) 등을 함유하는 다성분계 금속용액과 다염기 카복실산을 투입하고 전기를 공급하면, 음이온 교환막을 통해 염소이온이 양극전해조로 이동하여 염산(HCl)이 생성되며, 음극전해조에는 철(Fe)이 석출된다.Nickel (Ni), cobalt (Co) and iron (Fe), which are metal components dissolved in nitric acid (HNO 3 ) in the molybdenum sulfide (MoS 2 ) conversion reaction in the first step process, (Fe), cobalt (Co), nickel (Ni) and the like are added to the anode electrolytic cell, while the first electrochemical deposition process in the electrodialysis system inputs water into the anode electrolytic cell, (HCl) is generated through the anion exchange membrane, and iron (Fe) is precipitated in the anode electrolytic cell when the polybasic carboxylic acid and the polybasic carboxylic acid are supplied and electricity is supplied through the anion exchange membrane .
상기 다염기 카복실산은 옥살산(oxalic acid, C2H2O4), 시트릭산(citric acid, C6H8O7) 중에서 선택되는 어느 1종을 사용하는 것이 바람직한 것으로 조사되었고 이들의 수화물 또는 무수물 형태 모두 사용가능하며, 이는 특정 금속이온에 대하여 착화합물을 형성하는 성질을 가지고 있어 다성분계 금속용액 내에서 우선적으로 코발트(Co) 및 니켈(Ni)과 착화합물을 형성함으로써 이들을 선택적으로 침전시키게 된다. 그리고 다염기 카복실산의 사용량은 코발트(Co) 이온에 대비하여 2 ~ 5당량으로 사용하는 것이 바람직하며, 그 사용량이 2당량 미만인 경우 회수율이 떨어지는 문제가 발생하게 되고 5당량 초과 시엔 코발트(Co) 이외의 금속도 공침하는 문제가 발생될 우려가 있다.It is preferable that the polybasic carboxylic acid is any one selected from the group consisting of oxalic acid (C 2 H 2 O 4 ), citric acid (C 6 H 8 O 7 ), and their hydrates or anhydrides Type, which has the property of forming a complex with respect to a specific metal ion, and preferentially precipitates them by forming a complex with cobalt (Co) and nickel (Ni) in a multi-component metal solution. The amount of the polybasic carboxylic acid is preferably 2 to 5 equivalents relative to the amount of the cobalt (Co) ion. When the amount of the polybasic carboxylic acid is less than 2 equivalents, the recovery rate is lowered. When the amount is more than 5 equivalents, There is a possibility that a problem of co-precipitation of the metal may occur.
그리고 본 발명에서 질산(HNO3)을 사용하는 주된 이유로 상업화를 고려하였는데, 스텐재질은 반응용기나 기타 장치들에 적용하기 용이하고 이 경우에 황산(H2SO4) 또는 염산(HCl)은 반응기 혹은 생산장치의 유지 관리에 많은 제약을 받기 때문에 사용을 자제하였다. 또한, 질산(HNO3) 가열의 장점으로는 공정이 간단하여 생산 설비비가 적게 소요되고 생산속도가 빠르다는 장점이 있지만, 수산화나트륨(NaOH)과 질산(HNO3)의 소비량 증가로 전체적으로 소모되는 약품비용이 부담으로 작용한다. 특히, 몰리브덴(Mo) 또는 니켈(Ni), 코발트(Co) 등의 유가자원의 국제가격에 따라 약품비용이 적게는 30%에서 많게는 50%까지 소모될 수 있기 때문에 사용에 신중을 기해야 한다.The main reason for using nitric acid (HNO 3 ) in the present invention is commercialization. The stainless material is easy to apply to reaction vessels and other devices. In this case, sulfuric acid (H 2 SO 4 ) or hydrochloric acid (HCl) Or because it is subject to a lot of restrictions on the maintenance of production equipment. The advantages of nitric acid (HNO 3 ) heating are that the process is simple, the equipment cost is low and the production speed is fast. However, the consumption of sodium hydroxide (NaOH) and nitric acid (HNO 3 ) Costs are a burden. In particular, due to the international price of molten metals such as molybdenum (Mo) or nickel (Ni), cobalt (Co), drug costs may be as low as 30% to as much as 50%.
