CN114480843A - Application of industrial white oil as synergist in extraction process - Google Patents
Application of industrial white oil as synergist in extraction process Download PDFInfo
- Publication number
- CN114480843A CN114480843A CN202111595103.3A CN202111595103A CN114480843A CN 114480843 A CN114480843 A CN 114480843A CN 202111595103 A CN202111595103 A CN 202111595103A CN 114480843 A CN114480843 A CN 114480843A
- Authority
- CN
- China
- Prior art keywords
- white oil
- synergist
- industrial white
- extraction
- nickel
- 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
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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses application of industrial white oil as a synergist in an extraction process, and relates to the technical field of application of industrial white oil. The application of the industrial white oil with the molecular weight of 300-400 and composed of naphthene and/or olefin as a synergist is added into an extracting agent in an extraction process of recovering vanadium, nickel or tungsten from a waste catalyst. The application of the industrial white oil as the extraction synergist for recovering vanadium, nickel and tungsten in the waste catalyst has the advantages of simple use method, high comprehensive extraction rate increased by more than 10%, high metal content of the recovered product, stable process index, short process, obvious economic benefit and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of industrial white oil application, in particular to application of industrial white oil as a synergist in an extraction process.
Background
The industrial white oil is a special mineral oil product which is ultra-deeply refined, consists of cyclane and olefin with the general molecular weight of 300-400, and has chemical inertness and excellent light and heat stability. The industrial white oil is mainly used as a lubricant, a solvent, a coolant, a lubricant and the like in spinning of chemical fiber, white fiber and other industries. It is also suitable for lubricating textile machinery and precision instruments and sealing oil for compressors.
The chemical industry generates a large amount of waste catalysts every year, and the waste catalysts contain a large amount of noble metals, nonferrous metals or oxides thereof. With the development of petroleum and chemical industries, the production amount of waste catalysts is increased year by year, and the recycling of metals in the waste catalysts is beneficial to the development of circular economy and has great significance for resource recycling and environmental protection. The recovery of vanadium, nickel and tungsten which are main components in the waste catalyst is particularly important.
Disclosure of Invention
The invention provides application of industrial white oil as a synergist in an extraction process, and vanadium, nickel and tungsten in a waste catalyst are recycled.
In order to realize the technical purpose, the invention adopts the following scheme: the application of the industrial white oil with the molecular weight of 300-400 and composed of naphthene and/or olefin as a synergist is added into an extracting agent in an extraction process of recovering vanadium, nickel or tungsten from a waste catalyst.
Compared with the prior art, the invention has the beneficial effects that: the application of the industrial white oil as the extraction synergist for recovering vanadium, nickel and tungsten in the waste catalyst has the advantages of simple use method, high comprehensive extraction rate increased by more than 10%, high metal content of the recovered product, stable process index, short process, obvious economic benefit and environmental friendliness.
Furthermore, the addition amount of the industrial white oil is 5-12% of the total dosage of the medicament in the extraction process.
Further, the industrial white oil is any one of No. 5, No. 7, No. 10 and No. 15.
Further, the kinematic viscosity of the industrial white oil at 40 ℃ is 4.14-16.5 mm2And/s, a flash point (open) of 110 to 150 ℃.
Drawings
FIG. 1 is a process flow diagram for recovering vanadium from a spent catalyst according to example 1 of the present invention;
FIG. 2 is a flow chart of a process for recovering nickel from a spent catalyst according to example 2 of the present invention;
FIG. 3 is a flow chart of the process for recovering tungsten from the spent catalyst according to example 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
The industrial white oil is any one of No. 5, No. 7, No. 10 or No. 15, and the kinematic viscosity of the industrial white oil is 4.14-16.5 mm at 40 DEG C2And/s, a flash point (open) of 110 to 150 ℃.
Example 1
The vanadium catalyst is mainly used in sulfuric acid production, namely sulfur dioxide is converted into sulfur trioxide under the action of a vanadium pentoxide catalyst taking diatomite as a carrier. The vanadium content in the waste vanadium catalyst after the production and the use of the sulfuric acid is about 5 percent, and is mainly V2O5And VOSO4Form exists of, VOSO4The proportion of the alkaline leaching agent can reach 40-60% sometimes, and the alkaline leaching agent is not easy to leach. The acid dissolution method and the reduction oxidation method are generally adopted in China, but the problems of low yield, low purity, difficult filtration, serious equipment corrosion and the like exist. The method for recovering vanadium by adopting a solvent extraction method is a main technical development methodAnd (3) direction.
