CN114752768A - Method for recovering metal molybdenum in waste hydrogenation catalyst through leaching and extraction integration - Google Patents
Method for recovering metal molybdenum in waste hydrogenation catalyst through leaching and extraction integration Download PDFInfo
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- CN114752768A CN114752768A CN202210350147.8A CN202210350147A CN114752768A CN 114752768 A CN114752768 A CN 114752768A CN 202210350147 A CN202210350147 A CN 202210350147A CN 114752768 A CN114752768 A CN 114752768A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
Abstract
The invention provides a method for recovering metal molybdenum in a waste hydrogenation catalyst through leaching and extraction integration, which comprises the following steps: (1) oxidizing and roasting the waste hydrogenation catalyst in an oxidizing atmosphere, and then grinding to obtain a roasted sample to be recovered; (2) sequentially carrying out leaching extraction coupling reaction and separation on the mixed leaching solution, the extracted organic phase and the roasting sample to be recovered obtained in the step (1) to obtain a molybdenum-containing organic phase; (3) and (3) carrying out back extraction on the mixed stripping agent and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution. According to the invention, by designing a leaching-extraction integrated reaction separation coupling process, a liquid-solid three-phase separation system is established, the leaching and extraction steps are synchronously carried out, the reaction is mutually promoted to be carried out, the acid-base consumption in the original process is reduced, reaction products can be separated in time, the metal leaching rate and the reaction separation efficiency are improved, and the problem of limited efficiency of step-by-step leaching and extraction reaction is effectively solved.
Description
Technical Field
The invention belongs to the technical field of hazardous solid recycling, relates to a method for recycling metal molybdenum from a light oil waste hydrogenation catalyst, and particularly relates to a method for recycling metal molybdenum from a waste hydrogenation catalyst through leaching and extraction integration.
Background
The hydrogenation catalyst is one of the most commonly used catalysts in the process of petroleum refining, most of the waste hydrogenation catalysts are treated in a landfill mode, and only about 10 percent of the waste catalysts are treated in a resource mode. The oil refining waste catalyst still contains rare earth elements and heavy metals such as nickel and molybdenum, and the direct burying method not only wastes resources, but also pollutes the environment. The catalyst is regenerated by adopting a carbon chlorination method, a carbonyl method, a washing method and the like, and the activity of the catalyst is not completely recovered. Besides the waste catalyst, a part of fresh catalyst is needed for actual performance test, the vanadium content of the waste catalyst is low or even negligible, but the molybdenum contained in the waste catalyst still has recovery value. Therefore, the method carries out high-value recycling on the waste catalyst, can improve the resource utilization rate and avoid the environmental problems caused by the waste catalyst, and is the key of green sustainable development.
The existing wet method for recovering the waste catalyst mainly comprises two parts of leaching and separation and purification. The leaching method comprises alkaline leaching and acid leaching, and usually adopts ammonia or ammonium salt solution and inorganic acid (such as H) with different concentrations2SO4HCl or HNO3Etc.). In order to improve the leaching rate of each metal, a large amount of strong acid and strong base are required to be added in the leaching process. The separation and purification of the waste catalyst mainly comprises several methods of precipitation, adsorption, ion exchange and solvent extraction. The extraction separation has the advantages of high product purity, high recovery efficiency and the like, and is an effective method for separating and purifying metals at present. The prior art has the problems that: (1) a large amount of acid-base wastewater is easy to generate, and adverse effects are brought to the environment and resources; (2) at present, leaching and extraction reactions are carried out step by step in most processes, and the reaction separation efficiency is limited.
