CN100347318C - Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst - Google Patents
Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst Download PDFInfo
- Publication number
- CN100347318C CN100347318C CNB2005100315159A CN200510031515A CN100347318C CN 100347318 C CN100347318 C CN 100347318C CN B2005100315159 A CNB2005100315159 A CN B2005100315159A CN 200510031515 A CN200510031515 A CN 200510031515A CN 100347318 C CN100347318 C CN 100347318C
- Authority
- CN
- China
- Prior art keywords
- cobalt
- molybdenum
- extraction
- useless
- separating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010941 cobalt Substances 0.000 title claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 57
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011733 molybdenum Substances 0.000 claims abstract description 63
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 63
- 238000000605 extraction Methods 0.000 claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000003350 kerosene Substances 0.000 claims abstract description 9
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- 230000001172 regenerating effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims 3
- HOYKPPXKLRXDBR-UHFFFAOYSA-N [O].[Co].[Co] Chemical class [O].[Co].[Co] HOYKPPXKLRXDBR-UHFFFAOYSA-N 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002893 slag Substances 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 2
- 239000012467 final product Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for separating and recovering cobalt and molybdenum from waste cobalt-molybdenum catalyst, which mainly comprises the techniques of acid dissolution, molybdenum extraction, cobalt extraction, etc.: the calcined and comminuted powdery material of the waste cobalt-molybdenum catalyst is dissolved by concentrated hydrochloric acid for preparing acid dissolved clean solution, the molybdenum is extracted from the acid dissolved clean solution by the mixed liquor of tributyl phosphate and kerosene, and the cobalt is extracted from raffinate by trioctylamine solvent oil. With the technological method of the present invention, the yields of the cobalt and the molybdenum separated from the waste cobalt-molybdenum catalyst are high, the actual yield of the cobalt is more than 99.5 percent, and the actual yield of the molybdenum is more than 99.2 percent; the mutual separation among the elements is complete, and the final product quality is good; no process waste water and waste gas are discharged in the integral process, only small amount of waste slag is discharged in the technique of acid dissolution, the amount of the discharged waste slag which comprises less than 0.1 percent of cobalt oxide and less than 1.5 percent of molybdenum oxide is 2 percent of the amount of processed waste material, and the threat of the toxicity of the waste cobalt-molybdenum catalyst to the environment is eliminated.
Description
Technical field
The present invention relates to the method for comprehensive utilization of the toxic solid waste of a kind of chemical industry, particularly a kind of from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum.
Background technology
Useless cobalt-molybdenum catalyst results from the hydrodesulfurization process of the unifining process of refining of petroleum and oil head, gas head synthetic ammonia the earliest, contains cobalt oxide＞3%, molybdenum oxide＞10%, and the content of cobalt molybdenum is higher.Along with the development of technology, the content of cobalt molybdenum is more and more lower in the useless cobalt-molybdenum catalyst.Particularly at China's the mid-80, owing to successfully develop and be applied to the wide temperature shift of the anti-sulphur catalyzer of medium and small nitrogen fertilizer, its useless cobalt-molybdenum catalyst contains cobalt oxide＜1.5%, molybdenum oxide＜7%.After 1998, to the useless cobalt-molybdenum catalyst of the low levels that contains cobalt oxide＜1.5%, molybdenum oxide＜7%, unmanned purchase because extraction cost is high.At that time, the road was outwelled or filled out with the useless cobalt-molybdenum catalyst of this low levels by a lot of nitrogen fertilizer plants in the whole nation as rubbish.The whole nation only has 2～3 families that the industrialization retrieving arrangement of handling the useless cobalt-molybdenum catalyst of this low levels is arranged now, the imperial Fine Chemical Works in sky as inorganic saltworks of tafelberg, Henan Zhanhe District and Tianjin Hangu District, they have discharged waste residue after a large amount of processing, waste residue amount after the processing of its discharge approximates the treatment capacity of useless cobalt-molybdenum catalyst, chemically examine through the waste residue that they are discharged, contain cobalt oxide in the waste residue: 1.2～1.5%, molybdenum oxide: 1.3～2.0%.Obviously, it reclaims cobalt, and the yield of molybdenum also is lower than 80%, and a large amount of alumina catalyst supports do not utilize, poor effect, and the toxicity of spent catalyst remains unchanged to the threat of environment.
Can the method that whole elements reclaim there be " chemical industry environmental protection " 2004-24 (2): the 134-137 page or leaf, the alkali fusion of introducing in " alkali fusion reclaims cobalt, molybdenum and the aluminium in the spent catalyst " of work such as Liu Jin, its method is: take by weighing a certain amount of useless cobalt-molybdenum catalyst, add yellow soda ash and mix the back high-temperature roasting; The frit that roasting is formed leaches (making the meta-aluminate pass into solution that generates behind the alkali fusion), filters, separates with boiling water, the black slag that obtains containing the filtrate of meta-aluminate and Sodium orthomolybdate and contain ferro-cobalt; Filtrate neutralizes with sulfuric acid, transfers pH to 6～7, and aluminium hydroxide forms precipitation and separates out; Filtrate is concentrated through heating, and separates out sodium sulfate crystal, remaining filtrate is continued condensing crystal can obtain Sodium orthomolybdate; Boil with dilute sulphuric acid and to soak the black slag that contains ferro-cobalt, cobalt and iron all enter solution, transfer filtrate pH to 4～5 with alkali, and the iron in the filtrate forms ferric hydroxide precipitate and is removed; Continuation has the cobaltous hydroxide precipitation to form with adjusting PH with base to 9, and heat treated can obtain cobalt oxide.But add sulfuric acid precipitation aluminium in the alkali fusion, produce a large amount of aluminum hydroxide precipitations, a large amount of mother liquors, filtration washing difficulty are carried in absorption secretly.The purity of product aluminium hydroxide only is 90.9%, oxidation of impurities molybdenum＞0.5%, Na
2SO
4＞7%, the rate of recovery of molybdenum is difficult to surpass 80%, and to consume a large amount of sulfuric acid, soda ash could be produced the sodium sulfate of cheapness, the cost height, output is low.
The method that can reclaim whole elements also has potassium hydroxide dipping, roasting, water logging of introducing in " the cobalt-molybdenum spent catalyst comprehensive utilizating research " of work such as Cui Yan in " inorganic chemicals industry " 2002 01 34 (1) phase 36-38 pages or leaves, the actual recovered rate of molybdenum is lower than 90%, the actual recovered rate of sulfuric acid acidation precipitation molybdic acid is about 95%, the overall rate yield of molybdenum is lower than 85%, because the separation of molybdenum is incomplete, molybdenum oxide content is greater than 1.0% in the sodium aluminate, quality is not good, the repeated impregnations roasting, the energy consumption height, labour intensity is big, and product needs to purify repeatedly could be qualified.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art and provide a kind of from useless cobalt-molybdenum catalyst the method for separation of cobalt, molybdenum, realize that cobalt, the molybdenum in cobalt, the molybdenum spent catalyst separates fully, and rationally utilize.
Technical scheme of the present invention is: to be the useless cobalt that will pulverize through roasting, molybdenum catalyst powder make sour molten clear feed liquid with concentrated hydrochloric acid acid is molten to the method for separation of cobalt, molybdenum from useless cobalt-molybdenum catalyst, with the mixed solution extraction molybdenum of the molten clear feed liquid of acid with tributyl phosphate and kerosene, raffinate is extracting cobalt with the trioctylamine solvent oil.
The further technical scheme of the present invention is: the method for separation of cobalt, molybdenum specifically comprises following technology from useless cobalt-molybdenum catalyst:
(1), acid is molten: will be molten with concentrated hydrochloric acid acid through useless cobalt, molybdenum catalyst powder that roasting is pulverized, cross and make sour molten clear feed liquid after filtering to remove waste residue;
(2), extraction molybdenum: the above-mentioned sour molten clear feed liquid that makes is extracted with extraction agent I, get raffinate I and load extraction agent I, load extraction agent I with concentrated hydrochloric acid washing and back extraction after, obtain strip liquor I, washings I and regenerating extracting agent I, the further Separation of Molybdenum of strip liquor I, iron, make ammonium molybdate, Sodium orthomolybdate, ferric oxide more as required, the volume ratio that described extraction agent I composition is tributyl phosphate, kerosene is 20～80: 80～20;
(3), extraction cobalt: the raffinate I that obtains is previously extracted with extraction agent II, get raffinate II and load extraction agent II, load extraction agent II with concentrated hydrochloric acid washing and back extraction after, get strip liquor II, cleaning solution II and regenerating extracting agent II, strip liquor II makes cobalt salt series such as cobalt chloride, cobaltous carbonate, cobaltous hydroxide, cobalt oxide more as required, and described extraction agent II composition is 0.01～0.5mol trioctylamine solvent oil solution.
The further again technical scheme of the present invention is: will use more than the concentrated hydrochloric acid acid of stoichiometry 5% molten through useless cobalt, molybdenum catalyst powder that roasting is pulverized.
