CN115216650A - Method for separating and recovering molybdenum from hydrogenation catalyst waste material - Google Patents
Method for separating and recovering molybdenum from hydrogenation catalyst waste material Download PDFInfo
- Publication number
- CN115216650A CN115216650A CN202210952119.3A CN202210952119A CN115216650A CN 115216650 A CN115216650 A CN 115216650A CN 202210952119 A CN202210952119 A CN 202210952119A CN 115216650 A CN115216650 A CN 115216650A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- hydrogenation catalyst
- solution
- separating
- organic phase
- 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.)
- Pending
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000011733 molybdenum Substances 0.000 title claims abstract description 58
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 38
- 239000012074 organic phase Substances 0.000 claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 22
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 22
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 22
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 22
- 230000005496 eutectics Effects 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 19
- 239000012670 alkaline solution Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical group [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- YWACCMLWVBYNHR-UHFFFAOYSA-N 7-(5-ethylnonan-2-yl)quinolin-8-ol Chemical compound C1=CC=NC2=C(O)C(C(C)CCC(CC)CCCC)=CC=C21 YWACCMLWVBYNHR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 molybdate ions Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for separating and recovering molybdenum from hydrogenation catalyst waste, which belongs to the technical field of solid waste recycling and comprises the following steps: mixing the waste hydrogenation catalyst with magnesium oxide for primary roasting, and mixing with sodium carbonate for secondary roasting to obtain a roasted product; adding the roasted product into an alkaline solution for leaching, combining ultrasonic treatment and solid-liquid separation, wherein the liquid is molybdenum alkaline leaching liquid; adding a sulfuric acid solution into the molybdenum alkaline leaching solution to adjust the pH value to 6-7, filtering to obtain a filtrate to be extracted, adding a eutectic solvent and a diluent into the extract to form an organic phase, and extracting to obtain an extracted organic phase; carrying out back extraction on the extracted organic phase by using ammonia water to obtain an ammonium molybdate solution, and carrying out evaporative crystallization on the ammonium molybdate solution to obtain an ammonium molybdate precipitate; the method adopts the eutectic solvent as the extractant, avoids the use of the traditional extractant, combines ultrasonic treatment, improves the extraction rate of molybdenum metal, and is environment-friendly and healthy.
Description
Technical Field
The invention belongs to the technical field of solid waste recycling, and particularly relates to a method for separating and recycling molybdenum from hydrogenation catalyst waste.
Background
With the development of chemical industry, especially oil refining, chemical industry and other chemical industries using a large amount of catalyst, a large amount of waste catalyst is generated, and with the increasing strictness of environmental regulations, the disposal of the waste catalyst becomes an important problem.
Molybdenum is an important component of a hydrogenation catalyst and has wide application, but the storage capacity of molybdenum ore on the earth surface is limited, so that the recovery of molybdenum from a molybdenum-containing waste catalyst has important environmental significance and economic significance, at present, most of molybdenum and other metals are recovered from the molybdenum-containing catalyst by adopting a wet recovery method, namely, the molybdenum in the waste catalyst is soaked into a solution to form an ionic state and then extracted from the solution, so that various different provided process routes are formed, and the main process routes comprise a sodium carbonate soaking-roasting method, a roasting-leaching method, a roasting-organic matter extraction method and the like.
Chinese patent CN112813287A discloses a method for recovering molybdenum from waste hydrogenation catalyst, which comprises mixing waste hydrogenation catalyst and red mud in proportion, pulverizing, grinding, calcining, and soaking in water; adding acid into the leachate to adjust the pH value, and selectively extracting molybdenum from the molybdenum-containing acidic solution after aluminum hydroxide is separated out by using a chelating extraction agent; ammonia water for molybdenum-containing organic phaseBack-extracting ammonium salt or a mixed solution thereof; adding an impurity removing agent into the back extraction solution to remove impurities such as P, si and the like, adjusting the pH value with hydrochloric acid, and concentrating, evaporating and crystallizing to obtain an ammonium molybdate product. The chelating type extracting agent is adopted to realize the high-efficiency extraction of the metal molybdenum, but the adopted extracting agent is an organic chelating extracting agent, the toxicity, the volatility and the pollution to the environment are greatly influenced, the existing waste catalyst generally contains sulfur at the same time, for example, the sulfur content in the waste hydrogenation catalyst is 3 percent, and the waste hydrogenation catalyst also contains components such as silicon, phosphorus and the like, and the method in the patent is easy to generate SO in the roasting process 2 And the like, therefore, the technical problem to be solved at present is to provide a more environment-friendly method for separating and recovering molybdenum from the hydrogenation catalyst waste.