CN 112813287a discloses a method for recovering molybdenum from a spent hydrogenation catalyst, which comprises the following steps: step one, mixing the waste hydrogenation catalyst and the red mud and then performing ball millingGrinding and uniformly grinding by a machine, roasting and pretreating the uniformly ground powder at 300-500 ℃, leaching with water, and carrying out solid-liquid separation to obtain alkaline leaching solution containing molybdenum, wherein the molybdenum concentration of the leaching solution is 15-25 g/L; step two, adjusting the pH of the molybdenum-containing solution obtained in the step one to 6-8 by using an acid reagent, and precipitating A1(OH)3(ii) a The chelate extractant and the diluent form an organic phase, and the organic phase is mixed with the molybdenum-containing solution after aluminum precipitation for 1-3-level extraction; the ratio of 0/A of the extracted organic phase to the aqueous phase is (3: 1) (1: 3), the extraction time is 510min, and the extraction temperature is 25-45 ℃; step three, adding at least one of ammonia water and ammonium chloride solution into the molybdenum-containing organic phase extracted in the step two for back extraction, wherein the ratio of 0/A of the back extraction organic phase to the aqueous phase is (2: 1) - (1: 2), the back extraction time is 5-15 min, the back extraction temperature is 25-45 ℃, and the obtained back extraction solution is ammonium molybdate solution; and step four, adding an impurity removing agent into the ammonium molybdate solution subjected to back extraction in the step three for purification, adjusting the pH of the purified ammonium molybdate solution to 1.5-2.5 by using acid, and concentrating, evaporating and crystallizing to obtain pure ammonium molybdate. The method has the advantages of difficult operation and complex process.
CN 1544666C discloses a method for recovering nickel and aluminum from a waste aluminum-based nickel-containing catalyst. The method specifically comprises the steps of mixing waste catalyst powder with sodium carbonate, wherein the used amount of the waste catalyst is as follows: sodium hydroxide (weight ratio) 1: 0.7-1.3, carrying out a state conversion reaction in a sintering furnace at the temperature of 700-1250 ℃, after the constant temperature is kept for 1-6h, dissolving sodium aluminate with boiling water to separate aluminum, and reducing nickel slag to form matte and smelting. The process has high economic cost.
The existing wet process for recovering the waste catalyst mainly comprises two parts of leaching and separation and purification. The leaching method comprises alkaline leaching and acid leaching, and usually adopts ammonia or ammonium salt solution and inorganic acid (such as H) with different concentrations2SO4HCl or HNO3Etc.). In order to improve the leaching rate of each metal, a large amount of strong acid and strong base are required to be added in the leaching process. The separation and purification of the waste catalyst mainly comprises several methods of precipitation, adsorption, ion exchange and solvent extraction. The extraction separation has the advantages of high product purity, high recovery efficiency and the like, and is an effective method for separating and purifying metals at present. The prior art has the problems that: (1) easily generate a large amount of acid-base wastewater and supply ringEnvironmental and resource bring adverse effects; (2) at present, leaching and extraction reactions are carried out step by step in most processes, and the reaction separation efficiency is limited.
In summary, providing an economical, simple, easy to operate and environmentally friendly method for recovering molybdenum from waste catalyst has become one of the problems to be solved in the art.
Disclosure of Invention
The invention aims to provide a method for recovering metal molybdenum in a waste hydrogenation catalyst through leaching and extraction integration. In the leaching and extracting integrated recovery system provided by the invention, reaction products can be separated in time, the metal leaching rate and the reaction separation efficiency are improved, and the problem of limited efficiency of step-by-step leaching and extracting reaction is effectively solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recovering metal molybdenum in a waste hydrogenation catalyst through leaching and extraction integration, which comprises the following steps:
(1) oxidizing and roasting the waste hydrogenation catalyst in an oxidizing atmosphere, and then grinding to obtain a roasted sample to be recovered;
(2) sequentially carrying out leaching extraction coupling reaction and separation on the mixed leaching solution, the extracted organic phase and the roasting sample to be recovered obtained in the step (1) to obtain a molybdenum-containing organic phase;
(3) and (3) carrying out back extraction on the mixed stripping agent and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution.
The method for recovering the molybdenum metal in the waste hydrogenation catalyst by the integrated leaching and extracting system provided by the invention realizes the high-efficiency leaching and extracting of the molybdenum metal in the waste hydrogenation catalyst by the integrated leaching and extracting system, so that the comprehensive recovery rate of the molybdenum is more than 70%, a large amount of aluminum is enriched in solid residues, the loss is less than 0.1 wt%, and the method has a certain application value.
