CN115838873A - Method for step recovery of valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni - Google Patents
Method for step recovery of valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni Download PDFInfo
- Publication number
- CN115838873A CN115838873A CN202211530694.0A CN202211530694A CN115838873A CN 115838873 A CN115838873 A CN 115838873A CN 202211530694 A CN202211530694 A CN 202211530694A CN 115838873 A CN115838873 A CN 115838873A
- Authority
- CN
- China
- Prior art keywords
- waste
- leaching
- solution
- based catalyst
- valuable components
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 80
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 56
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 86
- 238000001914 filtration Methods 0.000 claims abstract description 31
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 91
- 239000000047 product Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000004131 Bayer process Methods 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims 7
- 239000003518 caustics Substances 0.000 claims 1
- 239000010802 sludge Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 7
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 50
- 239000003208 petroleum Substances 0.000 description 32
- 238000005984 hydrogenation reaction Methods 0.000 description 30
- 239000003921 oil Substances 0.000 description 28
- 239000003513 alkali Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
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)
Abstract
A method for recovering valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient manner belongs to the field of resource recovery. The invention respectively adopts the modes of oil removal, reduced pressure distillation, alkaline leaching, filtration precipitation, extraction and the like to respectively obtain black oil and Al (OH) from the waste aluminum-based catalyst 3 Precipitation, ammonium vanadate precipitation, molybdate precipitation and the like. The method for recovering valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient manner is green, efficient and environment-friendly. The separation of Mo and V from Co, ni and most of Al is realized in the oxidation alkaline leaching stage, so that the subsequent metalThe separation to obtain pure product becomes simple. Can make the recovery rate of Mo and V>99% Al recovery>95 percent and more than 99 percent of Co and Ni are enriched in the alkaline leaching residue, and the oil enriched on the surface of the waste catalyst can be simultaneously recovered, so that the full recovery of valuable components in the waste aluminum-based catalyst containing Mo, V, co and Ni is realized.
Description
Technical Field
The invention belongs to the technical field of secondary resource recovery, solid waste comprehensive utilization and nonferrous metal metallurgy, and particularly relates to a wet recovery method of valuable components in a waste catalyst.
Background
With the increasingly prominent environmental problems, people have an increasing demand for clean energy. The processes of hydrogenation, desulfurization, and demetallization in the petroleum refining process to obtain high quality petroleum products are collectively referred to as hydrotreating of petroleum. The service life of the petroleum hydrogenation catalyst is about 1 to 3 years, and the service life of the petroleum hydrogenation catalyst for treating high-sulfur heavy oil is 0.5 to 1 year. About 1.2X 10 of waste petroleum hydrogenation catalysts are generated annually worldwide 5 Ton, 1X 10 produced in China 4 Ton. The deactivated hydrogenation catalyst contains valuable metals such as Ni, co, mo, V and the like, and is listed as hazardous waste by the U.S. environmental protection agency and the European environmental protection agency. In the book of national hazardous waste revised and passed by the ministry of environmental protection in 2016, 3, month and 30, the petroleum hydrogenation catalyst is listed as toxic (T) hazardous waste.
After decades of mining, mineral resources in China are developed towards the characteristics of poverty, fineness and impurities, and the content of Al, ni, co, V and Mo in the waste petroleum hydrogenation catalyst is much higher than that of natural ores, so that the waste petroleum hydrogenation catalyst is a large-scale urban mine. These metals have wide applications in catalyst manufacture, lithium battery manufacture, and alloy manufacture. In 2020, the external dependence of molybdenum, cobalt and aluminum is 94.3%, 52.2% and 50% respectively. The method for recovering valuable metals such as Ni, co, mo, V and the like from the waste petroleum hydrogenation catalyst has great significance and prospect in terms of both environmental protection and national strategy.
At present, most processes for recovering the waste petroleum hydrogenation catalyst cannot be separated from roasting treatment. Through roasting process or removing oil on the surface of waste catalyst, and/or changing valuable metal in the waste catalyst into alloy product, and/or converting insoluble metal sulfide into soluble metal oxide or metal salt. However, the oil on the surface of the waste catalyst is easy to deflagrate in the roasting process, and the roasting temperature is difficult to control, so that insoluble NiMoO is generated 4 ,CoMoO 4 And the like, resulting in low metal recovery; the roasting process consumes a large amount of energy and generates a large amount of heat and CO 2 、SO 2 And the like, causing serious pollution to the environment; the surface oil content of the waste catalyst is about 20 percent of the mass of the waste petroleum catalyst, the property of the waste catalyst is similar to that of crude oil, the waste petroleum catalyst can be used as fuel and other various purposes, and the resource waste is undoubtedly caused by roasting.