Disclosure of Invention
The invention aims to provide a method for separating and recovering molybdenum from a hydrogenation catalyst waste material, which solves the problem that the method for recovering molybdenum from a waste gas hydrogenation catalyst in the prior art is not environment-friendly.
The purpose of the invention can be realized by the following technical scheme:
a method for separating and recovering molybdenum from hydrogenation catalyst waste material comprises the following steps:
firstly, mixing the waste hydrogenation catalyst and magnesium oxide, carrying out primary roasting, oil removal and carbon removal, then crushing to 80-120 meshes, mixing with sodium carbonate, and carrying out secondary roasting to obtain a roasted product;
secondly, adding the roasted product into an alkaline solution for leaching, performing ultrasonic treatment, performing solid-liquid separation, wherein the solid is residue, the liquid is a molybdenum alkaline leaching solution, and collecting the molybdenum alkaline leaching solution for later use;
thirdly, adding sulfuric acid solution into the molybdenum alkaline leachate to adjust the pH value to 6-7, and precipitating to obtain Al (OH) 3 Filtering, wherein the filtrate is to-be-extracted liquid, adding a eutectic solvent and a diluent into the to-be-extracted liquid to form an organic phase, extracting at the temperature of 25-45 ℃ for 5-10min, and the mass ratio of the organic phase to the to-be-extracted liquid is 1-3:3, obtaining an extracted organic phase after extraction is finished;
and fourthly, carrying out back extraction on the extracted organic phase by using ammonia water to obtain an ammonium molybdate solution, adjusting the pH of the ammonium molybdate solution to 2-3 by using nitric acid, and carrying out evaporative crystallization to obtain an ammonium molybdate precipitate.
Further, the primary roasting temperature is 500-550 ℃, the time is 3-4h, the magnesium oxide dosage is 3-5% of the mass of the waste hydrogenation catalyst, in the primary roasting process, sulfur in the waste gas hydrogenation catalyst reacts with magnesium oxide to generate magnesium sulfite and a small amount of magnesium sulfate, and SO is reduced 2 And the like, sulfur-containing waste gas.
Further, the secondary roasting temperature is 600-800 ℃, the time is 9-10h, the using amount of sodium carbonate is 0.4-1 time of the mass of the waste hydrogenation catalyst, molybdenum is converted into water-soluble sodium molybdate in the high-temperature roasting process, and the primary roasted magnesium sulfite is oxidized into magnesium sulfate while the secondary roasting is carried out.
Further, in the second step, the mass ratio of the roasted product to the alkaline solution is 1:5, preparing an alkaline solution from an ammonia water solution with the mass fraction of 28%, ammonium bicarbonate and deionized water according to the dosage ratio of 0.5-1mL:1.3-1.5mol:0.5mL of the molybdenum and the ammonium hydrogen carbonate are mixed, the leaching temperature is 80 ℃, the ultrasonic power is 400W, the time is 2-3h, in the solution leaching operation, ammonia water-ammonium hydrogen carbonate is used as a leaching aid, wherein the ammonia water is used as a leaching agent, the cost is low, and other impurity elements are not introduced, in the leaching process, the ammonium hydrogen carbonate can be slowly decomposed to generate the ammonia water, the leaching rate of molybdenum in a roasted product is improved, the molybdenum enters the solution in the form of sodium molybdate or ammonium molybdate, impurities such as silicon, phosphorus and the like in the solution react with magnesium and ammonium to generate magnesium silicate and ammonium magnesium phosphate precipitate, and the magnesium silicate and the ammonium magnesium phosphate precipitate enter residues, so that the effective leaching and impurity separation of the molybdenum are realized.
Further, in the third step, the mass ratio of the low eutectic solvent to the diluent is 1-3:10, eutectic solvent is benzyltripropylammonium chloride and n-decanoic acid according to a molar ratio of 1:2, the diluent is sulfonated kerosene, compared with the traditional organic extractant, the invention adopts eutectic solvent as the extractant, has no toxicity, no volatility, reproducibility and environmental friendliness, and uses an ammonium salt structure containing benzyl as a hydrogen bond acceptor, wherein the existence of benzyl groups not only enables the compound to have larger steric hindrance, and the formed eutectic solvent has more stable performance, but also can better wrap molybdate ions, and is more beneficial to forming stable molybdenum extract compounds, so that the extract compounds are more easily dissolved in an organic phase, thereby being beneficial to the selective extraction of molybdenum.