The waste hydrogenation catalyst used in the invention belongs to a light oil waste hydrogenation catalyst, the main active component is molybdenum and nickel, and the content of deposited vanadium is very little and can be ignored. Besides active metal, silicon and aluminum exist as carriers, and a small amount of impurities such as phosphorus, sulfur, iron, carbon deposition and the like exist. The color is gray black, no specific shape is formed, and the aggregation block appears.
The grinding in step (1) of the invention is carried out in a mortar to obtain a powder. And (3) after the separation in the step (2), obtaining a molybdenum-containing organic phase, solid residues and a molybdenum-containing aqueous phase solution.
Preferably, the oxidizing atmosphere of step (1) comprises an air atmosphere and/or an oxygen atmosphere.
Preferably, the temperature of the calcination in the step (1) is 400 to 600 ℃, for example, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ or 600 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The main component of the waste catalyst provided by the invention is molybdenum, nickel and aluminum, carbon is attached to the surface, and the carbon can be removed in the roasting process. And sulfur can form sodium sulfate to be left in solid matters, so that gas pollution is avoided. When the roasting temperature is too high, the molybdenum and the nickel can form a small amount of metal compounds, which is not beneficial to leaching; when the roasting temperature is too low, molybdenum exists in sulfide form in the waste catalyst, so that incomplete oxidation is caused, and leaching is not facilitated.
Preferably, the roasting time in the step (1) is 30-120 min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90mn, 100min, 110min or 120min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the average particle size of the calcined sample to be recovered in step (1) is 0.1 to 0.3mm, and may be, for example, 0.1mm, 0.12mm, 0.14mm, 0.16mm, 0.18mm, 0.2mm, 0.22mm, 0.24mm, 0.26mm, 0.28mm or 0.3mm, but is not limited to the values recited, and other values not recited within the range of values are also applicable.
Preferably, the leaching extraction coupling reaction in the step (2) comprises leaching and extraction which are carried out simultaneously.
Preferably, the reaction time of the leaching extraction coupling reaction is 10-30 min, for example, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the reaction temperature of the leaching extraction coupling reaction is 25 to 40 ℃, for example, 25 ℃, 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the stirring intensity in the leaching extraction coupling reaction is 200-400rpm, such as 200rpm, 230rpm, 260rpm, 290rpm, 320rpm, 350rpm, 380rpm or 400rpm, but not limited to the values listed, and other values not listed in the numerical range are also applicable
Preferably, the leach solution in the leach comprises aqueous ammonia.
Preferably, the concentration of the ammonia water is 0.05 to 0.2mol/L, for example, 0.05mol/L, 0.07mol/L, 0.09mol/L, 0.11mol/L, 0.13mol/L, 0.15mol/L, 0.17mol/L, 0.19mol/L or 0.2mol/L, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The ammonia water used as the leaching solution not only influences the leaching rate, but also influences the extraction rate of molybdenum in a leaching system; the ammonia water is used as the leaching solution and not only used as the leaching solution and MoO3The pH of a leaching system can be influenced by the reactant(s), and leaching is facilitated when the pH is more than 9; impurity ion NH4 +Is not beneficial to the extraction reaction, and is not beneficial to the extraction reaction in a strong alkaline environment.
Preferably, the mass ratio of the leachate to the roasted sample to be recovered obtained in the step (1) is (5-20): 1, for example, 5:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1 or 20:1, but the method is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the extraction solution in the extraction comprises an extracted organic phase.
Preferably, the extracted organic phase comprises the extractant N263, the diluent kerosene, and the organic solvent sec-octanol.
Preferably, the volume fraction of extractant in the organic phase is from 5 to 30%, for example 5%, 10%, 15%, 20%, 25% or 30%, but not limited to the values recited, and other values not recited in the range of values are equally applicable; the volume fraction of organic solvent is from 5 to 30%, for example 5%, 10%, 15%, 20%, 25% or 30%, but is not limited to the values listed, and other values not listed within the numerical range are equally applicable; the rest is diluent.
The volume ratio of N263 to secondary octanol in the extracted organic phase can affect the extraction rate of molybdenum and the phase separation effect of an extraction system, the viscosity of N263 is high, the solubility is changed after the N263 is combined with the molybdenum, and the extraction rate of the molybdenum is reduced and the phase separation effect is poor due to the fact that the volume ratio of N263 is too high and the volume ratio of secondary octanol is too low.