Valuable metals in the acidic leached waste petroleum hydrogenation catalyst have poor selectivity, mo, V, al, co, ni and the like enter a solution in the leaching process, and the existence forms of Mo, V, W and the like in the acidic solution are complex, so that the separation of metal ions is difficult. The acid medium has strong corrosivity and the equipment investment cost is high. Good selectivity of alkaline leaching, V 2 O 5 And MoO 3 Is a meta-acidic oxide, al 2 O 3 The oxide is amphoteric oxide, coO and NiO are basic oxide, and Mo, V and Al can be separated from Co and Ni in the alkaline leaching process. The alkaline medium has small corrosivity and relatively low investment cost on equipment.
Currently, there are few reports of recovering all valuable components of a spent petroleum hydrogenation catalyst without calcination. Park et Al (Park, K.H., mohapatra, D., reddy, B.R.,2006.Selective recovery of molybdenum from space HDS catalyst using oxidative soda ash space/carbon adsorption method.J.Hazard.Mater.138 (2), 311-316.) Wash the waste Mo-Ni/γ -Al with acetone 2 O 3 Oil on the surface of the catalyst, then Na 2 CO 3 -H 2 O 2 Mo in the waste catalyst is leached out through oxidation, and the leaching rate of Mo under the optimal condition is only 85%. Acetone has a poor effect of removing oil on the surface of the waste catalyst, is volatile, and causes serious hidden danger to safety production. Marynet al (Ma, z.y., liu, y., zhou, j.k., liu, m.d., liu, z.z.,2019.Recovery of vanadium and molybdenum from specific catalytic catalyst by microwave-assisted leaching. Int.j.min. Met.mater.26 (1), 33-40.) directly crushed the spent catalyst, and selectively leached Mo and V with NaOH, with leaching rates of Mo and V being 94.35% and 96.23% respectively under optimum conditions. Li Zhihua, etc. (Li Zhihua, zhang Gui Qing, guan Wen Juan, rojun. Research on wet extraction of Mo and V from HDS waste catalyst, rare metals and hard alloy 2016,44 (3): 12-16) also comprises crushing the waste catalyst directly, and then using NaOH + H 2 O 2 Oxidation by oxygenMo and V are leached out, and the leaching rates of the Mo and the V are optimized>90％。H 2 O 2 Is weak acid, will react with Na 2 CO 3 And the reaction with NaOH increases reagent consumption, lowers the pH value of the leaching solution, causes partial Ni to enter the solution, and makes the subsequent metal ion separation difficult. The leaching rates of Mo and V are low, and the leaching behavior of Al and the separation method of Mo, V and Al in the leaching solution are not mentioned. In addition, the oil content on the surface of the waste petroleum hydrogenation catalyst is about 20 percent, the particles are seriously adhered, and the direct crushing is difficult.
Disclosure of Invention
The invention provides a method for recovering valuable components from a waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient manner, aiming at solving the problem of recovering the surface oil quality of the waste aluminum-based catalyst and the problem of economically and efficiently recovering valuable metals Mo, V, al, co and Ni in the waste petroleum hydrogenation catalyst without roasting, so that the leaching rates of Mo and V are both more than 98%, the comprehensive leaching rate of Al is more than 92%, and more than 99% of Co and Ni are enriched in leaching residues.
The invention provides a method for recovering valuable components from a waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient way, which is characterized in that the substrate of the waste aluminum-based catalyst containing Mo, V, co and Ni is gamma-Al 2 O 3 The contents of Mo, V, co and Ni are respectively 1-15%, 0-15% and 0-15%, and the recovery steps of the valuable components are as follows:
(1) Extracting and washing oil on the surface of the waste catalyst by using tetrahydrofuran or/and 1, 4-dioxane to obtain the deoiled waste catalyst and an organic phase containing the oil; distilling the organic phase containing oil under reduced pressure at 40-100 ℃ and 0.01-1 atmospheric pressure to obtain black oil;
(2) Adding NaOH solution into the deoiled waste catalyst obtained in the step (1), wherein the liquid-solid ratio of the waste catalyst to the NaOH solution is 10-1 2 Leaching for 0.5-24 hours at 25-180 ℃ and 1-10 atmospheric pressure in the presence of the alkaline leaching agent, and filtering to obtain alkaline oxide leaching solution and alkaline oxide leaching residue;
(3) Adjusting the pH value of the alkaline oxide leaching solution obtained in the step (2) to 7-9, and filtering to obtain Al (OH) 3 Precipitation and filtrate containing Mo and V; extracting and separating Mo and V in the filtrate by using a quaternary ammonium salt extracting agent, wherein the concentration of the extracting agent is 5-50 wt%, and compared with the A/O ratio of 10;
(4) Adding an ammonium chloride solution into the organic phase loaded with V obtained in the step (3), and filtering to obtain an ammonium vanadate precipitate; addition of BaCl to the Mo-containing raffinate 2 Or CaCl 2 Filtering the solution until no precipitate is generated, and obtaining molybdate precipitate;
(5) Adding NaOH solution into the oxidized alkaline leaching residue obtained in the step (2), leaching for 0.5-24 hours at 25-180 ℃ under 1-10 atmospheric pressure, and filtering to obtain alkaline leaching residue rich in Ni and Co and alkaline leaching solution containing Al; adjusting the pH value of the alkaline leaching solution containing Al to 5-9, and filtering to obtain Al (OH) 3 And (4) precipitating.