Further, in the fourth step, back extraction is carried out by using 10-25% ammonia water by mass fraction, and the mass ratio of the extracted organic phase to the ammonia water is 1-2:1-2, molybdenum is put into solution in the form of sodium molybdate, and then is acidified by nitric acid to obtain ammonium molybdate precipitate.
The invention has the beneficial effects that:
the invention provides a method for separating and recovering molybdenum from hydrogenation catalyst waste, which realizes the recovery of molybdenum in waste catalysts by technical means such as roasting-alkaline leaching-extraction back-extraction-salting-out, saves mineral resources and reduces environmental pollution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The mass percentages of main components of the waste hydrogenation catalysts used in the following examples and comparative examples are as follows: al23.5%, mo11.0%, S2.88%, ni2.8%, si1.72%, P1.1%.
Example 1
A method for separating and recovering molybdenum from hydrogenation catalyst waste comprises the following steps:
firstly, mixing the waste hydrogenation catalyst and magnesium oxide, carrying out primary roasting, oil removal and carbon removal, then crushing to 80-120 meshes, mixing with sodium carbonate, and carrying out secondary roasting to obtain a roasted product;
secondly, adding the roasted product into an alkaline solution for leaching, performing ultrasonic treatment, performing solid-liquid separation, wherein the solid is residue, the liquid is molybdenum alkaline leachate, and collecting the molybdenum alkaline leachate for later use;
thirdly, adding sulfuric acid solution into the molybdenum alkaline leaching solution to adjust the pH value to be 6, and precipitating and separating out Al (OH) 3 Filtering, wherein the filtrate is to-be-extracted liquid, adding a eutectic solvent and a diluent into the to-be-extracted liquid to form an organic phase, extracting for 5min at the temperature of 25 ℃, and the mass ratio of the extracted organic phase to the to-be-extracted liquid is 1:3, obtaining an extracted organic phase after extraction is finished;
and fourthly, carrying out back extraction on the extracted organic phase by using ammonia water to obtain an ammonium molybdate solution, adjusting the pH of the ammonium molybdate solution to 2 by using nitric acid, and carrying out evaporative crystallization to obtain an ammonium molybdate precipitate.
Wherein the primary roasting temperature is 500 ℃, the time is 3 hours, the dosage of the magnesium oxide is 3 percent of the mass of the waste hydrogenation catalyst, the secondary roasting temperature is 600 ℃, the time is 9 hours, and the dosage of the sodium carbonate is 0.4 time of the mass of the waste hydrogenation catalyst.
In the second step, the mass ratio of the roasted product to the alkaline solution is 1:5, mixing an alkaline solution prepared from 28 mass percent of ammonia water solution, ammonium bicarbonate and deionized water according to a ratio of 0.5mL:1.3mol:0.5mL of the raw materials are mixed, the leaching temperature is 80 ℃, the ultrasonic power is 400W, and the time is 2h.
In the third step, the mass ratio of the low eutectic solvent to the diluent is 1:10, eutectic solvent is benzyltripropylammonium chloride and n-decanoic acid according to a molar ratio of 1:2, the diluent is sulfonated kerosene.
And in the fourth step, back extraction is carried out by using ammonia water with the mass fraction of 10%, and the mass ratio of the extracted organic phase to the ammonia water is 2:1.
example 2
A method for separating and recovering molybdenum from hydrogenation catalyst waste material comprises the following steps:
firstly, mixing the waste hydrogenation catalyst and magnesium oxide, carrying out primary roasting, oil removal and carbon removal, then crushing to 80-120 meshes, mixing with sodium carbonate, and carrying out secondary roasting to obtain a roasted product;
secondly, adding the roasted product into an alkaline solution for leaching, performing ultrasonic treatment, performing solid-liquid separation, wherein the solid is residue, the liquid is molybdenum alkaline leachate, and collecting the molybdenum alkaline leachate for later use;
thirdly, adding sulfuric acid solution into the molybdenum alkaline leaching solution to adjust the pH value to 6-7, and precipitating and separating out Al (OH) 3 Filtering, wherein the filtrate is to-be-extracted liquid, adding a eutectic solvent and a diluent into the to-be-extracted liquid to form an organic phase, extracting for 8min at the temperature of 30 ℃, and the mass ratio of the extracted organic phase to the to-be-extracted liquid is 2:3, obtaining an extracted organic phase after extraction is finished;
and fourthly, carrying out back extraction on the extracted organic phase by using ammonia water to obtain an ammonium molybdate solution, adjusting the pH of the ammonium molybdate solution to 2 by using nitric acid, and carrying out evaporative crystallization to obtain an ammonium molybdate precipitate.
Wherein the primary roasting temperature is 530 ℃ and the time is 3.5h, the dosage of the magnesium oxide is 4 percent of the mass of the waste hydrogenation catalyst, the secondary roasting temperature is 700 ℃ and the time is 9.5h, and the dosage of the sodium carbonate is 0.6 time of the mass of the waste hydrogenation catalyst.
In the second step, the mass ratio of the roasted product to the alkaline solution is 1:5, mixing an alkaline solution prepared from 28 mass percent ammonia water solution, ammonium bicarbonate and deionized water according to the proportion of 0.8mL:1.4mol:0.5mL of the mixture is mixed, the leaching temperature is 80 ℃, the ultrasonic power is 400W, and the time is 2.5h.
In the third step, the mass ratio of the low eutectic solvent to the diluent is 2:10, eutectic solvent is benzyltripropyl ammonium chloride and n-decanoic acid according to a molar ratio of 1:2 and the diluent is sulfonated kerosene.
And in the fourth step, back extraction is carried out by using ammonia water with the mass fraction of 15%, and the mass ratio of the extracted organic phase to the ammonia water is 1:2.
example 3
A method for separating and recovering molybdenum from hydrogenation catalyst waste comprises the following steps:
firstly, mixing the waste hydrogenation catalyst and magnesium oxide, carrying out primary roasting, oil removal and carbon removal, then crushing to 80-120 meshes, mixing with sodium carbonate, and carrying out secondary roasting to obtain a roasted product;
secondly, adding the roasted product into an alkaline solution for leaching, performing ultrasonic treatment, performing solid-liquid separation, wherein the solid is residue, the liquid is molybdenum alkaline leachate, and collecting the molybdenum alkaline leachate for later use;
thirdly, adding sulfuric acid solution into the molybdenum alkaline leaching solution to adjust the pH value to 7, and precipitating and separating out Al (OH) 3 Filtering to obtain filtrate to be extracted liquid, adding a eutectic solvent and a diluent into the to-be-extracted liquid to form an organic phase, extracting for 10min at the temperature of 45 ℃, wherein the mass ratio of the extracted organic phase to the to-be-extracted liquid is 1:1, obtaining an extracted organic phase after extraction is finished;
and fourthly, carrying out back extraction on the extracted organic phase by using ammonia water to obtain an ammonium molybdate solution, adjusting the pH value of the ammonium molybdate solution to 3 by using nitric acid, and carrying out evaporative crystallization to obtain an ammonium molybdate precipitate.
Wherein the primary roasting temperature is 550 ℃, the time is 4 hours, the dosage of the magnesium oxide is 5 percent of the mass of the waste hydrogenation catalyst, the secondary roasting temperature is 800 ℃, the time is 10 hours, and the dosage of the sodium carbonate is 1 time of the mass of the waste hydrogenation catalyst.
In the second step, the mass ratio of the roasted product to the alkaline solution is 1:5, mixing an alkaline solution prepared from 28 mass percent ammonia water solution, ammonium bicarbonate and deionized water according to a ratio of 1mL:1.5mol:0.5mL of the raw materials are mixed, the leaching temperature is 80 ℃, the ultrasonic power is 400W, and the time is 3h.
In the third step, the mass ratio of the low eutectic solvent to the diluent is 3:10, eutectic solvent is benzyltripropylammonium chloride and n-decanoic acid according to a molar ratio of 1:2, the diluent is sulfonated kerosene.
And in the fourth step, back extraction is carried out by using 25% ammonia water by mass fraction, and the mass ratio of the extracted organic phase to the ammonia water is 1:1.
comparative example 1
Compared with the example 1, the second ultrasonic treatment process step is removed, and the rest procedures are the same as the example 1.
Comparative example 2
Compared with the example 2, the low eutectic solvent in the third step is replaced by an organic extractant Kelex100, and the rest procedures are the same as the example 2.