Preferably, the O/A ratio of the extraction organic phase and the extraction aqueous phase in the extraction is 1 (1-5), and may be, for example, 1:1, 1:2, 1:3, 1:4 or 1:5, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the stripping agent comprises a mixed solution of NaOH and NaCl.
Preferably, the concentration of NaOH is 0.1 to 1mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, but not limited to the values listed, and other values not listed within the range of values are also applicable.
Preferably, the concentration of NaCl is 0.1-1.5 mol/L, for example, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, 1.1mol/L, 1.3mol/L or 1.5mol/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the back-extraction temperature in step (3) is 25 to 40 ℃, for example, 25 ℃, 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the back extraction time in step (3) is 1-10 min, such as 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the stripping oil phase and the water phase in the back extraction in the step (3) have O/A of (5-1): 1-3), and may be, for example, 5:1, 5:2, 5:3, 4:1, 4:3, 3:1, 3:2, 2:1, 2:3 or 1:3, but not limited to the enumerated values, and other unrecited values in the range of the enumerated values are also applicable.
As a preferred technical scheme, the method for recovering the metal molybdenum in the waste hydrogenation catalyst by integrating leaching and extraction provided by the invention comprises the following steps:
(1) roasting the waste hydrogenation catalyst for 30-120 min at the temperature of 400-600 ℃ in an air atmosphere and/or an oxygen atmosphere, and then grinding to obtain a roasted sample to be recovered, wherein the average particle size of the roasted sample is 0.1-0.3 mm;
(2) mixing ammonia water with the concentration of 0.05-0.2 mol/L, extracting an organic phase and the roasting sample to be recovered obtained in the step (1), performing leaching extraction coupling reaction for 10-30 min at the stirring intensity of 200-400rpm and the temperature of 25-40 ℃, and then separating to obtain a molybdenum-containing organic phase; the leaching extraction coupling reaction comprises leaching and extraction which are carried out simultaneously; the mass ratio of the ammonia water to the roasting sample to be recovered is (5-20) to 1; the extracted organic phase comprises 5-30% of extracting agent N263 by volume fraction and 5-30% of organic solvent sec-octanol by volume fraction, and the balance of diluent kerosene; the O/A ratio of the extracted organic phase to the water phase is 1 (1-5);
(3) carrying out back extraction on the mixed solution of NaOH with the concentration of 0.1-1 mol/L and NaCl with the concentration of 0.1-1.5 mol/L and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution; the back extraction temperature is 25-40 ℃, the time is 1-10 min, and the back extraction oil phase and the water phase O/A in the back extraction are (5-1): (1-3).
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method for recovering the metal molybdenum in the waste hydrogenation catalyst through the integrated leaching and extraction, provided by the invention, the metal molybdenum and nickel in the waste catalyst are leached at normal temperature by adopting low-concentration ammonia water, and the metal molybdenum is effectively extracted and separated by adopting the extracting agent N263 in an alkaline environment without adding acid to adjust the pH value of a leaching solution, so that compared with extraction in most alkaline leaching solution acidic environments, the process operation steps are reduced, and the acid consumption and the energy consumption are reduced;
(2) according to the invention, a liquid-solid three-phase separation system is established by designing a leaching-extraction integrated reaction separation coupling process, leaching and extraction steps are synchronously carried out, reaction is mutually promoted, acid and alkali consumption in the original process is reduced, and the solid-liquid ratio is greatly reduced;
(3) in the leaching and extracting integrated system, reaction products can be separated in time, the metal leaching rate and the reaction separation efficiency are improved, and the problem of limited efficiency of step-by-step leaching and extracting reaction is effectively solved.