The present invention further technical scheme is: the useless cobalt that will pulverize through roasting, the concentrated hydrochloric acid acid that molybdenum catalyst powder concentration is 18-26% are molten.
Washings I and cleaning solution II can be returned sour molten operation and be used for the molten clear feed liquid of next relieving haperacidity.
Regenerating extracting agent I can return extraction molybdenum operation and recycle; Regenerating extracting agent II can return extraction cobalt operation and recycle.
The present invention compared with prior art has following characteristics: utilize processing method of the present invention separation of cobalt from useless cobalt-molybdenum catalyst, the yield height of molybdenum, the actual recovery of cobalt is more than 99.5%, the actual recovery of molybdenum is more than 99.2%, each element separates fully each other, end product quality is good, whole process does not have the processing wastewater exhaust gas emission, only there is a small amount of waste residue to discharge in the molten operation of acid, the waste residue amount of discharging is only for handling 2% of waste material amount, contain cobalt oxide＜0.1% in the waste residue of discharging, contain molybdenum oxide＜1.5%, eliminated useless cobalt, the toxicity of molybdenum catalyst is to the threat of environment.
Embodiment
Embodiment one
To be the useless cobalt that will pulverize through roasting, molybdenum catalyst powder make sour molten clear feed liquid with concentrated hydrochloric acid acid is molten to the method for separation of cobalt, molybdenum from useless cobalt-molybdenum catalyst, with the mixed solution extraction molybdenum of the molten clear feed liquid of acid with tributyl phosphate and kerosene, raffinate is extracting cobalt with the trioctylamine solvent oil; Specifically comprise following technology:
(1), acid is molten: (main composition is an aluminum oxide for useless cobalt, the molybdenum catalyst powder that will pulverize through roasting, potassium oxide: 4-8%, cobalt: 0.5-5%, molybdenum: 0.5-15%) using more than stoichiometry 5%, concentration is that the concentrated hydrochloric acid of 18-26% keeps little boiling 2 hours under pressurization or normal pressure, crosses and makes the molten clear feed liquid of acid after filtering to remove waste residue, and the molten clear feed liquid of acid contains aluminium: 45-65g/L, cobalt: 0.7-3g/L, molybdenum: 0.7-8g/L, iron: 0.5-4g/L, potassium: 5-10g/L;
(2), extraction molybdenum: the above-mentioned sour molten clear feed liquid that makes is extracted with extraction agent I, get raffinate I and load extraction agent I, load extraction agent I with concentrated hydrochloric acid washing and back extraction after, obtain strip liquor I, washings I and regenerating extracting agent I, regenerating extracting agent I can return extraction molybdenum operation and recycle, washings I returns the molten molten clear feed liquid of next relieving haperacidity that is used for of acid again, the further Separation of Molybdenum of strip liquor I, iron, make ammonium molybdate more as required, Sodium orthomolybdate, ferric oxide, the actual recovered rate of molybdenum can reach 99.2%, described extraction agent I composition is a tributyl phosphate, the volume ratio of kerosene is 20～30: 80～70, and constituent content is aluminium: 45～65g/L in the described raffinate I composition, cobalt: 0.7～3g/L, molybdenum:＜0.001g/L, iron:＜0.0001g/L, potassium: 5～10g/L, constituent content is aluminium:＜0.01g/L in the described strip liquor I composition, cobalt:＜0.002g/L, molybdenum: 55～65g/L, iron: 5～40g/L, potassium:＜0.005g/L.
(3), extraction cobalt: the raffinate I that obtains is previously extracted with extraction agent II, get raffinate II and load extraction agent II, load extraction agent II is through washing, back extraction, get strip liquor II, cleaning solution II and regenerating extracting agent II, cleaning solution II can be returned sour molten operation and be used for the molten clear feed liquid of next relieving haperacidity, regenerating extracting agent II can return extraction cobalt operation and recycle, strip liquor II makes cobalt chloride more as required, cobaltous carbonate, cobaltous hydroxide, cobalt salt series such as cobalt oxide, the actual recovered rate of cobalt is more than 99.5%, described extraction agent II composition is 0.01～0.1mol/L trioctylamine solvent oil solution, described raffinate II is an aluminum chloride, Klorvess Liquid, its constituent content is aluminium: 45～65g/L, cobalt:＜1mg/L, molybdenum:＜0.1mg/L, iron＜0.1mg/L, potassium: 5～10g/L; Constituent content is aluminium:＜10mg/L among the strip liquor II, cobalt:＞40g/L, and molybdenum:＜1mg/L, iron＜1mg/L, potassium: 5mg/L, raffinate II can further make products such as non-iron aluminium sulfate, crystal aluminum chloride, Repone K, potassium aluminium sulfate as required.
Embodiment two: the volume ratio that described extraction agent I composition is tributyl phosphate, kerosene is 40～60: 60～40; Described extraction agent II composition is 0.2～0.3mol/L trioctylamine solvent oil solution; All the other technologies are identical with embodiment one.
Embodiment three: the volume ratio that described extraction agent I composition is tributyl phosphate, kerosene is 70～80: 30～20; Described extraction agent II composition is 0.4～0.5mol/L trioctylamine solvent oil solution; All the other technologies are identical with embodiment one.
Claims (9)
1, a kind of from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, the useless cobalt that it is characterized in that pulverizing through roasting, molybdenum catalyst powder are made sour molten clear feed liquid with concentrated hydrochloric acid acid is molten, with the mixed solution extraction molybdenum of the molten clear feed liquid of acid with tributyl phosphate and kerosene, raffinate is again with trioctylamine solvent oil extraction cobalt.
2, according to claim 1 from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that specifically comprising following technology:
(1), acid is molten: will be molten with concentrated hydrochloric acid acid through useless cobalt, molybdenum catalyst powder that roasting is pulverized, cross and make sour molten clear feed liquid after filtering to remove waste residue;
(2), extraction molybdenum: the above-mentioned sour molten clear feed liquid that makes is extracted with extraction agent I, get raffinate I and load extraction agent I, load extraction agent I with concentrated hydrochloric acid washing and back extraction after, obtain strip liquor I, washings I and regenerating extracting agent I, the further Separation of Molybdenum of strip liquor I, iron, make ammonium molybdate, Sodium orthomolybdate, ferric oxide more as required, the volume ratio that described extraction agent I composition is tributyl phosphate, kerosene is 20～80: 80～20;
(3), extraction cobalt: the raffinate I that obtains is previously extracted with extraction agent II, get raffinate II and load extraction agent II, load extraction agent II with concentrated hydrochloric acid washing and back extraction after, get strip liquor II, cleaning solution II and regenerating extracting agent II, strip liquor II makes cobalt chloride, cobaltous carbonate, cobaltous hydroxide, cobalt oxide cobalt salt series more as required, and described extraction agent II composition is 0.01～0.5mol/L trioctylamine solvent oil solution.
3, according to claim 2 from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that: will use more than the concentrated hydrochloric acid acid of stoichiometry 5% molten through useless cobalt, the molybdenum catalyst powder of roasting pulverizing.
4, according to claim 2 or 3 described from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that: will be molten through the useless cobalt of roasting pulverizing, concentrated hydrochloric acid acid that molybdenum catalyst powder concentration is 18-26%.
5, according to claim 2 or 3 described from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that: washings I and cleaning solution II can be returned sour molten operation and be used for the molten clear feed liquid of next relieving haperacidity.
6, according to claim 4 from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that: washings I and cleaning solution II can be returned sour molten operation and be used for the molten clear feed liquid of next relieving haperacidity.
7, according to claim 2 or 3 or 6 described from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that: regenerating extracting agent I can return extraction molybdenum operation and recycle; Regenerating extracting agent II can return extraction cobalt operation and recycle.
8, according to claim 4 from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that regenerating extracting agent I can return extraction molybdenum operation and recycle; Regenerating extracting agent II can return extraction cobalt operation and recycle.
9, according to claim 5 from useless cobalt-molybdenum catalyst the method for separating and recovering cobalt, molybdenum, it is characterized in that regenerating extracting agent I can return extraction molybdenum operation and recycle; Regenerating extracting agent II can return extraction cobalt operation and recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100315159A CN100347318C (en) | 2005-04-30 | 2005-04-30 | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100315159A CN100347318C (en) | 2005-04-30 | 2005-04-30 | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1814827A CN1814827A (en) | 2006-08-09 |
| CN100347318C true CN100347318C (en) | 2007-11-07 |
Family
ID=36907182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100315159A Expired - Fee Related CN100347318C (en) | 2005-04-30 | 2005-04-30 | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100347318C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427406C (en) * | 2006-10-25 | 2008-10-22 | 丁四宜 | Waste molybdenum nickel cobalt catalyst utilization method for environmental protection |
| EP1983066A1 (en) * | 2007-03-30 | 2008-10-22 | Paul Wurth S.A. | Method of recovering molybdenum, nickel, cobalt or their mixtures from spent or regenerated catalysts |
| CN102276146B (en) * | 2011-05-19 | 2013-09-18 | 长沙理工大学 | Method for producing ceramic and glass pigment by using waste chromium and cobalt catalysts from fluorination process as raw materials |
| CN109652649B (en) * | 2017-10-10 | 2021-08-03 | 中国石油化工股份有限公司 | Method for improving recovery rate of cobalt and molybdenum of waste catalyst |
| CN109652651A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of the useless activation of cobalt molybdenum base hydrotreating catalyst Call Provision and molybdenum |
| CN111088438A (en) * | 2020-03-03 | 2020-05-01 | 雅邦绿色过程与新材料研究院南京有限公司 | Method for recovering molybdenum from molybdenum-containing waste catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5468720A (en) * | 1977-11-11 | 1979-06-02 | Sumitomo Metal Mining Co | Recovering of valuable metal from desurfurising waste catalyst |
| US5431892A (en) * | 1994-03-11 | 1995-07-11 | Sumitomo Metal Mining Co., Ltd. | Process for recovering valuable metal from waste catalyst |
| JP2007117602A (en) * | 2005-10-31 | 2007-05-17 | Yoshino Kogyosho Co Ltd | Brush with comb |
-
2005
- 2005-04-30 CN CNB2005100315159A patent/CN100347318C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5468720A (en) * | 1977-11-11 | 1979-06-02 | Sumitomo Metal Mining Co | Recovering of valuable metal from desurfurising waste catalyst |
| US5431892A (en) * | 1994-03-11 | 1995-07-11 | Sumitomo Metal Mining Co., Ltd. | Process for recovering valuable metal from waste catalyst |
| JP2007117602A (en) * | 2005-10-31 | 2007-05-17 | Yoshino Kogyosho Co Ltd | Brush with comb |
Non-Patent Citations (1)
| Title |
|---|
| 钴提取分离技术分析与应用 刘三平，王海北，蒋开喜，王玉芳.有色金属，第56卷第2期 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1814827A (en) | 2006-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| CN101289704B (en) | A kind of processing method of high magnesium laterite nickel ore | |
| CN112095003A (en) | Method for recycling various valuable metals and acid-base double-medium regeneration cycle from laterite-nickel ore | |
| CN100584764C (en) | Method for recovering iron oxide from fly ash and coal gangue | |
| CN114132909A (en) | Method for recycling pure metal salt from retired manganese iron phosphate lithium battery waste | |
| CN108467939A (en) | A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst | |
| CN101457296A (en) | Method for recovering metal oxide from waste aluminum-based vanadium-molybdenum-nickel catalyst | |
| CN112226630B (en) | Method for extracting valuable metal elements from laterite-nickel ore by hydrochloric acid leaching method and acid-base regeneration circulation | |
| CN101760651A (en) | Process for extracting vanadium by acid leaching of stone coal | |
| CN104046786B (en) | A kind of method reclaiming metal from vanadium slag | |
| CN102876896B (en) | Method for recovering vanadium by decomposing vanadium extraction tailings by using sodium hydroxide solution | |
| CN104018011B (en) | Production method of vanadic oxide | |
| CN1827527A (en) | Process for preparing lithium chlorate by lithium extracted from lepidolite | |
| CN111575478B (en) | Method for separating metal in heavy oil | |
| CN102212683A (en) | Wet metallurgical method with comprehensive reclamation, basically no three wastes and zero discharge | |
| CN111778398A (en) | Method for extracting vanadium and tungsten from waste SCR denitration catalyst | |
| CN110218859A (en) | The method of the useless denitrating catalyst valuable element of middle temperature tunnel type solid-state activation extraction | |
| CN118531215A (en) | Metal recovery method for waste catalyst containing aluminum, nickel, molybdenum, vanadium and iron | |
| CN100347318C (en) | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst | |
| CN112813287B (en) | A kind of method of recovering molybdenum from spent hydrogenation catalyst | |
| CN100482814C (en) | Extraction of vanadium and molybdenum compound from refused materials containing vanadium and molybdenum etc. multiple elements | |
| CN109652652A (en) | The method that clean and environmental protection recycles valuable element from aluminium base petroleum refining dead catalyst | |
| CN111762804A (en) | A kind of iron removal method of acid leaching solution in aluminum extraction by acid method | |
| CN1631797A (en) | Method for extracting vanadium pentoxide from vanadium-containing spent catalyst and petroleum ash | |
| CN112746172B (en) | Treatment method of deactivated hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071107 Termination date: 20100430 |