The molybdenum recovery was calculated based on the mass of ammonium molybdate precipitate recovered according to the methods described in examples 1-3 and comparative examples 1-2, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, the recovery processes of examples 1-3 provide higher extraction of molybdenum from the off-gas hydrogenation catalyst than comparative examples 1-2.
In the description of the specification, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. A method for separating and recovering molybdenum from hydrogenation catalyst waste material is characterized by comprising the following steps:
firstly, mixing the waste hydrogenation catalyst and magnesium oxide, carrying out primary roasting, oil removal and carbon removal, crushing to 80-120 meshes, mixing with sodium carbonate, and carrying out secondary roasting to obtain a roasted product;
secondly, adding the roasted product into an alkaline solution for leaching, performing solid-liquid separation by combining ultrasonic treatment, wherein the solid is residue, the liquid is molybdenum alkaline leachate, and collecting the molybdenum alkaline leachate for later use;
adding a sulfuric acid solution into the molybdenum alkaline leaching solution to adjust the pH value to 6-7, filtering to obtain a filtrate, adding an organic phase consisting of a eutectic solvent and a diluent into the extract, extracting at the temperature of 25-45 ℃, and obtaining an extracted organic phase after extraction is finished;
and fourthly, carrying out back extraction on the extracted organic phase by using ammonia water to obtain an ammonium molybdate solution, adjusting the pH of the ammonium molybdate solution to 2-3 by using nitric acid, and carrying out evaporative crystallization to obtain an ammonium molybdate precipitate.
2. The method for separating and recovering molybdenum from hydrogenation catalyst waste material according to claim 1, wherein the primary roasting temperature is 500-550 ℃, the time is 3-4h, and the using amount of magnesium oxide is 3-5% of the mass of the waste hydrogenation catalyst.
3. The method for separating and recovering molybdenum from hydrogenation catalyst waste material according to claim 1, wherein the secondary roasting temperature is 600-800 ℃, the time is 9-10h, and the amount of sodium carbonate is 0.4-1 time of the mass of the waste hydrogenation catalyst.
4. The method for separating and recovering molybdenum from hydrogenation catalyst waste material according to claim 1, wherein the mass ratio of the roasted product to the alkaline solution in the second step is 1:5, the alkaline solution is prepared from 28 mass percent of ammonia water solution, ammonium bicarbonate and deionized water according to the dosage ratio of 0.5-1mL:1.3-1.5mol:0.5mL of the mixture is mixed, the leaching temperature is 80 ℃, the ultrasonic power is 400W, and the time is 2-3h.
5. The method for separating and recovering molybdenum from hydrogenation catalyst waste material according to claim 1, wherein the mass ratio of the low eutectic solvent to the diluent in the third step is 1-3:10, eutectic solvent is benzyltripropylammonium chloride and n-decanoic acid according to a molar ratio of 1:2.
6. The method for separating and recovering molybdenum from hydrogenation catalyst waste material according to claim 1, wherein the back extraction in the fourth step is performed by using 10-25% by mass of ammonia water, and the mass ratio of the extracted organic phase to the ammonia water is 1-2:1-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210952119.3A CN115216650A (en) | 2022-08-09 | 2022-08-09 | Method for separating and recovering molybdenum from hydrogenation catalyst waste material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210952119.3A CN115216650A (en) | 2022-08-09 | 2022-08-09 | Method for separating and recovering molybdenum from hydrogenation catalyst waste material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115216650A true CN115216650A (en) | 2022-10-21 |
Family
ID=83615586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210952119.3A Pending CN115216650A (en) | 2022-08-09 | 2022-08-09 | Method for separating and recovering molybdenum from hydrogenation catalyst waste material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115216650A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435027A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Method for recycling high purity molybdenum from molybdenum-containing spent catalyst |
| CN102051483A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for reclaiming metals from molybdenum-containing waste catalyst |
| CN110791656A (en) * | 2019-12-03 | 2020-02-14 | 浙江大学 | Method for extracting and separating molybdenum in waste catalyst leaching solution by multi-field synergistic enhancement |