상기와 같이 철(Fe)이 석출된 후의 코발트(Co), 니켈(Ni) 화합물 합성공정은 상기 1차 전기석출공정에서 생성된 음극전해조의 여액을 가열하여 Co-카복실산 및 Ni-카복실산 화합물이 침전되는 과정으로서, 상기 카복실산 화합물에 의해 코발트 및 니켈은 코발트옥살레이트, 니켈옥살레이트로 착화합물을 형성하거나 코발트시트레이트, 니켈시트레이트 등과 같은 카복실산 화합물 상태로 합성되어 Co, Ni 화합물을 회수하게 되며, 이에 연속적으로 Co, Ni 화합물 여과공정을 통해 여액과 고액분리하는 과정을 거치게 된다. 상기 Co, Ni 화합물은 수용액에 대한 불용성 화합물로 일반 여과설비로 쉽게 여과할 수 있으며, 세정이 용이하여 불순물의 혼입을 최소화할 수 있다.The step of synthesizing cobalt (Co) and nickel (Ni) compound after iron (Fe) is precipitated as described above is a step of heating the filtrate of the negative electrode electrolytic bath generated in the first electrodeposition step to precipitate Co-carboxylic acid and Ni- Wherein the cobalt and nickel are converted to a complex compound with cobalt oxalate or nickel oxalate or synthesized with a carboxylic acid compound such as cobalt citrate or nickel citrate to recover Co and Ni compounds, The filtrate is subjected to solid and liquid separation through filtration of Co and Ni compounds continuously. The Co and Ni compounds are insoluble compounds in an aqueous solution, and can easily be filtered by a general filtration facility, and cleaning can be easily performed, so that incorporation of impurities can be minimized.
또한, 상기 여액은 50 ~ 70℃의 온도로 가열한 상태에서 침전반응을 수행함으로써 불순물인 나트륨염의 용해도가 상승되어 코발트 화합물에 대한 선택성을 더욱 높일 수 있는바, 상기 반응이 50℃ 미만에서 행해지는 경우 카복실산 화합물의 순도가 저하될 우려가 있고 70℃를 초과할 경우 회수율이 저하되는 문제가 있어 바람직하지 않다.In addition, since the solubility of the sodium salt as the impurity is increased by performing the precipitation reaction in the state where the filtrate is heated at a temperature of 50 to 70 ° C, the selectivity to the cobalt compound can be further increased, There is a possibility that the purity of the carboxylic acid compound is lowered, and when it exceeds 70 캜, the recovery rate is lowered.
한편, 본 발명은 상기 Co, Ni 화합물 여과공정에서 분리된 Co-카복실산 및 Ni-카복실산 화합물을 질산(HNO3)에 재용해한 후, 양극전해조에 물을 투입하고 음극전해조에 상기 용액을 투입하고 전기를 공급하면, 음이온 교환막을 통해 염소이온이 양극전해조로 이동하여 질산(HNO3)이 생성되며, 음극전해조에는 초기에 코발트(Co)가 석출되고 말기에 니켈(Ni)이 석출되는 2차 전기석출공정을 거쳐 코발트(Co)와 니켈(Ni)을 회수하게 된다. 이는 음이온 교환막을 통해 염소이온이 양극전해조로 이동하여 질산(HNO3)이 생성되고, 금속성분의 전기음성도 차이에 따라 이온화 경향이 큰 코발트(Co)가 초기에 석출되고 이온화 경향이 작은 니켈(Ni)이 말기에 석출되는 과정을 거치게 된다.Meanwhile, in the present invention, the Co-carboxylic acid and the Ni-carboxylic acid compound separated in the Co and Ni compound filtration process are redissolved in nitric acid (HNO 3 ), water is introduced into the anode electrolytic bath, the solution is introduced into the cathode electrolytic bath When electricity is supplied, the chloride ion moves to the anode electrolytic cell through the anion exchange membrane to generate nitric acid (HNO 3 ), and the cathode electrolytic cell is charged with cobalt (Co) in the initial stage and nickel After the precipitation process, cobalt (Co) and nickel (Ni) are recovered. This is because the chloride ion moves to the anode electrolytic cell through the anion exchange membrane and nitric acid (HNO 3 ) is generated. The cobalt (Co) having a tendency of ionization tends to precipitate at an early stage according to the electronegativity difference of the metal component, Ni) is deposited at the end of the process.
