CN111876603B - Wet process for recovering Fe, Al, Ni, Mo and Co from waste hydrorefining catalyst - Google Patents
Wet process for recovering Fe, Al, Ni, Mo and Co from waste hydrorefining catalyst Download PDFInfo
- Publication number
- CN111876603B CN111876603B CN202010731298.9A CN202010731298A CN111876603B CN 111876603 B CN111876603 B CN 111876603B CN 202010731298 A CN202010731298 A CN 202010731298A CN 111876603 B CN111876603 B CN 111876603B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molybdenum
- sulfuric acid
- nickel
- iron
- 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.)
- Active
Links
Images
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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
- C22B21/003—Obtaining aluminium by wet processes from waste materials 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
-
- 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
Abstract
The invention discloses a wet method recovery process of iron, aluminum, nickel, molybdenum and cobalt from hydrofining waste catalyst, which comprises the steps of calcining and grinding the catalyst, roughing by a foam flotation method, impregnating the roughed catalyst by dilute sulfuric acid, filtering, feeding molybdenum-containing filter residue into the next process, precipitating the filtrate step by step to separate iron and aluminum, electrolyzing the filtered solution by using anion exchange resin and an electrolytic cell, wherein the cathode of the electrolytic cell can recover high-purity nickel and cobalt metals, and the anode recovers sulfuric acid solution under the action of the anion exchange resin. Dissolving the molybdenum-containing filter residue in the recovered sulfuric acid for electrolysis, obtaining high-purity molybdenum metal at the cathode, and recovering the sulfuric acid solution at the anode under the action of anion exchange resin. The catalyst has high recovery efficiency, no waste liquid is discharged, the sulfuric acid can be recycled, no other elements are introduced, and the catalyst has the advantages of simple and efficient process, high economic value, high atom utilization rate, no influence on the environment and the like.
Description
Technical Field
The invention relates to the technical field of catalyst recovery. Relates to a process for wet recovery of iron, aluminum, nickel, molybdenum and cobalt from a hydrofining waste catalyst, in particular to a method for wet recovery of iron, aluminum, nickel, molybdenum and cobalt from a nickel-molybdenum-containing catalyst, and the method has higher recovery rate.
Background
Due to the rapid development of science and technology, the development of economy is largely at the cost of sacrificing natural resources and ecological environment. Almost 80% of the chemical reactions in the rapidly developing chemical and petroleum industry since the last century have required catalysts. Each year, several thousand tons of the molybdenum-containing spent catalyst are discharged from the apparatus, and thus the recovery of valuable metals from the spent catalyst is receiving much attention.
Molybdenum is used as an alloy additive of iron, is beneficial to forming a complete pearlite matrix, can improve the strength and toughness of cast iron, improves the uniformity of the structure of a large casting, and can also improve the hardenability of a heat-treated casting. The grey cast iron containing molybdenum has good wear resistance and can be used as brake wheel and brake pad of heavy vehicle. Molybdenum is one of essential 'trace elements' in the plant body, and accounts for about 0.5ppm of the dry plant amount, and is indispensable and irreplaceable. In recent years, ammonium molybdate is widely used as a trace element fertilizer at home and abroad, and the quality and yield of legumes, pasture and other crops can be remarkably improved. Molybdenum can also accelerate the formation and transformation of carbohydrate in plants, improve the content and stability of phytoalexin and the content of vitamin C. Molybdenum, nickel, cobalt, etc. can be used to make various types of stainless steel, tool steel, high speed steel, alloy steel, etc. The produced stainless steel has good corrosion resistance, can be used for corrosion-resistant steel pipes for oil exploitation, and the stainless steel with molybdenum content of about 6 percent can also be used for seawater desalination devices, ocean vessels, offshore oil and natural gas exploitation pipelines instead of titanium. The stainless steel can also be used for automobile shells, sewage treatment equipment and the like.
The catalyst is gradually poisoned in the using process, and finally loses the catalytic activity and is discarded. According to Liu Gong summons and other reports, about 80 ten thousand of catalysts are consumed every year in the world, and 7 ten thousand of catalysts are consumed in China. The waste catalyst containing molybdenum has various varieties, the content of molybdenum is 3-20%, and if cobalt and molybdenum in the waste catalyst are not recycled, the total amount of the lost cobalt and molybdenum metal is very surprising. Therefore, the recovery work of recovering molybdenum, cobalt and other metals from the molybdenum-containing waste catalyst is carried out, so that the sustainable development of the cobalt and molybdenum industry is facilitated, the specific embodiment of changing waste into valuable and practicing the circular economy concept is realized, and the method has obvious ecological benefit, economic benefit and social benefit.
The catalyst recovery schemes mainly include the following three schemes:
acid leaching method: the acid leaching method is to use common sulfuric acid, hydrochloric acid or nitric acid as leaching agent, and the main principle is to dissolve molybdenum and other soluble impurities in the waste catalyst into acid, and then to remove impurities and recover molybdenum and other metals respectively by means of reagent supplement, extraction, precipitation and the like.
Alkaline leaching method: the main principle of the alkaline leaching method is to make the waste catalytic vitex in sulfide form (MoS)2) The molybdenum present is converted to molybdenum oxide (MoO) by calcination3) Then, alkali is used as a leaching agent to convert molybdenum oxide into soluble compounds, and then the metals such as molybdenum and the like are separated and recovered through operations such as acid regulation, impurity removal, extraction and the like.
Fire recovery:
the domestic research on the recovery of molybdenum from waste catalysts by a pyrogenic process is not many, mainly the waste catalysts are smelted by a plasma furnace, the slag-iron separation effect is good, valuable metals in the enriched alloy account for about 70%, the average recovery rate of the metals reaches 93%, and the load of separating and purifying the valuable metals by a hydrometallurgical process can be greatly reduced. But the process obviously has the defects of high energy consumption, immature process and the like and needs to be further improved. Although the three schemes are all applicable, the defects are obvious, the recovery rate is low, and particularly, the waste of energy recovered by a pyrogenic process is high, and the recovery efficiency is low.
In the methods of "CN 202010139641.0 a method for recovering molybdenum from molybdenum-containing spent catalyst" and "the research on extraction and separation of molybdenum, vanadium, nickel and cobalt in acidic solution, it was thought" and the like, molybdenum is extracted and recovered from pickle liquor by adding an extracting agent, the method not only has high production cost, but also has great influence on the environment when the extracting agent is used. In the experimental research of comprehensive recovery of the waste catalyst containing molybdenum, nickel, bismuth and cobalt, a marten and a CN201610631967.9 process for recovering molybdenum, bismuth, cobalt and nickel from the waste catalyst are realized by regulating the pH value to precipitate different metal salts step by step, so that the method has the advantages of low recovery rate, low purity and large adverse effect on the environment. In addition, in the existing recovery and separation processes of many molybdenum-containing catalysts, only single recovery of molybdenum metal is mostly considered, other metal components do not have specific separation requirements, and different metal components are recovered in one system at one time, so compared with the recovery of single molybdenum metal, the recovery and separation processes have more influence factors to be considered and greater difficulty. In addition, in the existing recovery reaction, an intermittent reaction process is adopted, namely, a large amount of acid waste liquid is discharged after the catalyst is recovered once, the waste liquid can be discharged or reused after special treatment, the generation of acid liquor has great harm to the environment and high treatment cost, and metals which are not fully recovered may exist in the discharged acid waste liquid, which is obviously not beneficial to the full recovery of all metal components of the molybdenum-containing waste catalyst.
Therefore, how to fully recover iron, aluminum, nickel, molybdenum and cobalt metals in the nickel-molybdenum catalyst and effectively improve the common problem of waste liquid treatment in catalyst recovery is one of the technical problems to be solved by the invention.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a continuous recovery nickel-molybdenum catalyst system, in which not only can iron, aluminum, nickel, molybdenum and cobalt catalyst components be respectively recovered, but also the recovery of each metal can reach more than 95%. And meanwhile, a byproduct sulfuric acid solution can be obtained and can be continuously recycled in the system, so that the problem that the traditional intermittent reaction acid waste liquid is difficult to directly reuse is solved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
(1) calcining the waste nickel-molybdenum catalyst, cooling, crushing the catalyst into powder, performing rough separation by using a foam flotation method, and defoaming.
Furthermore, the crushed particles of the catalyst are 180-1800 meshes, and the crushed particles of the catalyst are further optimized to be 1000-1600 meshes.
Further, the adopted foaming agent is fatty alcohol, and the foam flotation method adopts a centrifugal mode to defoam, and further optimizes that the centrifugal speed is 600-800 r/min.
(2) And (3) putting the roughly-selected catalyst into dilute sulfuric acid, filtering, respectively collecting filtrate and filter residues, wherein the filter residues are reserved, adjusting the pH value of the filtrate, gradually settling, and respectively recovering iron and aluminum metals.
Further, the temperature during acid leaching is 40-90 ℃, the concentration of dilute sulfuric acid is 2-4 mol/L, and the acid leaching time is 1-3 hours; further optimizing the temperature of the acid leaching to be about 60-70 ℃, the concentration of the dilute sulfuric acid to be 3-4 mol/L and the time to be 1-2 hours.
Further, recovering iron metal when the pH value is adjusted to 1.5-3.5, and recovering iron metal when the pH value is adjusted to 3.5-5.5; further, the pH of iron is 2 to 3, and the pH of aluminum is 4 to 5.
(3) Adjusting the pH value of the catalyst acid solution after recovering iron and aluminum metals, placing the adjusted catalyst acid solution in an electrolytic cell for electrolysis, recovering nickel and cobalt metals, and obtaining a high-concentration sulfuric acid solution after recovery;
further, the pH value is adjusted to 2-3.
Further, in the electrolysis step, filtered catalyst acid liquid is introduced into an electrolytic cell, the voltage applied during nickel metal recovery is 2-20V Ni, and the voltage is adjusted to recover 20-50V Co after recovery; further optimizing the Ni to 10-20V; co is 30-40V.
Wherein the electrolytic cell consists of a cathode, an anode and an anion exchange resin membrane; wherein the recovered metal element is used as a cathode, the graphite is used as an anode, and the anion exchange resin is sulfate anion exchange resin.
In the above steps, after the electrolysis reaction is finished, a high-concentration sulfuric acid solution can be obtained in the cathode chamber and used for the next reaction.
Furthermore, the concentration of the sulfuric acid solution on the side of the semipermeable membrane (anion exchange resin) close to the cathode is 2-8 mol/L. The concentration of the sulfuric acid solution on the side, close to the cathode, of the semipermeable membrane is optimized to be 3-4 mol/L.
(4) Adding the filter residue obtained in the step (2) into the sulfuric acid obtained in the step (3), adjusting the sulfuric acid to a specific concentration, performing acid leaching for a period of time, filtering, adjusting the pH value of the filtrate, and adding NH4And F and HF solution are then placed in an electrolytic cell for electrolysis, molybdenum metal is recovered through electrolysis, and a by-product sulfuric acid solution is obtained and is directly used for the next step of cyclic reaction.
Wherein the concentration of acid leaching sulfuric acid is 6-10 mol/L, the acid leaching temperature is 40-60 ℃, and the acid leaching time is 1-3 hours. Further optimizing the concentration of sulfuric acid to be 8-9 mol/L, the acid leaching temperature to be 50-60 ℃, and the acid leaching time to be 1-2 hours.
Further, step (4) adding NH4F and HF until the concentration of the F and HF in the filtrate reaches 1-5 g/L, and electrolyzing MThe voltage of o is 30-60V. Further optimized to filtrate NH4The concentration of F and HF is 3-4 g/L, and Mo is 40-50V.
The catalyst recovery process of the invention has the following advantages:
the invention provides a circular processing system capable of continuously processing a large amount of catalysts, in the system, under the premise of introducing ions as little as possible, the recovery rate of aluminum, nickel, molybdenum and cobalt can be improved, in addition, the invention introduces anion exchange resin in catalyst recovery for the first time, the circular use mode of concentrated sulfuric acid solution can be realized, the environmental problem caused by catalyst recovery is basically eliminated, wherein, the added NH4F and HF are also recycled, so that the electrolytic voltage is greatly reduced, and the recovery effect of the catalyst is obviously improved.
The method controls the step of recovering the metal by adjusting the concentration of the sulfuric acid, and combines electrolysis and the sulfuric acid for repeated use, so that the recovery rate of the metal component in the catalyst is higher. The treatment capacity of the system is far higher than that of the current catalyst recovery system, and basically no waste liquid is produced. Other atoms are hardly introduced from the aspect of atom utilization rate, so that the pollution caused by catalyst recovery can be eliminated, good economic benefit can be obtained, and the full recovery of the metal components of the catalyst is facilitated.
The electrolysis operation of the invention is a continuous reaction, the electrolyte continuously flows from beginning to end, the oxide dissolved by sulfuric acid is electrolyzed in the cathode chamber, the voltage is adjusted, and the electrolysis is carried out step by step, thereby realizing the flow operation and the continuous reaction recovery. The method has the advantages of high catalyst recovery rate, simple and efficient process, environmental protection, high economic value and the like. The catalyst can obtain high-purity molybdenum metal simple substance, and can also separate high-purity metals such as nickel, cobalt and the like.
Drawings
FIG. 1 is a block diagram of the steps of the catalyst recovery process of the present invention.
FIG. 2 is a schematic diagram of an electrolytic cell according to the present invention.
FIG. 3 is a flow diagram of the catalyst recovery process of the present invention.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example one
(1) 1000g of the spent catalyst were initially calcined at 550 ℃ (in% by mass, in which MoO was present)315% of Co, 10% of NiO, and Al2O360% of Fe2O3Content 5%), after cooling, the catalyst was crushed into 1200 mesh powder, divided into 5 parts on average, and 1 part of the powder was first put into an aliphatic alcohol having a concentration of 3g/L (for example: c8-10 alcohol), performing foam flotation, performing centrifugal defoaming on the floated catalyst at the rotating speed of 700 r/min, performing acid leaching on the defoamed catalyst at the acid leaching temperature of about 50 ℃, the concentration of acid (sulfuric acid) being 3mol/L, the acid leaching time being 2 hours, filtering, and reserving filter residues for later use;
(2) adjusting the pH value of the filtered filtrate by using an alkali solution with the concentration of 5g/L of alkali (caustic soda), respectively adjusting the pH value of aluminum to be 5 and the pH value of iron to be 3, and gradually filtering and recovering the aluminum and the iron;
(3) filtering the filtrate to remove iron and aluminum, adjusting pH to 3, and electrolyzing, wherein the electrolytic cell has a structure shown in figure 2: adjusting the electrolytic voltage to Ni-15V; co 40V, and the sulfuric acid solution obtained on the semi-permeable membrane (sulfate anion exchange resin) side close to the cathode has a concentration of 2mol/L, and the electrolysis step recovers nickel and cobalt, and a high-concentration sulfuric acid solution can be obtained for the next step.
(4) Adding the filter residue left in the step (1) into the recovered concentrated sulfuric acid, controlling the concentration of the sulfuric acid to be 7mol/L, the acid leaching temperature to be 50 ℃, the acid leaching time to be 2 hours, filtering after acid leaching, adjusting the pH value of the filtrate to be 3 by using a 3mol/L NaOH solution, and respectively adding NH4F and HF to make the concentration of the mixed solution reach 3g/L, and carrying out electrolysis as shown in the attached figure 2: mo is 50V, the concentration of the sulfuric acid solution on the side of the semipermeable membrane close to the cathode is 4mol/L, and then the subsequent recovery of 4 parts of catalyst is carried out.
The recovery rate of the metals including nickel, cobalt, iron and molybdenum is determined by titration.
After the first recovery, the recovery rate of molybdenum was 97.9%, the recovery rate of nickel was 99.0%, the recovery rate of cobalt was 97.2%, the recovery rate of iron was 98.1%, and the recovery rate of aluminum was 98.3%.
After 5 times of complete recovery, the total recovery rate of molybdenum is 98.6%, the total recovery rate of nickel is 99.3%, the total recovery rate of cobalt is 98.5%, the total recovery rate of iron is 98.6%, and the recovery rate of aluminum is 99.3%.
The invention realizes the recycling mode of the concentrated sulfuric acid solution, and can obviously improve the total recovery rate of the catalyst after repeated recycling operation of continuous reaction recovery.
Example two
Ni in example one is 15V; co 40V instead of Ni 10V; co ═ 30V. The scheme is as follows: the total recovery rate of molybdenum is 99.2%, the total recovery rate of nickel is 98.5%, the total recovery rate of cobalt is 97.9%, the total recovery rate of iron is 98.9% and the recovery rate of aluminum is 99.0%.
EXAMPLE III
Adding NH in example one4The concentration of the F and HF solutions was 3g/L instead of adding NH4The concentration of the F and HF solutions was 2 g/L. The scheme is as follows: the total recovery rate of molybdenum is 97.6%, the total recovery rate of nickel is 98.8%, the recovery rate of cobalt is 98%, the total recovery rate of iron is 98.4% and the recovery rate of aluminum is 99.4%.
Example four
Instead of Mo being 60V, Mo in example one is 50V. The scheme is as follows: the total recovery rate of molybdenum is 94%, the total recovery rate of nickel is 98.6%, the total recovery rate of cobalt is 98%, the total recovery rate of iron is 98% and the recovery rate of aluminum is 99.3%.
Comparative example 1
Comparative example 1 is different from example 1 in that: the electrolytic cell is not provided with a sulfate radical type anion exchange resin membrane, and the non-impurity sulfuric acid solution electrolyte is added again during each electrolysis operation. The other conditions were the same as in example 1,
after 5 total recoveries, the total recovery rate of molybdenum is 88%, the total recovery rate of nickel is 87%, the total recovery rate of cobalt is 87%, and the total recovery rate of iron is 84%.
The absence of a sulfate-type anion exchange resin membrane not only prevents recovery of the sulfuric acid solution which is directly used, but also affects the metal recovery rate, and is not favorable for sufficient recovery of each metal component in the nickel-molybdenum catalyst.
Comparative example 2
Comparative example 2 differs from example 1 in that: without addition of NH4F and HF, and the voltage for recovering the molybdenum metal at this time is 150V.
The overall recovery of molybdenum of comparative example 2 was 59%.
Without addition of NH4F. HF, not only the voltage for recovering molybdenum metal increased, but also the effect of recovering molybdenum at high voltage was unstable, and the recovery rate of molybdenum metal was significantly reduced compared to comparative example 1.
Claims (4)
1. A process for wet recovery of iron, aluminum, nickel, molybdenum and cobalt from hydrofining spent catalyst is characterized in that: the method comprises the following steps:
(1) calcining the waste nickel-molybdenum catalyst, cooling, crushing the catalyst into powder, performing rough separation by using a foam flotation method, and defoaming;
(2) placing the roughly-selected catalyst into dilute sulfuric acid for acid leaching, wherein the temperature during acid leaching is 40-90 ℃, the concentration of the sulfuric acid is 2-4 mol/L, the acid leaching time is 1-3 hours, filtering, collecting filter residues for later use, adjusting the pH value of filtrate for gradual sedimentation, recovering iron with the pH = 1.5-3.5 and aluminum with the pH = 3.5-5.5, and respectively recovering iron and aluminum metals;
(3) adjusting the pH value of the catalyst acid solution after recovering iron and aluminum metals to 2-3, placing the catalyst acid solution in an electrolytic cell for electrolysis after adjustment, respectively recovering nickel and cobalt metals, applying a voltage of 2-20V when recovering the nickel metal by electrolysis, and then adjusting the voltage to 20-50V to recover the cobalt metal; the electrolytic cell consists of a cathode, an anode and an anion exchange resin membrane; wherein the metal to be recovered is used as a cathode, the graphite is used as an anode, the anion exchange resin is sulfate anion exchange resin, and a sulfuric acid solution is obtained by collecting;
(4) adding the filter residue obtained in the step (2) into concentrated sulfuric acid obtained by recycling in the step (3), adjusting the concentration, performing acid leaching, wherein the concentration of sulfuric acid is 6-10 mol/L, the acid leaching temperature is 40-60 ℃, the acid leaching time is 1-3 hours, filtering after acid leaching, and utilizingAdjusting the pH value of the filtrate to 2-4 by using NaOH solution, and adding NH4F and HF solutions with the concentration of 1-5 g/L respectively are electrolyzed in an electrolytic cell to recover molybdenum metal, the voltage for electrolyzing Mo is 30-60V, and the obtained sulfuric acid solution is recycled.
2. The process of claim 1 for the wet recovery of iron, aluminum, nickel, molybdenum and cobalt from spent hydrofinishing catalysts, wherein: the foaming agent adopted by the foam flotation method in the step (1) is fatty alcohol; the crushed particles of the catalyst are 180-1800 meshes, and the defoaming rotating speed is 600-800 revolutions per minute.
3. The process of claim 1 for the wet recovery of iron, aluminum, nickel, molybdenum and cobalt from spent hydrofinishing catalysts, wherein: the pH of the recovered iron is = 2-3, and the pH of the aluminum is = 4-5.
4. The process of claim 1 for the wet recovery of iron, aluminum, nickel, molybdenum and cobalt from spent hydrofinishing catalysts, wherein: the voltage for recovering nickel by electrolysis is 10-20V, and the voltage for recovering cobalt is 30-40V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010731298.9A CN111876603B (en) | 2020-07-27 | 2020-07-27 | Wet process for recovering Fe, Al, Ni, Mo and Co from waste hydrorefining catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010731298.9A CN111876603B (en) | 2020-07-27 | 2020-07-27 | Wet process for recovering Fe, Al, Ni, Mo and Co from waste hydrorefining catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111876603A CN111876603A (en) | 2020-11-03 |
| CN111876603B true CN111876603B (en) | 2022-03-25 |
Family
ID=73202062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010731298.9A Active CN111876603B (en) | 2020-07-27 | 2020-07-27 | Wet process for recovering Fe, Al, Ni, Mo and Co from waste hydrorefining catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111876603B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156375A (en) * | 1991-12-05 | 1993-06-22 | Taiyo Koukou Kk | Method for leaching valuable metal from waste catalyst |
| WO2009038379A2 (en) * | 2007-09-21 | 2009-03-26 | Research Institute Of Industrial Science & Technology | Method of manufacturing fe and ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the fe and ni containing material and method of manufacturing fe-ni alloy |
| KR20090114619A (en) * | 2008-04-30 | 2009-11-04 | 주식회사 코캣 | A Separation and Recovery Process of Metals from Petroleum Desulfurization Waste Catalyst |
| CN102808082A (en) * | 2011-05-30 | 2012-12-05 | 深圳市格林美高新技术股份有限公司 | Method for selective leaching separation of cobalt, nickel and molybdenum from high grade cobalt-nickel-molybdenum waste material |
| CN102952954A (en) * | 2011-08-26 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Processing method of trivalent cobalt nickel oxide waste material and waste cobalt nickel alloy |
| CN108467939A (en) * | 2018-06-11 | 2018-08-31 | 江苏北矿金属循环利用科技有限公司 | A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst |
| CN108728653A (en) * | 2018-06-11 | 2018-11-02 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN111321296A (en) * | 2018-12-13 | 2020-06-23 | 有研工程技术研究院有限公司 | Method for recovering vanadium and nickel from waste petroleum catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228834A (en) * | 2011-04-19 | 2011-11-02 | 常州大学 | Catalyst for catalytic hydrogenation and application thereof |
-
2020
- 2020-07-27 CN CN202010731298.9A patent/CN111876603B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156375A (en) * | 1991-12-05 | 1993-06-22 | Taiyo Koukou Kk | Method for leaching valuable metal from waste catalyst |
| WO2009038379A2 (en) * | 2007-09-21 | 2009-03-26 | Research Institute Of Industrial Science & Technology | Method of manufacturing fe and ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the fe and ni containing material and method of manufacturing fe-ni alloy |
| KR20090114619A (en) * | 2008-04-30 | 2009-11-04 | 주식회사 코캣 | A Separation and Recovery Process of Metals from Petroleum Desulfurization Waste Catalyst |
| CN102808082A (en) * | 2011-05-30 | 2012-12-05 | 深圳市格林美高新技术股份有限公司 | Method for selective leaching separation of cobalt, nickel and molybdenum from high grade cobalt-nickel-molybdenum waste material |
| CN102952954A (en) * | 2011-08-26 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Processing method of trivalent cobalt nickel oxide waste material and waste cobalt nickel alloy |
| CN108467939A (en) * | 2018-06-11 | 2018-08-31 | 江苏北矿金属循环利用科技有限公司 | A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst |
| CN108728653A (en) * | 2018-06-11 | 2018-11-02 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN111321296A (en) * | 2018-12-13 | 2020-06-23 | 有研工程技术研究院有限公司 | Method for recovering vanadium and nickel from waste petroleum catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 65#丙烯腈废催化剂综合回收的研究;刘秀庆;《无机盐工业》;20020930;第35-36页 * |
| 含钼、镍、铋、钴废催化剂综合回收的实验研究;马成兵等;《中国钼业》;20071030(第05期);表1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111876603A (en) | 2020-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101161596B (en) | A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical | |
| CN103849775B (en) | A kind of method reclaiming nickel and cobalt from high-temperature alloy waste material | |
| CN103168109A (en) | Processing of manganous sulphate/dithionate liquors | |
| CN111172390B (en) | Method for treating valuable metal sulfide concentrate by using oxygen pressure | |
| CN111304446A (en) | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching | |
| CN109763003B (en) | Method for extracting tungsten and molybdenum by decomposing high-molybdenum scheelite by electrooxidation method | |
| CN107419111A (en) | A kind of method that production zinc powder is leached in alloy zinc gray in-pulp electrolysis | |
| CN111118544A (en) | Method for treating iron-containing acidic waste liquid | |
| CN109321745A (en) | Utilize the method for Treatment of Metal Surface waste preparation nickel plate | |
| CN107585789B (en) | A method of high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concentrate | |
| CN111876603B (en) | Wet process for recovering Fe, Al, Ni, Mo and Co from waste hydrorefining catalyst | |
| CN106893859B (en) | A method of processing nickel cobalt waste material | |
| CN108251648A (en) | Nanofiltering membrane efficiently separates recovery method to metallic element in waste and old lithium ion battery | |
| CN109576494B (en) | Method for preparing sodium sulfate by utilizing metal surface treatment waste | |
| CN113026056B (en) | Method for producing electrolytic cobalt by adopting secondary electrolysis of cobalt intermediate product | |
| US20230124749A1 (en) | Ammonium complex system-based method for separating and purifying lead, zinc, cadmium, and copper | |
| CN113621835A (en) | Method for efficiently removing molybdenum based on extraction-precipitation combination | |
| CN111410240A (en) | Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste | |
| CN113249579A (en) | Resource recovery method for electroplating sludge with high copper and nickel content | |
| CN114075623A (en) | Resource utilization method for two-stage extraction of vanadium-containing waste petroleum catalyst | |
| CN115571925B (en) | Method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries | |
| CN114735765B (en) | Production process of battery grade nickel sulfate | |
| CN108950254B (en) | Method for extracting rhenium by combining high-rhenium arsenic filter cake and copper-containing waste liquid | |
| CN114672656B (en) | Resource treatment method for waste diamond tool bits | |
| CN115231631A (en) | Continuous production process for preparing nickel sulfate by ammonia leaching based on ammonia circulation |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230619 Address after: 462500 No. 60, East Road, Intersection of Keji Road and Xinglong Road, Shilong District, Pingdingshan, Henan Province Patentee after: Henan Jinhao Environmental technology Co.,Ltd. Address before: No.13, 3rd floor, building 1, No.1, Tidu street, Qingyang District, Chengdu, Sichuan 610000 Patentee before: Chengdu yishenrui Technology Co.,Ltd. Effective date of registration: 20230619 Address after: No.13, 3rd floor, building 1, No.1, Tidu street, Qingyang District, Chengdu, Sichuan 610000 Patentee after: Chengdu yishenrui Technology Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
|
| TR01 | Transfer of patent right |