Drawings
FIG. 1 is a flow chart of a method for recovering molybdenum metal from a spent hydrogenation catalyst by integrated leaching and extraction provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
To demonstrate the recovery effectiveness of the process of the present invention, the spent hydroprocessing catalyst treated according to embodiments of the present invention was the same spent hydroprocessing catalyst having a molybdenum content of 12.5 wt%, a nickel content of 2.42 wt%, and an aluminum content of 25.25 wt%
Example 1
The embodiment provides a method for recovering metallic molybdenum in a waste hydrogenation catalyst by integrating leaching and extraction, which comprises the following steps:
(1) oxidizing and roasting 6g of the waste hydrogenation catalyst for 120min at the temperature of 400 ℃ in an air atmosphere, wherein the total mass is 3.52g after roasting is finished, the loss mass is 0.2g, the mass reduction rate is 3.3%, slight oil stains on the surface of the catalyst disappear, the color of the catalyst is changed from gray black to yellow white and agglomerates appear, and then the roasted sample to be recovered with the average particle size of 0.15mm is obtained after grinding;
(2) mixing 0.1mol/L ammonia water, an extracted organic phase and 1g of a roasting sample to be recovered, carrying out leaching extraction coupling reaction for 15min at the temperature of 250 ℃ of stirring strength of 300rpm, and then separating to obtain a molybdenum-containing organic phase; the leaching extraction coupling reaction comprises leaching and extraction which are carried out simultaneously; the mass ratio of the ammonia water to the roasting sample to be recovered is 10: 1; the extracted organic phase comprises 20 volume percent of extracting agent N263 and 20 volume percent of organic solvent sec-octanol, and the balance is diluent kerosene; the O/A ratio of the extraction organic phase to the water phase is 1: 3;
(3) carrying out back extraction on the mixed solution of NaOH with the concentration of 0.2mol/L and NaCl with the concentration of 1mol/L and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution; the back extraction temperature is 25 ℃, the time is 5min, and the back extraction oil phase and the water phase O/A in the back extraction are 1: 3.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 81.0% × 99.9% × 96.9% ═ 78.4%.
Example 2
The embodiment provides a method for recovering molybdenum metal in a waste hydrogenation catalyst through leaching and extraction integration, which comprises the following steps:
(1) oxidizing and roasting 6g of the waste hydrogenation catalyst for 120min at the temperature of 400 ℃ in an air atmosphere and an oxygen atmosphere, wherein the total mass is 5.8g after roasting is finished, the mass loss is 0.2g, the mass reduction rate is 3.3%, slight oil stain on the surface of the catalyst disappears, the color of the catalyst is changed from gray black to yellow white and agglomeration appears, and then the roasted sample to be recovered with the average particle size of 0.15mm is obtained after grinding;
(2) mixing ammonia water with the concentration of 0.05mol/L, the extracted organic phase and the roasted sample to be recovered obtained in the step (1), carrying out leaching extraction coupling reaction for 15min at the stirring intensity of 200rpm and the temperature of 30 ℃, and then separating to obtain a molybdenum-containing organic phase; the leaching extraction coupling reaction comprises leaching and extraction which are carried out simultaneously; the mass ratio of the ammonia water to the roasting sample to be recovered is 5: 1; the extracted organic phase comprises 5 volume percent of extracting agent N263 and 5 volume percent of organic solvent sec-octanol, and the balance is diluent kerosene; the O/A ratio of the extraction organic phase to the water phase is 1: 5;
(3) carrying out back extraction on the mixed solution of NaOH with the concentration of 0.2mol/L and NaCl with the concentration of 0.5mol/L and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain an aqueous phase sodium molybdate solution; the back extraction temperature is 40 ℃, the time is 1min, and the back extraction oil phase and the water phase O/A in the back extraction are 1: 1.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, the leaching rate of molybdenum, the extraction rate of molybdenum, and the back extraction rate of molybdenum, were 79.6% × 99.9% × 96.9% ═ 77.1%
Example 3
The embodiment provides a method for recovering molybdenum metal in a waste hydrogenation catalyst through leaching and extraction integration, which comprises the following steps:
(1) oxidizing and roasting 6g of the waste hydrogenation catalyst for 120min at the temperature of 400 ℃ in an oxygen atmosphere, wherein the total mass is 5.8g after roasting is finished, the loss mass is 0.2g, the mass reduction rate is 3.3%, slight oil stains on the surface of the catalyst disappear, the color of the catalyst is changed from gray black to yellow white and agglomerates appear, and then the roasted sample to be recovered with the average particle size of 0.15mm is obtained after grinding;
(2) mixing ammonia water with the concentration of 0.2mol/L, an extracted organic phase and the roasted sample to be recovered obtained in the step (1), carrying out leaching extraction coupling reaction for 10min at the stirring intensity of 300rpm and the temperature of 40 ℃, and then separating to obtain a molybdenum-containing organic phase; the leaching extraction coupling reaction comprises leaching and extraction which are carried out simultaneously; the mass ratio of the ammonia water to the roasting sample to be recovered is 20: 1; the extracted organic phase comprises 5 volume percent of extracting agent N263 and 30 volume percent of organic solvent sec-octanol, and the balance is diluent kerosene; O/A of the extraction organic phase and the water phase is 1: 2;
(3) carrying out back extraction on the mixed solution of NaOH with the concentration of 1mol/L and NaCl with the concentration of 0.1mol/L and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution; the back extraction temperature is 400 ℃, the time is 6min, and the ratio of the back extraction oil phase to the water phase O/A in the back extraction is 5: 1.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 77.0% × 99.9% × 79.0% ═ 60.8%.
Example 4
The embodiment provides a method for recovering molybdenum metal in a waste hydrogenation catalyst through leaching and extraction integration, which comprises the following steps:
(1) oxidizing and roasting 6g of the waste hydrogenation catalyst for 120min at the temperature of 400 ℃ in the air atmosphere, wherein the total mass is 5.8g after roasting is finished, the loss mass is 0.2g, the mass reduction rate is 3.3%, slight oil stains on the surface of the catalyst disappear, the color of the catalyst is changed from gray black to yellow white and agglomerates appear, and then the roasted sample to be recovered with the average particle size of 0.15mm is obtained after grinding;
(2) mixing 0.15mol/L ammonia water, an extracted organic phase and the roasted sample to be recovered obtained in the step (1), carrying out leaching extraction coupling reaction for 30min at the stirring intensity of 400rpm and the temperature of 35 ℃, and then separating to obtain a molybdenum-containing organic phase; the leaching extraction coupling reaction comprises leaching and extraction which are carried out simultaneously; the mass ratio of the ammonia water to the roasting sample to be recovered is 5: 1; the extracted organic phase comprises 25 volume percent of extracting agent N263 and 25 volume percent of organic solvent sec-octanol, and the balance of diluent kerosene; the O/A ratio of the extraction organic phase to the water phase is 1: 3;
(3) carrying out back extraction on the mixed solution of NaOH with the concentration of 1mol/L and NaCl with the concentration of 1.5mol/L and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution; the back extraction temperature is 36 ℃, the time is 4min, and the ratio of the back extraction oil phase to the water phase O/A in the back extraction is 5: 3.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, 82.3% × 99.9% × 90.5% ═ 74.4%.
Example 5
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: this example changed the stripped oil and water phase ratio of the strip in step (3) to 1: 1.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 81.0% × 99.9% × 94.0% ═ 76.0%.
Example 6
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: in the embodiment, the stripping agent in the back extraction in the step (3) is changed into a mixed solution of 0.2mol/L NaOH and 0.5mol/L NaCl, and the ratio O/A of the stripped oil phase to the stripped water phase is changed into 1: 1.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, the leaching rate of molybdenum, the extraction rate of molybdenum, and the back extraction rate of molybdenum, 81.0% × 99.9% × 85.9% × 70.0%
Example 7
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: this example changed the average particle size of the calcined sample to be recovered in step (1) to 0.5 mm.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, the leaching rate of molybdenum, the extraction rate of molybdenum, and the back extraction rate of molybdenum, 80.0% × 99.9% × 96.9% ═ 77.4%
Example 8
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: this example changed the organic phase extraction from step (2) to: 35% by volume of extracting agent N263 and 35% by volume of organic solvent sec-octanol, the balance being diluent kerosene;
by the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 81.0% × 99.6% × 87.0% ═ 70.2%.
Example 9
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: in this example, the concentration of the ammonia water in step (2) was changed to 0.3 mol/L.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, that is, the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, that is, 84.0% × 80.0% × 87.0% × 65.1%, were obtained.