위와 같이, 본 공정에서 유입되는 석출여액에서 니켈(Ni), 코발트(Co)를 회수하기 위한 전처리 공정으로 석출여액 중 니켈(Ni), 코발트(Co)에 대한 성분 분리 전에 철(Fe) 성분이 제거되어야 용매 재사용률이 증가하는데, 일반적인 용매에 철(Fe) 성분이 포함되면 탈거가 어려워 재사용률이 급격히 감소되기 때문이다.As described above, in the pretreatment step for recovering nickel (Ni) and cobalt (Co) from the precipitation filtrate flowing in the present process, iron (Fe) component is removed before the components are separated from nickel (Ni) and cobalt This is because the use rate of the solvent is increased when the iron (Fe) component is contained in a general solvent, and the re-use rate is rapidly reduced because it is difficult to remove.
다음으로, 제2 단계공정은 상기 산화몰리브덴(MoO3) 형태의 고형분을 알카리 용액에 용해시킨 몰리브덴염(Na2MoO4)을 양극전해조에 투입하고 전기를 공급하면, 양극전해조에는 알카리 이온이 양이온 교환막을 통해 음극전해조로 이동하여 몰리브덴산(H2MoO4)이 생성되고, 음극전해조에는 알카리 용액이 생성되며, 제3 단계공정은 상기 몰리브덴산(H2MoO4)을 여과하여 생성된 고형물은 건조하여 최종 제품인 산화몰리브덴(MoO3)으로 회수하는 과정으로서, 이에 관하여는 앞서본 제1 단계공정에서의 전기투석시스템을 이용한다.Next, in the second step, a molybdenum salt (Na 2 MoO 4 ) obtained by dissolving the solid component in the form of molybdenum oxide (MoO 3 ) in an alkali solution is introduced into a cathode electrolytic cell and electricity is supplied. In the anode electrolytic bath, (H 2 MoO 4 ) is generated through the exchange membrane, and an alkaline solution is produced in the cathode electrolyzer. In the third step, the solids produced by filtering the molybdic acid (H 2 MoO 4 ) And drying it to recover molybdenum oxide (MoO 3 ) as a final product. In this regard, the electrodialysis system in the first step is used.
상기 제2 단계공정에 있어 산화몰리브덴(MoO3) 형태의 고형분을 알카리 용액에 용해시키면 몰리브덴염(Na2MoO4)이 생성되고, 그 용해과정에서 산화물이나 납(Pb) 등의 산불용성 물질을 제거할 수 있게 된다.Molybdenum salt (Na 2 MoO 4 ) is produced by dissolving the solid component in the form of molybdenum oxide (MoO 3 ) in the alkali solution in the second step process, and an acid insoluble substance such as oxide or lead (Pb) Can be removed.
상기와 같이 수산화나트륨(NaOH)으로 용해한 용해액에는 몰리브덴(Mo) 성분이 몰리브덴염(Na2MoO4)의 형태로 존재하는데, 이 몰리브덴염이 용해되어 있는 용액을 양극전해조와 음극전해조 사이에 양이온 교환막이 설치된 전기투석시스템을 이용하여 양극전해조에 투입하고 전기를 공급하면, 양극전해조와 음극전해조에 각각 몰리브덴산(H2MoO4)과 알카리 용액이 생성되는데, 본 발명에서는 상기 전기석출공정에 공급되는 전기는 직류전압 3 ~ 15V 범위로 일정하게 조절한 정전압법으로 용액의 pH와 전압을 유지하고 전기석출을 시행함으로써 몰리브덴(Mo), 니켈(Ni), 코발트(Co), 철(Fe) 성분의 선택성 및 순도를 향상시킬 수 있는 것으로 연구되었다.As described above, in the solution dissolving with sodium hydroxide (NaOH), a molybdenum (Mo) component is present in the form of a molybdenum salt (Na 2 MoO 4 ), and a solution in which the molybdenum salt is dissolved is placed between a positive electrode electrolytic bath and a negative electrode electrolytic bath. Molybdic acid (H 2 MoO 4 ) and an alkaline solution are generated in the anode electrolyzer and the cathode electrolyzer, respectively, when the electrolytic cell is charged into the anode electrolyzer using the exchange membrane and electricity is supplied. In the present invention, (Mo), nickel (Ni), cobalt (Co), and iron (Fe) components by electrostatic precipitation by maintaining the pH and voltage of the solution by a constant voltage method, And the selectivity and purity of the polymer can be improved.