The process of recovering vanadium from waste vanadium catalyst with industrial white oil as extraction synergist is shown in figure 1. The composition of the spent vanadium catalyst for the experiments is shown in table 1:
TABLE 1 composition of waste vanadium catalyst
| Component name | V2O5 | K2SO4 | SiO2 | Fe | S |
| Mass percent/%) | 4~6 | 17~24 | 70~75 | 1~2 | ≤0.5 |
The specific recovery operation method comprises the following steps:
will contain V2O54.3% (V2.4%) of the spent vanadium catalyst was calcined at 700 ℃ for 3 h. And (3) adding 600kg of 15wt% soda ash solution into 200kg of roasted product, soaking for 90min, filtering the leachate through a plate-and-frame filter press, and washing a filter cake with water.
500kg of the obtained V1.3% containing vanadium solution was added to the vanadium solutionAdding sulfuric acid to adjust the pH value to 2, adding 20kg of mixed extracting agent which is mixed according to the proportion (extracting agent P204: diluent kerosene: No. 7 industrial white oil = 26.5: 65: 8.5), stirring uniformly, standing for 2h, and separating a vanadium-containing organic phase and a vanadium-containing water phase. Adding 25kg of 15wt% ammonium carbonate aqueous solution into the organic phase for back extraction, and obtaining vanadium-containing aqueous solution by back extraction. Adding 92.5wt% industrial sulfuric acid into vanadium-containing water solution to adjust pH to 5, adding solid industrial ammonium sulfate, reacting for a period of time to measure free acid (as H) in the solution2SO4Metering) 2-3 mg/L, completing ammonium polyvanadate precipitation. And filtering and separating the mixed solution containing the precipitate to obtain an ammonium polyvanadate filter cake, heating the filter cake to 690 ℃, decomposing ammonia and melting to generate vanadium pentoxide. The vanadium pentoxide grade in the product is analyzed to be 99.10%, and the extraction yield is 95.1%.
The recovery rate of vanadium in the waste vanadium catalyst is improved to more than 90 percent from 80 percent of the original recovery rate (without processing the white oil synergist, and the other contents are the same as the flow), and the purity of vanadium pentoxide is detected to reach more than 99 percent by adopting a potassium permanganate-ferrous titration method.
Example 2
The nickel is used as an active component of the catalyst and is mainly applied to hydrogenation processes, such as hydrofining of petroleum fractions, grease hydrogenation and the like. The nickel content in the waste nickel catalyst generated in the hydrogenation process reaches 6-20 percent and is far higher than that in lean ores, and solid waste represented by the waste nickel catalyst is called secondary resources. Nickel is present in the spent nickel catalyst in both Ni and NiO forms. Generally, nickel is recovered by oxidizing nickel to nickel oxide at high temperature, and then extracting nickel in the form of nickel sulfate by acid leaching, iron removal by oxidation and filtering of the nickel solution.
The process of recovering nickel from waste nickel catalyst with industrial white oil as extraction synergist is shown in FIG. 2. The composition of the spent nickel catalyst used for the experiment is shown in table 2 below:
TABLE 2 composition of waste nickel catalysts
| Component name | NiO | α-Al2O3 | FeO | Fe2O3 | C | ZnO |
| Percent by mass/%) | 10~15 | 75~85 | ≤0.5 | ≤1.0 | 5~10 | 3~5 |
The specific recovery operation method comprises the following steps:
step one, oxidizing and roasting the waste nickel catalyst in a rotary kiln at the roasting temperature of 800-850 ℃ for 4 hours, allowing sulfur to enter flue gas in the form of hydrogen sulfide or sulfur dioxide, neutralizing and removing the sulfur in lime, and removing impurities such as sulfide. The desulfurized material is crushed and sieved, 92.5wt% of sulfuric acid is added into the material with the granularity smaller than 100 meshes for leaching for 60-90 min, and the end point of the acid leaching reaction ensures that free acid (as H) in the leaching solution2SO4Calculated) the content was 7 g/L.
And step two, adding hydrogen peroxide with the mass concentration of 25% into the leachate after the leaching reaction is finished, oxidizing for 30min (the dosage of the hydrogen peroxide is 5% of the total amount of the leachate), adding powdered industrial sodium carbonate to neutralize until the pH of the solution is =10, and filtering to remove iron and aluminum.
Adding an extracting agent P204, a diluent kerosene and No. 7 industrial white oil, wherein the dosage ratio of the extracting agent P204 to the diluent kerosene to the No. 7 industrial white oil is 17-19: 70-75: 8-12, performing extraction-back extraction to obtain an organic phase and a water phase containing nickel sulfate, and returning the organic phase to the extraction process for secondary extraction.