Further, the concentration of the NaOH solution in the step (2) is 0.1-5 mol/L, and the NaClO solution is 2 The dosage of the catalyst is 1 to 25 percent of the mass of the waste catalyst after oil removal.
Further, the alkaline oxidation leaching process in the step (2) can be enhanced by an ultrasonic field or a microwave field.
Further, al in the alkaline oxide leaching residue obtained in the step (2) can be recovered by a Bayer process.
Further, the diluent of the quaternary ammonium salt extracting agent in the step (3) is one or more of kerosene, sulfonated kerosene, toluene, xylene and isooctanol.
Further, the concentration of the ammonium chloride solution in the step (4) is 0.01-5 mol/L, compared with the A/O ratio of 5; the BaCl 2 Or CaCl 2 The concentration of the solution is 0.1-3 mol/L.
Further, the liquid-solid ratio of the oxidized alkali leaching residue to the NaOH solution in the step (5) is 15-1.
Further, al (OH) obtained in the step (3) and the step (5) 3 The precipitate can be calcined at 900-1200 ℃ to prepare Al 2 O 3 And (5) producing the product.
The method is different from the traditional oxidation alkaline leaching and roasting-alkaline leaching technologies.The surface of the waste petroleum hydrogenation catalyst contains about 20 percent of black organic matters, the property of the waste petroleum hydrogenation catalyst is similar to that of crude oil, the method for roasting to remove oil not only causes resource waste, but also generates a large amount of harmful gas to pollute the environment in the roasting process, and therefore, the recovery of the black organic matters is considered. Researches show that the main component of the black organic matter is heterocyclic organic matter, and the structure of the black organic matter is more similar to that of tetrahydrofuran and 1, 4-dioxane. According to the principle of similarity and compatibility, the method adopts tetrahydrofuran and/or 1, 4-dioxane to carry out oil removal treatment on the waste petroleum hydrogenation catalyst, and compared with the traditional acetone oil removal method, the method has higher efficiency and higher oil removal efficiency. In the traditional oxidation alkaline leaching, metal sulfide in the waste petroleum hydrogenation catalyst is oxidized by hydrogen peroxide to obtain easily leached metal oxide. However, in the oxidation leaching process, hydrogen peroxide generally reacts with an alkaline solvent due to weak acidity, so that the oxidation efficiency is reduced, and the metal leaching rate is reduced due to consumption of alkali. Moreover, the addition of excessive hydrogen peroxide causes the leachate to be acidic, which results in the leaching of Ni, and the types of metal ions in the solution become more, which is contrary to the original intention of alkaline leaching. NaClO 2 The alkaline oxidizing agent has stronger oxidability in an alkaline solution, does not react with a solvent, can ensure higher oxidation efficiency, does not introduce other metal ions, and simplifies the subsequent separation process. Adding NaClO to deoiled waste petroleum hydrogenation catalyst in the first step 2 The oxidant is used for oxidizing alkaline leaching, and because the solubility of each metal compound in the alkaline liquor is different, the concentration of NaOH needs to be strictly controlled in the leaching process, so that all Mo and V are leached, al is leached as little as possible, and the problems of low oxidation efficiency, low metal leaching rate and complex metal ions in the solution are solved; the second step of alkaline leaching adjusts NaOH concentration, temperature and time to ensure that more than 95 percent of Al is leached, and Al (OH) is added 3 Seed crystal and slow cooling method to ensure that AlO in the solution 2 With Al (OH) 3 The form of (2) is precipitated and recycled, and the problem of substrate recycling is solved. The quaternary ammonium salt extracting agent can be used under alkaline conditions, and Mo and V can be separated under alkaline conditions. The pH of the completely Al-depleted oxidation alkaline leach solution is less than 8.6, at which pH the quaternary ammonium salt extractant is effectiveThe extraction of V leaves Mo in the raffinate, and the concentration of the extractant, the composition of the diluent, the initial pH and the phase ratio determine the efficiency of the extraction separation of V and Mo.