| CN111945007A (en) * | 2020-08-27 | 2020-11-17 | 中国科学院过程工程研究所 | Method for recovering vanadium and molybdenum from waste catalyst containing vanadium and molybdenum |
| CN112501458A (en) * | 2020-11-12 | 2021-03-16 | 浙江大学 | Method for selectively extracting and separating molybdenum in waste catalyst leaching solution by using benzyl quaternary ammonium salt eutectic solvent |
| CN113289680A (en) * | 2021-06-02 | 2021-08-24 | 河北科技大学 | Two-phase catalyst, preparation method thereof and application thereof in lignocellulose biomass conversion |
| CN114207163A (en) * | 2019-07-08 | 2022-03-18 | 雪佛龙美国公司 | Recovery of metals from spent catalysts |
| CN114657396A (en) * | 2022-03-30 | 2022-06-24 | 中国科学院过程工程研究所 | Method for leaching molybdenum metal in waste hydrogenation catalyst through external field strengthening |
-
2022
- 2022-08-09 CN CN202210952119.3A patent/CN115216650A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435027A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Method for recycling high purity molybdenum from molybdenum-containing spent catalyst |
| CN102051483A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for reclaiming metals from molybdenum-containing waste catalyst |
| CN114207163A (en) * | 2019-07-08 | 2022-03-18 | 雪佛龙美国公司 | Recovery of metals from spent catalysts |
| CN110791656A (en) * | 2019-12-03 | 2020-02-14 | 浙江大学 | Method for extracting and separating molybdenum in waste catalyst leaching solution by multi-field synergistic enhancement |
| CN111945007A (en) * | 2020-08-27 | 2020-11-17 | 中国科学院过程工程研究所 | Method for recovering vanadium and molybdenum from waste catalyst containing vanadium and molybdenum |
| CN112501458A (en) * | 2020-11-12 | 2021-03-16 | 浙江大学 | Method for selectively extracting and separating molybdenum in waste catalyst leaching solution by using benzyl quaternary ammonium salt eutectic solvent |
| CN113289680A (en) * | 2021-06-02 | 2021-08-24 | 河北科技大学 | Two-phase catalyst, preparation method thereof and application thereof in lignocellulose biomass conversion |
| CN114657396A (en) * | 2022-03-30 | 2022-06-24 | 中国科学院过程工程研究所 | Method for leaching molybdenum metal in waste hydrogenation catalyst through external field strengthening |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108002408B (en) | Method for preparing nickel sulfate, manganese, lithium, cobalt and cobaltosic oxide from battery waste | |
| CN106319218B (en) | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum-silicon waste | |
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| CN112375910B (en) | Recovery processing method of waste power battery powder | |
| CN104928475B (en) | A kind of recovery method of the aluminium scrap silicon containing rare earth | |
| CN103160689B (en) | Method of iron extraction and removal with solvent extraction agent | |
| WO2020196046A1 (en) | Method for manufacturing nickel and cobalt-containing solution from hydroxide containing nickel and cobalt | |
| CN112342389A (en) | Method for recovering valuable metal from waste chemical catalyst | |
| CN112831660B (en) | Process for comprehensively utilizing molybdenum ore leaching slag | |
| CN101450814A (en) | Novel method for extracting vanadic anhydride from stone coal vanadium ore | |
| CN114959261B (en) | Method for recovering tungsten, molybdenum, nickel and cobalt from multi-metal alloy in full wet process | |
| CN112795784A (en) | Method for comprehensively recovering valuable components in red mud | |
| CN114436328B (en) | Method for preparing vanadyl sulfate electrolyte from sodium vanadate-containing solution | |
| WO2004099079A1 (en) | A method for producing an electrolytic solution containing vanadium | |
| CN116377243A (en) | Method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw material | |
| CN117327930B (en) | Method for recovering vanadium from primary shale stone coal | |
| CN110468277A (en) | The method of rhenium is recycled from Copper making waste acid | |
| CN112813287B (en) | Method for recovering molybdenum from waste hydrogenation catalyst | |
| CN110229964B (en) | Method for extracting rubidium from fly ash | |
| CN115216650A (en) | Method for separating and recovering molybdenum from hydrogenation catalyst waste material | |
| JP3831805B2 (en) | Treatment method for petroleum combustion ash | |
| WO2004090179A1 (en) | Method of recovering vanadium oxide flake from diesel oil fly-ash or orimulsion fly-ash | |
| CN114988382A (en) | Method for recovering waste lithium iron phosphate battery powder | |
| JP2002166244A (en) | Method for treating petroleum combustion ash | |
| CN115141933B (en) | Method for purifying ternary lithium battery recovery leaching liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221021 |