And step four, carrying out evaporative crystallization on the water phase containing the nickel sulfate at 105 ℃ for 4h to produce refined nickel sulfate, and testing the nickel in the nickel sulfate with the grade of 22.1% and Zn of less than 0.0005% by adopting a gravimetric method (GB/T26524-2011 national standard for refined nickel sulfate, which requires Zn to be less than or equal to 0.0005%).
The key of the technology is that the extraction rate is improved by adding the industrial white oil (5-12 percent of the industrial white oil is added) during extraction, the recovery rate of nickel is improved to 95 percent from 82 percent of the same process flow without processing the industrial white oil, and the extraction yield is improved by more than 10 percent. The purity of the nickel reaches the refined nickel sulfate grade (conforms to the GB/T26524-2011 national standard for refined nickel sulfate).
Example 3
The catalyst used in the process of petroleum desulfurization and hydrogenation is mainly RN-1 and 3581, when the catalyst is used for a period of time, the activity is reduced and the catalyst needs to be replaced, and the replaced waste catalyst contains valuable metal tungsten (WO)3Calculated) content of about 25 percent, is a precious resource. After the tungsten-containing catalyst is used for a period of time, the catalyst needs to be replaced because of the reduction of the catalytic activity, and tungsten is used as a rare metal, so that the resource is limited, and the recycling significance is great. At present, the recovery method of the waste hydrogenation catalyst is widely applied, and the technology is mature and is an organic solvent extraction method.
The flow of the application of industrial white oil as an extraction synergist for recovering tungsten from waste catalysts is shown in fig. 3, and the components of the waste tungsten-containing catalysts in the experiment are shown in table 3:
TABLE 3 composition of waste tungsten-containing catalyst
| Component name | WO3 | MoO3 | SiO2 | α-Al2O3 | S | Others |
| Mass percent/%) | 10~20 | 5~9 | 12~20 | 36~42 | ≤0.5 | 10~20 |
The specific recovery operation method comprises the following steps:
step one, carrying out oxidation roasting on the waste tungsten-containing catalyst (roasting temperature is 650-750 ℃, roasting time is 2 hours), wherein sulfur in impurities enters flue gas in the form of hydrogen sulfide or sulfur dioxide, and is neutralized and removed by lime; and (3) crushing and screening the desulfurized material, pouring the material with the particle size of less than 100 meshes into liquid caustic soda (25 wt% NaOH solution) for leaching, and controlling the pH value of the leaching solution to be 9-10 to form a sodium metatungstate solution. And step two, adding a 21wt% magnesium chloride solution into the sodium metatungstate solution to carry out precipitation and impurity removal. When the reaction solution had pH =10, the precipitation reaction was completed, and the solution was filtered to remove impurities such As P, As, and Si.
And step three, adding sodium sulfide into the solution after impurity removal, precipitating again to remove impurities, and filtering to remove Mo. And sequentially adding an extracting agent N235, a diluent kerosene and No. 7 industrial white oil into the purified solution in a dosage ratio of 22-26: 72-78: and 10-12, extracting to obtain a loaded organic phase and an extraction residual liquid.
Step four, carrying out back extraction on the loaded organic phase by using 20-25% of industrial-grade ammonia water, wherein the ammonia water is used in an amount that the loaded organic phase contains 2-4 mol/L of NH4OH is the standard. And (3) carrying out back extraction to obtain an organic phase and an ammonium metatungstate solution, returning the organic phase to the extraction process for re-extraction, carrying out evaporative crystallization on the ammonium metatungstate solution at 105 ℃ for 3.5h to produce ammonium metatungstate crystals, and directly returning the mother solution as a dilute ammonium metatungstate solution to the evaporative crystallizer for recycling.
The extraction rate of tungsten after the efficiency is increased by adding the industrial white oil is increased to 96.9 percent from the original 90 percent (adopting the same process flow without adding the industrial white oil), and the final product of the tungsten is WO in the ammonium metatungstate3The content is 91.2 percent, is superior to the national standard GB/T3460-2017, and can be directly used.
Finally, it is noted that: the above-mentioned list is only the preferred embodiment of the present invention, and naturally those skilled in the art can make modifications and variations to the present invention, which should be considered as the protection scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.
Claims (4)
1. The application of the industrial white oil as the synergist for the extraction process is characterized in that the industrial white oil with the molecular weight of 300-400 and composed of naphthene and/or olefin is added into the extractant for the extraction process of recovering vanadium, nickel or tungsten from a waste catalyst to be used as the synergist.
2. The application of the industrial white oil as the synergist for the extraction process according to claim 1, wherein the addition amount of the industrial white oil is 5-12% of the total dosage of the extraction agent.
3. The use of technical white oil as an extraction process synergist according to claim 1, wherein the technical white oil is any one of No. 5, No. 7, No. 10, and No. 15.