Example 10
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: in this example, the concentration of the ammonia water in step (2) was changed to 0.05 mol/L.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 79.6% by 99.9% by 96.9% by 77.1%.
Example 11
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: in this example, the stripping agent in step (3) was changed to 0.2mol/L NaOH.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 81.0% × 99.9% × 43.0% ═ 38.4%.
Example 12
This example provides a process for the integrated leaching extraction recovery of molybdenum metal from spent hydrogenation catalysts, which differs from example 1 only in that: in the embodiment, the stripping agent in the step (3) is changed into 1mol/L NaCl.
By the method provided in this example, the recovery rate of molybdenum metal in the spent hydrogenation catalyst, i.e., the leaching rate of molybdenum, the extraction rate of molybdenum, and the stripping rate of molybdenum, i.e., 81.0% × 99.9% × 19.6% × 15.9%, were determined.
Comparative example 1
This comparative example provides a process for recovering molybdenum metal from spent hydrogenation catalyst which differs from example 1 only in that: in the comparative example, the leaching extraction coupling reaction in the step (2) is changed into leaching and extraction which are sequentially carried out, wherein the leaching temperature is 35 ℃, and the leaching time is 30 min; the extraction temperature is 35 ℃, and the extraction time is 20 min.
By adopting the method provided by the comparative example, the recovery rate of the metal molybdenum in the waste hydrogenation catalyst is 51.0% x 99.9% x 96.9% and 49.4% of the leaching rate of the molybdenum and the extraction rate of the molybdenum.
Comparative example 2
This comparative example provides a process for recovering molybdenum metal from spent hydrogenation catalyst which differs from example 1 only in that: this comparative example changed the oxidizing atmosphere described in step (1) to a nitrogen atmosphere.
The molybdenum in the waste hydrogenation catalyst exists in a mode of sulfide MoS2Molybdenum sulfide is not easy to dissolve in ammonia water, so that the metal molybdenum in the waste catalyst cannot be extracted through leaching extraction coupling reaction. 2MoS under an oxidizing atmosphere only2+7O2＝2MoO3+4SO2The oxidation of sulfide into oxide can react with ammonia water, and the extraction of molybdenum from waste catalyst is carried out by leaching extraction coupling reaction.
In conclusion, the method for recovering the metal molybdenum in the waste hydrogenation catalyst by integrating leaching and extraction adopts low-concentration ammonia water to leach the metal molybdenum and nickel in the waste catalyst at normal temperature, and adopts the extracting agent N263 to effectively extract and separate the metal molybdenum in the alkaline environment without adding acid to adjust the pH value of the leachate, so that compared with the extraction in the acidic environment of most alkaline leachate, the method reduces the process operation steps, and reduces the acid consumption and the energy consumption; by designing a leaching-extraction integrated reaction separation coupling process, a liquid-solid three-phase separation system is established, leaching and extraction steps are synchronously carried out, reaction is mutually promoted, acid and alkali consumption in the original process is reduced, reaction products can be separated in time, the metal leaching rate and the reaction separation efficiency are improved, and the problem of limited efficiency of stepwise leaching and extraction reactions is effectively solved.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for recovering metal molybdenum in a waste hydrogenation catalyst through leaching and extraction integration is characterized by comprising the following steps:
(1) roasting the waste hydrogenation catalyst in an oxidizing atmosphere, and grinding to obtain a roasted sample to be recovered;
(2) sequentially carrying out leaching extraction coupling reaction on the mixed leaching solution, the extracted organic phase and the roasting sample to be recovered obtained in the step (1), and separating to obtain a molybdenum-containing organic phase;
(3) and (3) carrying out back extraction on the mixed stripping agent and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution.
2. The method for recovering metallic molybdenum in waste hydrogenation catalyst by integrating leaching and extraction as claimed in claim 1, wherein the oxidizing atmosphere in step (1) comprises air atmosphere and/or oxygen atmosphere;
preferably, the roasting temperature in the step (1) is 400-600 ℃;
preferably, the roasting time in the step (1) is 30-120 min;
preferably, the average particle size of the roasted sample to be recovered in the step (1) is 0.1 to 0.3 mm.