The method for recovering valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient way belongs to the all-wet process flow, and avoids the generation of insoluble metal compounds (NiMoO) caused by roasting 4 ,CoMoO 4 ) Resulting in the difficult problem of low leaching rate of valuable metals without CO 2 、SO 2 The organic solvent for extracting and washing the oil on the surface of the waste catalyst can be separated from the oil by reduced pressure distillation and recycled for removing the oil on the surface of the waste catalyst.
The method for recovering valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient manner is simple and has low reagent consumption. NaOH + NaClO 2 The efficiency of oxidizing Mo and V in the alkaline leaching waste catalyst is high, and the leaching rate of Mo and V can be high>99 percent, impurity elements except Na and Cl are not introduced, the influence on the purity of the product is small, the separation of Mo and V from Co, ni and most of Al is realized in the oxidation alkaline leaching stage, and the subsequent metal separation to obtain the pure product is simple. The Al selectivity of the NaOH leached alkali oxide leaching residue is good, and the separation of Co, ni and Al is realized in the leaching stage. By NaOH + NaClO 2 The process comprises two procedures of oxidation alkaline leaching and NaOH leaching, the comprehensive leaching rate of Al can be more than or equal to 95 percent, and more than 99 percent of Co and Ni are enriched in alkaline leaching residues.
The method for recovering valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient manner can realize the recovery of all valuable components in the waste catalyst, and has the advantages of simple process, high efficiency and environmental protection.
Drawings
FIG. 1: the appearance of the waste aluminum-based petroleum hydrogenation catalyst before oil removal,
FIG. 2 is a schematic diagram: the appearance of the deoiled waste aluminum-based petroleum hydrogenation catalyst,
FIG. 3: the oil recovered from the waste aluminum-based petroleum hydrogenation catalyst,
FIG. 4: naOH + NaClO 2 Oxidation alkali after oxidation alkali leachingXPS spectra of elements in the leaching residue,
FIG. 5: al (aluminum) 2 O 3 The XRD pattern of the product is shown,
FIG. 6: baMoO 4 The SEM and XRD patterns of the product,
FIG. 7: NH (NH) 4 VO 3 SEM and XRD patterns of the product.
Table 1 concentration change of metal ions in the separation process of Mo, V, al in the oxidation alkali leaching solution.
Detailed Description
The process of the present invention is further illustrated below with reference to examples. The examples of the present invention are provided for the purpose of explanation and are not to be construed as limiting the invention.
Example 1
(1) 20.0g of the waste petroleum hydrogenation catalyst is weighed, wrapped by filter paper and placed in a Soxhlet extractor. Tetrahydrofuran having a volume of two thirds of that of the flask was added to the single-neck flask connected to the lower end of the Soxhlet extractor, and then placed in a water bath. The upper end of the Soxhlet extractor is connected with a reflux condenser pipe. The water bath was heated and the temperature was set at 80 ℃ and extracted for 24 hours. And taking out the waste catalyst in the extractor, and drying at 60 ℃ to obtain the deoiled waste petroleum hydrogenation catalyst. Distilling the extract in the round-bottom flask at 60 deg.C under reduced pressure to remove tetrahydrofuran to obtain black oil.
(2) 12.0g of deoiled waste petroleum hydrogenation catalyst is weighed and placed in a 100mL polytetrafluoroethylene reaction kettle lining, 60mL of 1.0mol/L NaOH solution and 2.4g of NaClO are added 2 The reaction kettle is screwed down and then placed in a vertical reaction furnace with magnetic stirring, and leaching is carried out for 1 hour at 90 ℃. And cooling to room temperature, and performing suction filtration to obtain the oxidation alkali leaching residue and the oxidation alkali leaching solution.
(3) 50mL of the alkali oxide extract obtained in the step (2) was added dropwise with 6mol/L hydrochloric acid to adjust the pH of the solution to 8.6, and after standing for 0.5 hour, filtration was carried out to obtain Al (OH) 3 Precipitating and filtering the solution containing Mo and V. 5g of methyltrioctylammonium chloride extractant is weighed and dissolved in 20g of mixed solution (V) of kerosene and isooctyl alcohol Kerosene oil :V Isooctyl alcohol = 9). 20mL of the filtrate containing Mo and V was placed in a 60mL separatory funnel, 20mL of the above extractant solution was added, and 2 60mL separatory funnels were usedAnd simulating 3-stage countercurrent extraction, and separating the lower-layer aqueous phase when the concentration of V in the aqueous phase is not changed any more to obtain a V-loaded organic phase and Mo-containing raffinate.