4. Use of an industrial white oil according to any one of claims 1 to 3 as a synergist in an extraction process, wherein the kinematic viscosity of the industrial white oil at 40 ℃ is 4.14 to 16.5mm2And/s, the open flash point is 110-150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111595103.3A CN114480843A (en) | 2021-12-24 | 2021-12-24 | Application of industrial white oil as synergist in extraction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111595103.3A CN114480843A (en) | 2021-12-24 | 2021-12-24 | Application of industrial white oil as synergist in extraction process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114480843A true CN114480843A (en) | 2022-05-13 |
Family
ID=81494796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111595103.3A Pending CN114480843A (en) | 2021-12-24 | 2021-12-24 | Application of industrial white oil as synergist in extraction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114480843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400448A (en) * | 2022-08-30 | 2022-11-29 | 华东理工大学 | Application of No. 5 industrial white oil as MTBE (methyl tert-butyl ether) extraction anti-coking agent and MTBE desulfurization method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109207724A (en) * | 2018-09-12 | 2019-01-15 | 哈尔滨工业大学（威海） | It is a kind of from containing vanadium and chromium solution simultaneously extraction and separation vanadium chromium extractant and extracting process |
| CN110983040A (en) * | 2019-12-04 | 2020-04-10 | 杨秋良 | Method for precipitating vanadium in acidic vanadium-rich solution without ammonia |
-
2021
- 2021-12-24 CN CN202111595103.3A patent/CN114480843A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109207724A (en) * | 2018-09-12 | 2019-01-15 | 哈尔滨工业大学（威海） | It is a kind of from containing vanadium and chromium solution simultaneously extraction and separation vanadium chromium extractant and extracting process |
| CN110983040A (en) * | 2019-12-04 | 2020-04-10 | 杨秋良 | Method for precipitating vanadium in acidic vanadium-rich solution without ammonia |
Non-Patent Citations (1)
| Title |
|---|
| 张启修，赵秦生主编: "《中国生态环境问题的探讨》", 冶金工业出版社, pages: 542 - 371 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400448A (en) * | 2022-08-30 | 2022-11-29 | 华东理工大学 | Application of No. 5 industrial white oil as MTBE (methyl tert-butyl ether) extraction anti-coking agent and MTBE desulfurization method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| Sahu et al. | Hazardous waste to materials: Recovery of molybdenum and vanadium from acidic leach liquor of spent hydroprocessing catalyst using alamine 308 | |
| CN102051483B (en) | Method for reclaiming metals from molybdenum-containing waste catalyst | |
| CN101457296B (en) | Method for recovering metallic oxide from waste aluminum base V-Mo-Ni catalyst | |
| US7837960B2 (en) | Process for separating and recovering base metals from used hydroprocessing catalyst | |
| CN108467939A (en) | A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst | |
| CN102586606A (en) | Method for recovering rare earth, vanadium and nickel from waste FCC/ROC catalyst containing vanadium and nickel | |
| CN101914678B (en) | Method for producing industry molybdenum oxide from molybdenum concentrate | |
| CN104263946A (en) | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst | |
| CN103290223B (en) | Comprehensive recovery method for multiple metals of waste catalyst | |
| Liu et al. | A new process of extracting vanadium from stone coal | |
| CN104911359A (en) | Process method for extracting cobalt and nickel from manganese waste slag | |
| CN102199710B (en) | Method for extracting and separating nickel and molybdenum from nickel-molybdenum-containing coal gangue | |
| CN105271632A (en) | Comprehensive recovery method for electroplating sludge | |
| CN103526013A (en) | Comprehensive recovery method of complex molybdenum sulfide ore | |
| CN115109936B (en) | Method for recovering valuable metals from waste batteries | |
| KR101487549B1 (en) | A Separation and Recovery Process of Metals from Petroleum Desulfurization Waste Catalyst | |
| CN110512095A (en) | A method of arsenic is extracted and stablized from tungsten metallurgy phosphorus and arsenic slag | |
| Nasimifar et al. | A review on the extraction of vanadium pentoxide from primary, secondary, and co-product sources | |
| Han et al. | A leaching, solvent extraction, stripping, precipitation and calcination process for the recovery of MoO3 and NiO from spent hydrofining catalysts | |
| CN106636661A (en) | Method for selectively separating and recovering tellurium and antimony from tellurium residues | |
| CN113800569B (en) | Recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag | |
| CN101724758A (en) | Method for recycling molybdenum of molybdenum-contained waste catalyst | |
| CN114480843A (en) | Application of industrial white oil as synergist in extraction process | |
| CN104229893A (en) | Complete-wet-method production technology for producing ammonium molybdate from nickel-molybdenum ore |
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 |