3. The integrated leaching extraction method for recovering molybdenum metal in the spent hydrogenation catalyst according to claim 1 or 2, wherein the leaching extraction coupling reaction in the step (2) comprises leaching and extraction which are carried out simultaneously;
preferably, the reaction time of the leaching extraction coupling reaction is 10-30 min;
preferably, the reaction temperature of the leaching extraction coupling reaction is 25-40 ℃;
preferably, the stirring intensity in the leaching extraction coupling reaction is 200-400 rpm.
4. The method for recovering the metallic molybdenum in the spent hydrogenation catalyst by integrating leaching and extraction according to any one of claims 1 to 3, wherein the leachate in the leaching comprises ammonia water;
preferably, the concentration of the ammonia water is 0.05-0.2 mol/L.
5. The method for recovering the metal molybdenum in the waste hydrogenation catalyst by integrating leaching and extraction as claimed in any one of claims 1 to 4, wherein the mass ratio of the leaching solution to the roasted sample to be recovered obtained in the step (1) is (5-20): 1.
6. The integrated leaching extraction method for recovering metallic molybdenum in waste hydrogenation catalysts according to any one of claims 1 to 5, wherein the extraction liquid in the extraction comprises an extraction organic phase;
preferably, the extracted organic phase comprises extractant N263, diluent kerosene, and organic solvent sec-octanol;
preferably, the volume fraction of the extracting agent in the extraction organic phase is 5-30%, the volume fraction of the organic solvent is 5-30%, and the rest is the diluent.
7. The method for recovering the metal molybdenum in the waste hydrogenation catalyst through the integration of leaching and extraction as recited in any one of claims 1-6, wherein O/A of the organic phase and the aqueous phase extracted in the extraction is 1 (1-5).
8. The integrated leaching extraction process for recovering molybdenum from waste hydrocatalyst according to any one of claims 1 to 7, wherein the stripping agent comprises a mixed solution of NaOH and NaCl;
preferably, the concentration of the NaOH is 0.1-1 mol/L;
preferably, the concentration of the NaCl is 0.1-1.5 mol/L.
9. The method for recovering the metal molybdenum in the spent hydrogenation catalyst through the integration of leaching and extraction according to any one of claims 1 to 8, wherein the back extraction temperature in the step (3) is 25 to 40 ℃;
preferably, the back extraction time in the step (3) is 1-10 min;
preferably, the O/A of the stripping oil phase and the water phase in the back extraction in the step (3) is (5-1): (1-3).
10. The integrated leaching extraction process for recovering molybdenum from spent hydroprocessing catalysts according to any of claims 1-9, characterized in that it comprises the following steps:
(1) roasting the waste hydrogenation catalyst for 30-120 min at the temperature of 400-600 ℃ in an air atmosphere and/or an oxygen atmosphere, and then grinding to obtain a roasted sample to be recovered, wherein the average particle size of the roasted sample is 0.1-0.3 mm;
(2) mixing ammonia water with the concentration of 0.1-1 mol/L, extracting an organic phase and the roasting sample to be recovered obtained in the step (1), performing leaching extraction coupling reaction for 10-30 min at the stirring intensity of 200-400rpm and the temperature of 25-40 ℃, and then separating to obtain a molybdenum-containing organic phase; the leaching extraction coupling reaction comprises leaching and extraction which are carried out simultaneously; the mass ratio of the ammonia water to the roasting sample to be recovered is (5-20) to 1; the extracted organic phase comprises 5-30% of extracting agent N263 by volume fraction and 5-30% of organic solvent sec-octanol by volume fraction, and the balance of diluent kerosene; the O/A ratio of the extracted organic phase to the water phase is 1 (1-5);
(3) carrying out back extraction on the mixed solution of NaOH with the concentration of 0.1-1 mol/L and NaCl with the concentration of 0.1-1.5 mol/L and the molybdenum-containing organic phase obtained in the step (2), and standing to obtain a molybdenum-containing solution; the back extraction temperature is 25-40 ℃, the time is 1-10 min, and the back extraction oil phase and the water phase O/A in the back extraction are (5-1): (1-3).
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