(4) Adding 20mL of 3mol/L NH into the V-loaded organic phase obtained in the step (3) 4 Shaking Cl solution for 0.5 hr, standing for 0.1 hr, separating the lower suspension, filtering, washing with water, and drying at 60 deg.C for 24 hr to obtain NH 4 VO 3 And (5) producing the product. To the raffinate was added 10g of BaCl 2 Solid, stirred for 1 hour and filtered to obtain BaMoO-containing 4 Precipitation of (4). To contain BaMoO 4 Adding 50mL deionized water to the precipitate, adjusting pH =5.0 with 6mol/L HCl, filtering to remove insoluble matter, adjusting pH =8.6 with 2mol/L NaOH, filtering, washing with water, and drying at 60 deg.C for 24 hr to obtain pure BaMoO 4 And (5) producing the product.
(5) And (3) placing the alkaline oxide leaching residues obtained in the step (2) into a 100mL polytetrafluoroethylene reaction kettle lining, adding 25mL of 4mol/L NaOH solution, sealing the reaction kettle, placing the reaction kettle in a vertical reaction furnace with a magnetic stirring function, and leaching for 6 hours at 180 ℃. And cooling to room temperature, and performing suction filtration to obtain Ni and Co-rich alkaline leaching residue and Al-containing alkaline leaching solution. Adding 6mol/L HCl into alkali immersion liquid containing Al dropwise to adjust pH to 8.6, standing for 0.5 hr, filtering, and washing with water to obtain Al (OH) 3 And (4) precipitating. Mixing the Al (OH) 3 Precipitating and Al (OH) obtained in step (3) 3 Calcining the precipitate at 1000 ℃ for 5 hours respectively to obtain Al 2 O 3 And (5) producing the product.
Example 2
(1) 20.0g of the waste petroleum hydrogenation catalyst is weighed, wrapped by filter paper and placed in a Soxhlet extractor. To a single-neck flask connected to the lower end of a Soxhlet extractor was added 1, 4-dioxane having two-thirds of its volume, and then placed in an oil bath. The upper end of the Soxhlet extractor is connected with a reflux condenser pipe. The oil bath was heated and the temperature was set at 110 ℃ and extracted for 24 hours. And taking out the waste catalyst in the extractor, and drying at 60 ℃ to obtain the deoiled waste petroleum hydrogenation catalyst. Distilling the extract in round-bottom flask at 90 deg.C under reduced pressure to remove 1, 4-dioxane to obtain black oil.
(2) Weighing 10.0g of deoiled waste petroleum, and hydrogenatingThe catalyst was placed in the inner liner of a 100mL Teflon reactor, 50mL of 1.5mol/L NaOH solution and 2.0g of NaClO were added 2 The reaction kettle is screwed down and then placed in a microwave reaction furnace, the microwave power is set to be 600W, and leaching is carried out for 0.5 hour at 120 ℃. And cooling to room temperature, and performing suction filtration to obtain the oxidation alkali leaching residue and the oxidation alkali leaching solution.
(3) Taking 40mL of the alkaline oxide leaching solution obtained in the step (2), dropwise adding 6mol/L hydrochloric acid to adjust the pH of the solution to 8.0, standing for 0.5 hour, and filtering to obtain Al (OH) 3 Precipitating and filtering the solution containing Mo and V. Weighing 4g of methyl trioctyl ammonium chloride extractant, and dissolving in 20g of mixed solution (V) of kerosene and isooctyl alcohol Kerosene oil :V Isooctyl alcohol 1) =5. And (3) putting 30mL of filtrate containing Mo and V into a 60mL separating funnel, adding 20mL of the extracting agent solution, simulating 4-stage countercurrent extraction by using 3 60mL separating funnels, and separating a lower aqueous phase when the concentration of V in the aqueous phase is not changed any more to obtain an organic phase loaded with V and raffinate containing Mo.
(4) 20mL of 2.5mol/L NH is added into the V-loaded organic phase obtained in the step (3) 4 The Cl solution is shaken for 1 hour and then is kept stand for 0.1 hour, the lower suspension is separated out, filtered, washed and dried for 24 hours at the temperature of 60 ℃, and NH is obtained 4 VO 3 And (5) producing the product. To the raffinate was added 15g of BaCl 2 Solid, stirred for 1 hour and filtered to obtain BaMoO-containing 4 Precipitation of (4). To contain BaMoO 4 Adding 50mL deionized water to the precipitate, adjusting pH =5.0 with 6mol/L HCl, filtering to remove insoluble matter, adjusting pH =8.6 with 2mol/L NaOH, filtering, washing with water, and drying at 60 deg.C for 24 hr to obtain pure BaMoO 4 And (5) producing the product.