또한, 상기 제2 단계공정에서의 음극전해조에 생성된 알카리 용액은 폐촉매 슬러리에 포함된 산화몰리브덴(MoO3)을 용해하는 용해공정에 재사용함으로써 환경에 매우 친화적이고 경제적이며, 또한 상기 제2 단계공정에서의 알카리 용액은 수산화나트륨(NaOH)을 사용하는 것이 고순도의 몰리브덴(Mo) 성분을 선택적으로 회수하는 것이 가능할 뿐만 아니라 회수율도 높은 것으로 조사되었다. 나아가 니켈(Ni), 코발트(Co), 철(Fe)과 같은 금속성분들도 복합적으로 분리 회수할 수 있는 장점이 있다.In addition, the alkali solution produced in the cathode electrolytic bath in the second step process is reused in the dissolving process for dissolving molybdenum oxide (MoO 3 ) contained in the waste catalyst slurry, so that it is very environmentally friendly and economical, The use of sodium hydroxide (NaOH) in the alkali solution in the process not only enables the selective recovery of the high purity molybdenum (Mo) component, but also the recovery rate is high. Furthermore, metallic materials such as nickel (Ni), cobalt (Co), and iron (Fe) can also be separated and recovered in a complex manner.
이상에서 살펴본 바와 같이, 본 발명의 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정은 화학적 반응(습식 배소)에 의해 MoS2로부터 고순도 MoO3(Mo 63% 이상) 생산이 가능하고 황(S)을 제품화하는 것이 가능한 공정으로, 고불순물(high Cu, Pb 등)이 함유되어 있는 폐촉매 처리 및 MoS2 60% 이하의 저품위 폐촉매로부터 몰리브덴 성분을 회수할 수 있으며, 또 MoS2을 MoO3로 가공할 시 회수율을 98% 이상 정도로 실현할 수 있으므로 환경에 친화적인 공정이라 할 수 있다.As described above, the environmentally-friendly wet process for recovering molybdenum from the refinery-desulfurized spent catalyst of the present invention can produce high-purity MoO 3 (Mo 63% or more) from MoS 2 by chemical reaction (wet roasting) (Molybdenum component) can be recovered from waste catalyst treatment containing high impurities (high Cu, Pb, etc.) and low-grade waste catalyst of MoS 2 60% or less, and MoS 2 can be recovered as MoO 3 It is possible to realize a recovery rate of 98% or more at the time of processing, which is an environmentally friendly process.
또한, 본 발명은 MoS2가 화학적 반응를 통해 MoO3로 전환되는 초기 가동 에너지 외에는 대부분의 공정이 자체 반응열로 가동되기 때문에 탁월한 에너지 효율은 물론 모든 유용 원료에 대한 회수 및 제품화가 가능하기 때문에 매우 경제적인 공정임을 알 수 있다.In addition, since most of the processes are operated by their own reaction heat other than the initial operating energy at which MoS 2 is converted into MoO 3 through chemical reaction, the present invention can provide excellent economic efficiency as well as recovery and commercialization of all useful raw materials. Process.
따라서 본 발명의 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정으로 제조된 산화몰리브덴(MoO3)은 촉매를 이용하여 나노상태의 몰리브덴(Mo)을 제조하기 위한 원료 등 다양한 용도와 형태로 사용되어 질 수 있다.Accordingly, molybdenum oxide (MoO 3 ) produced by the environmentally-friendly wet process for recovering molybdenum from the refined deasphalted spent catalyst of the present invention is used in various applications and forms such as raw materials for producing nano-state molybdenum (Mo) Can be.
Claims (6)
폐촉매 슬러리 속의 황화몰리브덴(MoS2)을 질산(HNO3)을 이용하여 전환반응을 수행하면, 몰리브덴(Mo) 성분은 산화몰리브덴(MoO3) 형태의 고형분으로 존재하고, 금속성분인 니켈(Ni), 코발트(Co), 철(Fe), 알루미나(Al2O3)는 질산(HNO3)에 용해되어 다성분계 금속용액을 형성하는 제1 단계;
상기 산화몰리브덴(MoO3) 형태의 고형분을 알카리 용액에 용해시킨 몰리브덴염(Na2MoO4)을 양극전해조에 투입하고 전기를 공급하면, 양극전해조에는 알카리 이온이 양이온 교환막을 통해 음극전해조로 이동하여 몰리브덴산(H2MoO4)이 생성되고, 음극전해조에는 알카리 용액이 생성되는 제2 단계;
상기 몰리브덴산(H2MoO4)을 여과하여 생성된 고형물은 건조하여 최종 제품인 산화몰리브덴(MoO3)으로 회수하는 제3 단계;
로 이루어지는 것을 특징으로 하는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정.