(5) And (3) placing the oxidized alkali leaching residue obtained in the step (2) into a 100mL polytetrafluoroethylene reaction kettle lining, adding 30mL 5mol/L NaOH solution, sealing the reaction kettle, placing the reaction kettle into a vertical reaction furnace with a magnetic stirring function, and leaching for 4 hours at 150 ℃. And cooling to room temperature, and performing suction filtration to obtain Ni and Co-rich alkaline leaching residue and Al-containing alkaline leaching solution. Adding 6mol/L HCl into alkali immersion liquid containing Al dropwise to adjust pH to 8.0, standing for 0.5 hr, filtering, and washing with water to obtain Al (OH) 3 And (4) precipitating. Mixing the Al (OH) 3 Precipitating and Al (OH) obtained in step (3) 3 Precipitating at 1100 deg.C, calcining respectivelyFiring for 2 hours to obtain Al 2 O 3 And (5) producing the product.
Example 3
(1) 100.0g of the waste petroleum hydrogenation catalyst is weighed, wrapped by filter paper and placed in a Soxhlet extractor. Tetrahydrofuran was added in two thirds of its volume in a single-neck flask connected to the lower end of a Soxhlet extractor, and then placed in a water bath. The upper end of the Soxhlet extractor is connected with a reflux condenser pipe. The water bath was heated and the temperature was set at 80 ℃ and extracted for 72 hours. And taking out the waste catalyst in the extractor, and drying at 60 ℃ to obtain the deoiled waste petroleum hydrogenation catalyst. Distilling the extract in the round-bottom flask at 60 deg.C under reduced pressure to remove tetrahydrofuran to obtain black oil.
(2) 100.0g of deoiled waste petroleum hydrogenation catalyst is weighed and placed in a 1L of polytetrafluoroethylene reaction kettle lining, 500mL of 1.5mol/L NaOH solution and 20.0g of NaClO are added 2 The lining was placed in a high temperature autoclave with mechanical stirring paddles, screwed down and leached at 90 ℃ for 1.5 hours. And cooling to room temperature, and performing suction filtration to obtain the oxidation alkali leaching residue and the oxidation alkali leaching solution.
(3) Taking 100mL of the alkaline oxide leaching solution obtained in the step (2), dropwise adding 12mol/L hydrochloric acid to adjust the pH of the solution to 8.5, standing for 0.5 hour, and filtering to obtain Al (OH) 3 Precipitating and filtering the solution containing Mo and V. 20g of methyltrioctylammonium chloride extractant are weighed out and dissolved in 100g of toluene solution. And (3) putting 70mL of filtrate containing Mo and V into a 250mL separating funnel, adding 70mL of the extractant solution, simulating 3-stage countercurrent extraction by using 2 250mL separating funnels, and separating a lower-layer aqueous phase when the concentration of V in the aqueous phase is not changed any more to obtain a V-loaded organic phase and a Mo-containing raffinate.
(4) Adding 70mL of 4mol/L NH into the V-loaded organic phase obtained in the step (3) 4 Shaking Cl solution for 0.5 hr, standing for 0.1 hr, separating the lower suspension, filtering, water washing, and drying at 60 deg.c for 24 hr to obtain NH 4 VO 3 And (5) producing the product. To the raffinate was added 50g of BaCl 2 Solid, stirred for 1 hour and filtered to obtain BaMoO-containing 4 Precipitation of (4). To contain BaMoO 4 Adding 50mL of deionized water to the precipitate, adjusting pH =5.0 with 6mol/L HCl, filtering to remove insoluble matter, and addingAdjusting pH =8.6 with 2mol/L NaOH, filtering, washing with water, and drying at 60 deg.C for 24 hours to obtain pure BaMoO 4 And (5) producing the product.
(5) And (3) placing the oxidized alkali leaching residue obtained in the step (2) into the liner of a 1L polytetrafluoroethylene reaction kettle, adding 500mL of 5mol/L NaOH solution, placing the liner into the reaction kettle, screwing down, and leaching at 200 ℃ for 5 hours. And cooling to room temperature, and performing suction filtration to obtain Ni and Co-rich alkaline leaching residue and Al-containing alkaline leaching solution. Adding 6mol/L HCl into alkali immersion liquid containing Al dropwise to adjust pH to 8.5, standing for 0.5 hr, filtering, and washing with water to obtain Al (OH) 3 And (4) precipitating. Mixing the Al (OH) 3 Precipitating and Al (OH) obtained in step (3) 3 Calcining the precipitate at 1200 ℃ for 3 hours respectively to obtain Al 2 O 3 And (5) producing the product.