A method for recovering molybdenum from an essential desulfurization spent catalyst by using an electrodialysis system in which a cation exchange membrane is provided between a cathode electrolyzer and a cathode electrolyzer,
When molybdenum sulfide (MoS 2 ) in the waste catalyst slurry is subjected to a conversion reaction using nitric acid (HNO 3 ), the molybdenum (Mo) component is present as solid content in the form of molybdenum oxide (MoO 3 ) ), Cobalt (Co), iron (Fe), and alumina (Al 2 O 3 ) are dissolved in nitric acid (HNO 3 ) to form a multi-component metal solution;
When molybdenum salt (Na 2 MoO 4 ) obtained by dissolving the solid component in the form of molybdenum oxide (MoO 3 ) in an alkali solution is supplied to the anode electrolytic cell and electricity is supplied, the alkaline ion moves to the anode electrolytic bath through the cation- A second step in which molybdic acid (H 2 MoO 4 ) is generated and an alkali solution is produced in the cathode electrolyzer;
A third step of filtering the molybdic acid (H 2 MoO 4 ) and drying the resulting solid to recover molybdenum oxide (MoO 3 ) as a final product;
And an eco-friendly wet process for recovering molybdenum from an essential hydrodesulfurized waste catalyst.
상기 제1 단계에서의 황화몰리브덴(MoS2) 전환반응에서 발생하는 황산(H2SO4)은 소석회(Ca(OH)2)를 투입하여 황산석고(CaSO4)로 침전 수거하는 것을 특징으로 하는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정.
The method according to claim 1,
Wherein the sulfuric acid (H 2 SO 4 ) generated in the molybdenum sulfide (MoS 2 ) conversion reaction in the first step is precipitated with calcium sulfate (CaSO 4 ) by adding calcium hydroxide (Ca (OH) 2 ) Environmentally friendly wet process for recovery of molybdenum from refinery oil desulfurized spent catalyst.
상기 제1 단계에서의 황화몰리브덴(MoS2) 전환반응에서 발생되는 NO기체는 공기 또는 산소를 투입하고 산화시켜 질산(HNO3)으로 전환시킨 후, 황화몰리브덴(MoS2) 전환반응에 재사용하는 것을 특징으로 하는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정.
The method according to claim 1,
The NO gas generated in the molybdenum sulfide (MoS 2 ) conversion reaction in the first step is converted into nitric acid (HNO 3 ) by introducing air or oxygen and oxidizing it, and then reusing it for molybdenum sulfide (MoS 2 ) conversion reaction An environmentally friendly wet process for recovering molybdenum from a petroleum refinery waste catalyst.
상기 제2 단계에서의 음극전해조에 생성된 알카리 용액은 폐촉매 슬러리에 포함된 산화몰리브덴(MoO3)을 용해하는 용해공정에 재사용하는 것을 특징으로 하는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정.
The method according to claim 1,
Wherein the alkaline solution produced in the anode electrolytic cell in the second step is reused in a dissolving step for dissolving molybdenum oxide (MoO 3 ) contained in the waste catalyst slurry. .
상기 제2 단계에서 사용되는 알카리 용액은 수산화나트륨(NaOH)인 것을 특징으로 하는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정.
5. The method according to any one of claims 1 to 4,
Wherein the alkaline solution used in the second step is sodium hydroxide (NaOH).
상기 제1 단계에서의 황화몰리브덴(MoS2) 전환반응에서 질산(HNO3)에 용해된 금속성분인 니켈(Ni), 코발트(Co), 철(Fe)은 용매추출법 또는 전기투석시스템을 통해 분리하는 것을 특징으로 하는 정유 탈황 폐촉매로부터 몰리브덴 회수를 위한 친환경 습식공정.
The method according to claim 1,
Nickel (Ni), cobalt (Co), and iron (Fe), which are metal components dissolved in nitric acid (HNO 3 ) in the conversion of molybdenum sulfide (MoS 2 ) in the first step are separated by a solvent extraction method or an electrodialysis system Wherein the molten metal is recovered from the desulfurized waste catalyst.
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