TABLE 1 concentration variation of metal ions in Mo, V, al separation process in oxidation alkali immersion liquid
Claims (8)
1. The method for recovering valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni in a gradient way is characterized in that the substrate of the waste aluminum-based catalyst containing Mo, V, co and Ni is gamma-Al 2 O 3 The contents of Mo, V, co and Ni are respectively 1-15%, 0-15% and 0-15%, and the recovery steps of the valuable components are as follows:
(1) Extracting and washing oil on the surface of the waste catalyst by using tetrahydrofuran or/and 1, 4-dioxane to obtain the oil-removed waste catalyst and an organic phase containing oil; distilling the organic phase containing oil under reduced pressure at 40-100 ℃ and 0.01-1 atmospheric pressure to obtain black oil;
(2) Adding NaOH solution into the deoiled waste catalyst obtained in the step (1), wherein the liquid-solid ratio of the waste catalyst to the NaOH solution is 10-1 2 Leaching for 0.5-24 hours at 25-180 ℃ and 1-10 atmospheric pressure in the presence of the alkaline leaching agent, and filtering to obtain alkaline oxide leaching solution and alkaline oxide leaching residue;
(3) Adjusting the alkaline oxide leaching solution obtained in the step (2)To pH 7-9, filtering to obtain Al (OH) 3 Precipitating and filtering liquid containing Mo and V; extracting and separating Mo and V in the filtrate by using a quaternary ammonium salt extracting agent, wherein the concentration of the extracting agent is 5-50 wt%, and compared with the A/O ratio of 10;
(4) Adding an ammonium chloride solution into the organic phase loaded with V obtained in the step (3), and filtering to obtain an ammonium vanadate precipitate; addition of BaCl to the Mo-containing raffinate 2 Or CaCl 2 Filtering the solution until no precipitate is generated, and obtaining molybdate precipitate;
(5) Adding NaOH solution into the oxidized alkaline leaching residue obtained in the step (2), leaching for 0.5-24 hours at 25-180 ℃ under 1-10 atmospheric pressure, and filtering to obtain alkaline leaching residue rich in Ni and Co and alkaline leaching solution containing Al; adjusting the pH value of the Al-containing alkaline leaching solution to 5-9, and filtering to obtain Al (OH) 3 And (4) precipitating.
2. The method for step recovery of valuable components from waste aluminum-based catalyst containing Mo, V, co, ni as claimed in claim 1, wherein the NaOH solution in step (2) has a concentration of 0.1-5 mol/L and NaClO 2 The dosage of the catalyst is 1 to 25 percent of the mass of the waste catalyst after oil removal.
3. The method for step recovery of valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni as claimed in claim 1, wherein the alkaline oxidation leaching process in step (2) is enhanced by an ultrasonic field or a microwave field.
4. The method for step recovery of valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni as claimed in claim 1, wherein the Al in the caustic soda leach residue obtained in step (2) is recovered by Bayer process.
5. The method for step recovery of valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni as claimed in claim 1, wherein the diluent of the quaternary ammonium salt extractant in step (3) is one or more of kerosene, sulfonated kerosene, toluene, xylene and isooctanol.
6. The method for the step recovery of valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni as claimed in claim 1, wherein the concentration of the ammonium chloride solution in the step (4) is 0.01-5 mol/L, compared with the A/O of 5; the BaCl 2 Or CaCl 2 The concentration of the solution is 0.1-3 mol/L.
7. The method for step recovery of valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni as claimed in claim 1, wherein the liquid-solid ratio of the oxidized caustic sludge and NaOH solution in step (5) is 15 to 1, and the concentration of the NaOH solution is 0.1 to 5mol/L.
8. The method for step recovery of valuable components from the waste aluminum-based catalyst containing Mo, V, co and Ni as claimed in claim 1, wherein Al (OH) obtained in step (3) and step (5) 3 The precipitate can be calcined at 900-1200 ℃ to prepare Al 2 O 3 And (5) producing the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211530694.0A CN115838873B (en) | 2022-12-01 | 2022-12-01 | Method for stepwise recovering valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211530694.0A CN115838873B (en) | 2022-12-01 | 2022-12-01 | Method for stepwise recovering valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115838873A true CN115838873A (en) | 2023-03-24 |
| CN115838873B CN115838873B (en) | 2024-03-26 |
Family
ID=85577842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211530694.0A Active CN115838873B (en) | 2022-12-01 | 2022-12-01 | Method for stepwise recovering valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115838873B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925690A (en) * | 2011-08-11 | 2013-02-13 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from waste and old Raney nickel catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN104130853A (en) * | 2014-07-04 | 2014-11-05 | 重庆工商大学 | Method for regenerating waste oil by extracting novel combination solvent |
| CN104805298A (en) * | 2015-05-22 | 2015-07-29 | 北京赛科康仑环保科技有限公司 | Method for recovering waste SCR (Selective Catalytic Reduction) denitration catalyst |
| CN108531733A (en) * | 2018-03-27 | 2018-09-14 | 昆明理工大学 | A kind of method that useless aluminium-based catalyst of microwave sodium roasting consolidates sulphur decarburization |
| CN112322901A (en) * | 2020-11-04 | 2021-02-05 | 中国地质科学院郑州矿产综合利用研究所 | Method for selectively leaching rhenium from molybdenum concentrate roasting soot |
| CN112646977A (en) * | 2020-12-18 | 2021-04-13 | 北京普能世纪科技有限公司 | Method for recovering vanadium, molybdenum, nickel and aluminum from petroleum refining waste catalyst |
| CN113789446A (en) * | 2021-08-23 | 2021-12-14 | 常州大学 | Method for recovering molybdenum, vanadium and nickel metals from waste catalyst |
| CN114438332A (en) * | 2022-01-25 | 2022-05-06 | 中南大学 | Treatment method and application of waste hydrogenation catalyst |
-
2022
- 2022-12-01 CN CN202211530694.0A patent/CN115838873B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925690A (en) * | 2011-08-11 | 2013-02-13 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from waste and old Raney nickel catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN104130853A (en) * | 2014-07-04 | 2014-11-05 | 重庆工商大学 | Method for regenerating waste oil by extracting novel combination solvent |
| CN104805298A (en) * | 2015-05-22 | 2015-07-29 | 北京赛科康仑环保科技有限公司 | Method for recovering waste SCR (Selective Catalytic Reduction) denitration catalyst |
| CN108531733A (en) * | 2018-03-27 | 2018-09-14 | 昆明理工大学 | A kind of method that useless aluminium-based catalyst of microwave sodium roasting consolidates sulphur decarburization |
| CN112322901A (en) * | 2020-11-04 | 2021-02-05 | 中国地质科学院郑州矿产综合利用研究所 | Method for selectively leaching rhenium from molybdenum concentrate roasting soot |
| CN112646977A (en) * | 2020-12-18 | 2021-04-13 | 北京普能世纪科技有限公司 | Method for recovering vanadium, molybdenum, nickel and aluminum from petroleum refining waste catalyst |
| CN113789446A (en) * | 2021-08-23 | 2021-12-14 | 常州大学 | Method for recovering molybdenum, vanadium and nickel metals from waste catalyst |
| CN114438332A (en) * | 2022-01-25 | 2022-05-06 | 中南大学 | Treatment method and application of waste hydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115838873B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103468949B (en) | A kind for the treatment of process containing scandium nickel hydroxide cobalt | |
| CN105274344A (en) | Method for recycling vanadium and molybdenum from waste petroleum catalyst | |
| CN103468979B (en) | The method of scandium is reclaimed from smelting laterite-nickel ores iron aluminium slag | |
| CN103484695B (en) | Treatment method for comprehensively recovering valuable elements from laterite-nickel ore | |
| CN103468978B (en) | A kind of method carrying scandium from laterite nickel ore by sulfuric acid leaching liquid | |
| CN102534209B (en) | Reduction leaching method of manganese oxide ores | |
| CN103468972B (en) | The treatment process of red soil nickel ore synthetical recovery scandium and nickel cobalt | |
| CN112342389A (en) | Method for recovering valuable metal from waste chemical catalyst | |
| CN101225470A (en) | Method for extracting nickel and cobalt from lateritic nickel by hydrochloric acid process | |
| CN103468948B (en) | Method for comprehensive recycling of metals from scandium-containing cobalt nickel hydroxide | |
| CN112226630B (en) | Method for extracting valuable metal elements from laterite-nickel ore by hydrochloric acid leaching method and acid-base regeneration circulation | |
| CN103468980B (en) | A kind of red soil nickel ore extracts the method for scandium | |
| CN114959261B (en) | Method for recovering tungsten, molybdenum, nickel and cobalt from multi-metal alloy in full wet process | |
| CN111628202B (en) | VOSO4Preparation method of sulfuric acid solution and VOSO4Electrolyte solution | |
| CN109811132A (en) | A method of comprehensive reutilization carbon, iron, aluminium, zinc, lead from blast furnace gas mud | |
| CN114622102A (en) | Method for comprehensively extracting valuable metals from laterite-nickel ore | |
| CN103173619A (en) | Method for recovering nickel and tungsten by waste nickel and tungsten catalyst | |
| CN107674976B (en) | A method of with cobalt and manganese in ammonia-ammonium hydrogen carbonate separation and recovery high manganese waste material of low cobalt | |
| CN107739828B (en) | A method of with cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt | |
| CN112410560A (en) | Method for recycling nickel-based waste catalyst | |
| CN115838873B (en) | Method for stepwise recovering valuable components from waste aluminum-based catalyst containing Mo, V, co and Ni | |
| CN113845455B (en) | Recycling method of Fumei slag | |
| CN114058859A (en) | Method for preparing nickel vanadate from petroleum POX slag | |
| CN114807606A (en) | Full component recovery method of waste hydrogenation catalyst | |
| CN112746172B (en) | Treatment method of deactivated hydrogenation catalyst |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |