Method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst

Abstract

The present invention belongs to the technical field of extraction and separation, and specifically relates to a method for preparing vanadyl sulfate using a waste residue oil hydrogenation catalyst, including the steps of preparing a leaching solution, reducing, recovering molybdenum, recovering vanadium, and preparing vanadyl sulfate. The present invention optimizes the extraction process for elements such as molybdenum and vanadium in the waste catalyst, effectively separates vanadium from molybdenum and other impurities during the extraction process, and obtains a high-purity vanadyl sulfate product.

Description

Technical Field

[0001] The invention belongs to the technical field of extraction and separation, and specifically relates to a method for preparing vanadyl sulfate by utilizing waste residue oil hydrogenation catalyst. Background Art

[0002] Vanadium is a rare metal element that is used in aerospace, chemical industry, new energy and other industrial fields. However, the natural resources of vanadium are relatively limited, so how to enrich and recover vanadium from secondary resources is a hot topic in current research. Since vanadium and molybdenum are diagonally adjacent in the periodic table and have similar properties, it is currently difficult to recover vanadium from resources such as waste catalysts and waste catalytic agents.

[0003] At present, there are mainly chemical precipitation, ion exchange, solvent extraction, etc. for the separation of vanadium and molybdenum. Among them, chemical precipitation cannot achieve deep separation of vanadium and molybdenum; ion exchange is only suitable for small-scale vanadium and molybdenum separation and is costly; extraction is the most mature vanadium and molybdenum separation technology currently used in industry.

[0004] The Chinese patent application document with publication number CN110817944A discloses a method for recovering waste SCR denitration catalysts. The method includes pretreatment, TiO2 separation, extraction and purification, titanium recovery, vanadium recovery, tungsten / molybdenum recovery and other steps. Through the recovery technology process, V2O5, ammonium tungstate / ammonium molybdate and BaTiO3 and other products can be recovered from the waste SCR denitration catalyst, and efficient resource utilization of waste SCR denitration catalysts can be achieved. However, this method uses an extractant to extract vanadium and tungsten / molybdenum elements in the solution at the same time, and then uses a stripping agent to strip and separate vanadium and tungsten / molybdenum elements in turn; after the stripping agent is first introduced, the chemical composition in the organic phase will change, which may change the extraction ability and selectivity of the extractant for elements such as molybdenum, affecting the extraction efficiency and the depth of separation of vanadium and molybdenum. Summary of the invention

[0005] There is a problem of difficulty in separating vanadium and molybdenum in the existing waste catalyst leaching solution; in order to solve this problem, the present invention provides a method for preparing vanadyl sulfate using waste residual oil hydrogenation catalyst.

[0006] In order to achieve the purpose of the present invention, the present invention adopts the following technical solutions:

[0007] The present invention provides a method for preparing vanadyl sulfate by using a waste residue oil hydrogenation catalyst, comprising the following steps:

[0008] (1) Preparation of leachate

[0009] Pre-treating the waste oil hydrogenation catalyst to obtain a leaching solution;

[0010] (2) Restoration

[0011] The pH value of the leaching solution is adjusted to 1.5-2.2, and a reducing agent is added to react to obtain a pre-extraction solution;

[0012] (3) Molybdenum recovery

[0013] (3.1) adjusting the pH value of the pre-extraction liquid to 1.5-2, adding 3,4,5-trihydroxybenzoic acid and mixing evenly, extracting with an imidazoline quaternary ammonium salt extraction system to obtain a molybdenum-rich extract and a vanadium-rich raffinate; the imidazoline quaternary ammonium salt extraction system comprises an imidazoline quaternary ammonium salt extractant and sulfonated kerosene;

[0014] (3.2) centrifuging and washing the molybdenum-rich extract, and stripping the molybdenum-rich extract with an alkaline solution to obtain a molybdenum-containing solution;

[0015] (4) Recovery of vanadium

[0016] (4.1) adjusting the pH value of the vanadium-rich raffinate to 1-2, heating the solution to 40-50° C. and mixing the solution evenly, extracting the solution using a phosphate ester extraction system to obtain a vanadium-rich extract; the phosphate ester extraction system comprises a phosphate ester extractant, triisoamyl phosphate and sulfonated kerosene;

[0017] (4.2) centrifuging and washing the vanadium-rich extract, and stripping the vanadium-rich extract with a sulfuric acid solution to obtain a vanadyl sulfate solution;

[0018] (5) Preparation of Vanadyl Sulfate

[0019] The vanadyl sulfate solution is evaporated and crystallized to obtain vanadyl sulfate.

[0020] Preferably, in (3.1), the method for preparing the imidazoline quaternary ammonium salt extractant comprises the following steps:

[0021] S1: uniformly mixing alkyl imidazoline, N-(4-butylphenyl)-2-chloro-acetamide and acetonitrile to react, removing acetonitrile by rotary evaporation, and drying to obtain imidazoline quaternary ammonium salt;

[0022] S2: Evenly mix imidazoline quaternary ammonium salt, diisooctyl phosphate, sodium bicarbonate aqueous solution and isopropanol, heat and stir; cool and filter to remove sodium chloride, rotary evaporate to remove isopropanol and water, and dry to obtain imidazoline quaternary ammonium salt extractant.

[0023] Preferably, in S1, the molar ratio of alkyl imidazoline to N-(4-butylphenyl)-2-chloro-acetamide is 1:(1-1.5); the reaction temperature is 70-80° C., and the reaction time is 6-8 h.

[0024] Preferably, in S2, the molar ratio of imidazoline quaternary ammonium salt to diisooctyl phosphate is (1.2-2):1; the reaction temperature is 50-60°C, and the reaction time is 10-12h.

[0025] Preferably, in (1), the pretreatment is oxidative roasting-sodium roasting-leaching; the oxidative roasting temperature is 500-600°C, and the oxidative roasting time is 3-8h;

[0026] The sodium calcination is to mix the waste oil hydrogenation catalyst after oxidation calcination with Na2CO3, grind and calcine; the mass ratio of Na2CO3 to the waste oil hydrogenation catalyst after oxidation calcination is (1.5-2.5):1; the temperature of the sodium calcination is 500-900°C, and the time of the sodium calcination is 3-8h;

[0027] By adopting the above technical solution, sufficient leaching of vanadium and molybdenum is ensured, while volatilization of vanadium and molybdenum and generation of additional impurities can be avoided.

[0028] The leaching is performed by adding 2.5-5 times the mass parts of water to the waste oil hydrogenation catalyst after sodium roasting, the leaching temperature is 60-90° C., and the leaching time is 1-4 hours.

[0029] By adopting the above technical scheme, the sulfides of molybdenum and vanadium are converted into soluble sodium salts during the roasting process, the mass ratio of Na2CO3 to the waste oil hydrogenation catalyst after oxidative roasting is optimized, and the process conditions such as roasting and leaching of the waste oil hydrogenation catalyst are controlled at the same time, thereby reducing the impurity content in the leachate.

[0030] Preferably, in (2), the reducing agent is one of sodium sulfite and sodium bisulfite; the reaction temperature is 25-60° C., and the reaction time is 1-2 h.

[0031] By adopting the above technical scheme, V(V) in the leaching solution is reduced to V(IV), the valence state of vanadium is unified, and at the same time, impurities introduced by iron and reducing agent in the leaching solution are prevented from being brought into the vanadium sulfate solution.

[0032] Preferably, in (3.1), the volume ratio of the imidazoline quaternary ammonium salt extraction system to the pre-extraction solution is 1:(1-4).

[0033] Preferably, in (3.1), the extraction temperature is 20-30°C, and the extraction time is 5-10 min.

[0034] Preferably, in (3.1), the imidazoline quaternary ammonium salt extraction system comprises 6%-10% by volume of the imidazoline quaternary ammonium salt extractant and 90%-94% by volume of sulfonated kerosene.

[0035] Preferably, in (3.2), the alkaline solution is an ammonia solution with a concentration of 1-3 mol / L, and the volume ratio of the molybdenum-rich extract to the alkaline solution is (1-4):1.

[0036] Preferably, in (3.2), the extraction temperature is 20-30° C., and the extraction time is 5-10 min.

[0037] Preferably, in (4.1), the phosphate ester extractant is one of P204 and P507; and the volume ratio of the phosphate ester extraction system to the vanadium-rich raffinate is 1:(1-3).

[0038] Preferably, in (4.1), the mixing time is 15-25 min.

[0039] Preferably, in (4.1), the extraction temperature is 20-30°C, and the extraction time is 5-10 min.

[0040] Preferably, in (4.1), the phosphate ester extraction system comprises 10%-15% by volume of a phosphate ester extractant, 10%-15% by volume of triisoamyl phosphate and 70%-80% by volume of sulfonated kerosene.

[0041] Preferably, in (4.2), the sulfuric acid solution is a sulfuric acid aqueous solution with a concentration of 0.5-4 mol / L, and the volume ratio of the vanadium-rich raffinate to the sulfuric acid aqueous solution is (1-6):1.

[0042] Preferably, in (4.2), the extraction temperature is 20-30° C., and the extraction time is 5-10 min.

[0043] The reaction equation of the imidazoline quaternary ammonium salt and the imidazoline quaternary ammonium salt extractant is as follows:

[0044] ;

[0045] ;

[0046] The alkyl imidazoline n=5, 6, 7, 8.

[0047] The extraction mechanism of imidazoline quaternary ammonium salt extractants is as follows:

[0048] First, the V(V) in the leaching solution is reduced to V(IV) by a reducing agent such as sodium sulfite. In the pH range of 1.5-2, V(IV) is present in the solution in the form of cations (VO 2+ ) exists, Mo(VI) exists in the form of polymerized anions (Mo7O 24 6- 、H3Mo7O 24 4-etc.); the cations in the imidazoline quaternary ammonium salt extractants combine with the larger and more hydrophobic polymerized molybdenum anions. The N in the cations of the imidazoline quaternary ammonium salt extractants contains a lone electron pair, which combines with the polymerized molybdenum anions through hydrogen bonds or directly coordinates with the metal ions to form macromolecules, and the anions play a synergistic role.

[0049] Add 3,4,5-trihydroxybenzoic acid to the pre-extraction solution. 3,4,5-trihydroxybenzoic acid can react with VO 2+ A complex reaction occurs, leaving vanadium in the raffinate, increasing the separation coefficient of vanadium and molybdenum; when extracting vanadium, the temperature is raised to cause it to dissociate, and V (IV) is more inclined to combine with phosphate extractants, extracting vanadium into the organic phase for enrichment.

[0050] In summary, the beneficial effects of the present invention are:

[0051] (1) The present invention introduces -NH groups into the cations of the imidazoline quaternary ammonium salt extractants, which can combine with O and H atoms in the polymerized molybdenum anions through hydrogen bonds, thereby ensuring a high extraction rate of molybdenum; at the same time, the introduction of phenyl groups into the cations of the imidazoline quaternary ammonium salt extractants has a large structural spatial effect, and its presence can increase the contact area and interaction opportunities between the extractants and the molybdenum ions, thereby improving the extraction capacity; the imidazoline quaternary ammonium salt extractants use diisooctyl phosphate containing a branched structure as an anion, which can improve the extraction capacity and extraction capacity; the imidazoline quaternary ammonium salt extractants prepared by the present invention have good extraction performance;

[0052] (2) In the present invention, 3,4,5-trihydroxybenzoic acid is added to the pre-extraction solution. 3,4,5-trihydroxybenzoic acid contains three hydroxyl groups. The oxygen atom on the hydroxyl group has a lone pair of electrons. The lone pair of electrons of the oxygen atom of the hydroxyl group can react with VO 2+ The empty orbitals of vanadium form coordination bonds, resulting in a complex reaction, which allows vanadium to remain in the raffinate. Compared with molybdenum ions, vanadium ions have a smaller ionic radius and a higher charge density, which makes vanadium ions more inclined to interact with 3,4,5-trihydroxybenzoic acid in the solution to form a stable complex, further promoting the separation of vanadium and molybdenum.

[0053] (3) The present invention uses imidazoline quaternary ammonium salt extractants as extractants for extracting and separating vanadium and molybdenum. Compared with extractants with ion exchange mechanisms, the internal synergistic effect between anions and cations greatly improves the extraction capacity of the extractant, while avoiding the problem of extractant loss caused by ion exchange. In addition, the extractant has stable performance and is not easy to volatilize, which reduces the proportion of traditional volatile organic solvents used.

[0054] (4) The present invention uses waste oil hydrogenation catalyst as raw material. On the one hand, it solves the problem of environmental pollution caused by waste oil hydrogenation catalyst. On the other hand, it optimizes the extraction process for elements such as molybdenum and vanadium in the waste catalyst, and effectively separates vanadium from molybdenum and other impurities during the extraction process. The purity of the vanadyl sulfate product obtained by the method of the present invention exceeds 99%. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 The present invention is a flow chart for the preparation of vanadyl sulfate. DETAILED DESCRIPTION

[0056] The technical solution of the present invention is explained in detail below with reference to specific embodiments of the present invention.

[0057] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0058] Example 1

[0059] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst in this embodiment has the following specific steps and the preparation flow chart is shown in FIG. Figure 1 :

[0060] (1) Preparation of leachate

[0061] The waste oil hydrogenation catalyst is placed in a muffle furnace and roasted at 500°C for 3h; 50g of the waste oil hydrogenation catalyst after oxidation roasting is mixed evenly with 75g of Na2CO3, ground into 80 meshes with a mortar, transferred to a muffle furnace, and roasted at 600°C for 3-8h; 30g of the waste oil hydrogenation catalyst after roasting is added to 120g of water in a beaker, stirred at 80°C for 2h, filtered, and the filtrate is the leaching liquid, and the filter residue is recovered;

[0062] (2) Restoration

[0063] The pH value of the leaching solution was adjusted to 1.5 with a 2 mol / L sulfuric acid aqueous solution, and 110% of the theoretical molar amount of sodium sulfite was added, and the mixture was reacted at 30°C for 2 h to obtain a pre-extraction solution;

[0064] (3) Molybdenum recovery

[0065] (3.1) The pH value of 10 mL of the pre-extraction solution was adjusted to 1.5, 0.1 g of 3,4,5-trihydroxybenzoic acid was added and stirred evenly, and 10 mL of oxazoline quaternary ammonium salt extraction system was oscillated and extracted in an extraction purification oscillator at an extraction temperature of 25° C. and an extraction time of 10 min to obtain a molybdenum-rich extract and a vanadium-rich raffinate; in this embodiment, the oxazoline quaternary ammonium salt extraction system is 10% by volume of an imidazoline quaternary ammonium salt extractant and 90% by volume of sulfonated kerosene;

[0066] (3.2) centrifuging the molybdenum-rich extract, removing the aqueous phase carried by the molybdenum-rich extract, washing the molybdenum-rich extract with water, and back-extracting 20 mL of the molybdenum-rich extract with 10 mL of 1 mol / L ammonia solution at an extraction temperature of 25° C. for 10 min to obtain a molybdenum-containing solution;

[0067] (4) Recovery of vanadium

[0068] (4.1) Adjust the pH value of 20 mL of vanadium-rich raffinate to 1, heat to 45° C. and stir for 15 min, and oscillate and extract with 10 mL of phosphate ester extraction system in an extraction purification oscillator at an extraction temperature of 25° C. for 10 min to obtain a vanadium-rich extract; in this embodiment, the phosphate ester extraction system is 10% by volume of P204, 10% by volume of triisoamyl phosphate and 80% by volume of sulfonated kerosene;

[0069] (4.2) Centrifuge the vanadium-rich extract, remove the aqueous phase carried by the vanadium-rich extract, wash the vanadium-rich raffinate with water, and back-extract 60 mL of the vanadium-rich extract with 10 mL of a 0.5 mol / L sulfuric acid aqueous solution at a temperature of 25° C. for 10 min to obtain a vanadyl sulfate solution;

[0070] (5) Preparation of Vanadyl Sulfate

[0071] The vanadyl sulfate solution is evaporated and crystallized to obtain vanadyl sulfate. After testing, the purity of the vanadyl sulfate is 99.5%.

[0072] In this embodiment, the recovery rate of vanadium element from the leaching solution to the stripping process is 98.68%, and the recovery rate of molybdenum element is 98.84%.

[0073] The specific steps of the preparation method of the imidazoline quaternary ammonium salt extractant of the present embodiment are as follows:

[0074] S1: 10.55 g alkyl imidazoline (g = 7), 13.53 g N-(4-butylphenyl)-2-chloro-acetamide and 200 mL acetonitrile were stirred evenly and reacted at 70 ° C for 7 h, and the acetonitrile was removed by rotary evaporation at 80 ° C, and dried to obtain imidazoline quaternary ammonium salt;

[0075] S2: 43.65g of imidazoline quaternary ammonium salt, 16.12g of diisooctyl phosphate, 10mL of 6mol / L sodium bicarbonate aqueous solution and 100mL of isopropanol were stirred evenly, and reacted at 55°C for 10h; cooled and filtered to remove sodium chloride, and isopropanol and water were removed by rotary evaporation at 80°C, and dried to obtain an imidazoline quaternary ammonium salt extractant.

[0076] Example 2

[0077] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst in this embodiment has the following specific steps:

[0078] (1) Preparation of leachate

[0079] The waste oil hydrogenation catalyst is placed in a muffle furnace and roasted at 550°C for 5h; 50g of the waste oil hydrogenation catalyst after oxidation roasting is mixed evenly with 125g of Na2CO3, ground into 80 meshes with a mortar, transferred to a muffle furnace, and roasted at 500°C for 3h; 30g of the waste oil hydrogenation catalyst after roasting is added to 150g of water in a beaker, stirred at 90°C for 1h, filtered, and the filtrate is the leaching liquid, and the filter residue is recovered;

[0080] (2) Restoration

[0081] The pH value of the leaching solution was adjusted to 1.7 with a 2 mol / L sulfuric acid aqueous solution, and 120% of the theoretical molar amount of sodium sulfite was added, and the mixture was reacted at 25°C for 2 h to obtain a pre-extraction solution;

[0082] (3) Molybdenum recovery

[0083] (3.1) The pH value of 20 mL of the pre-extraction solution was adjusted to 1.8, 0.2 g of 3,4,5-trihydroxybenzoic acid was added and stirred evenly, and 10 mL of oxazoline quaternary ammonium salt extraction system was oscillated and extracted in an extraction purification oscillator at an extraction temperature of 20° C. and an extraction time of 5 min to obtain a molybdenum-rich extract and a vanadium-rich raffinate; in this embodiment, the oxazoline quaternary ammonium salt extraction system is 8% by volume of an imidazoline quaternary ammonium salt extractant and 92% by volume of sulfonated kerosene;

[0084] (3.2) centrifuging the molybdenum-rich extract, removing the aqueous phase carried by the molybdenum-rich extract, washing the molybdenum-rich extract with water, and stripping 20 mL of the molybdenum-rich extract with 10 mL of 2 mol / L ammonia solution at an extraction temperature of 20° C. for an extraction time of 5 min to obtain a molybdenum-containing solution;

[0085] (4) Recovery of vanadium

[0086] (4.1) Adjust the pH value of 10 mL of vanadium-rich raffinate to 1, heat to 40° C. and stir for 20 min, and oscillate and extract with 10 mL of phosphate ester extraction system in an extraction purification oscillator at 20° C. for 5 min to obtain a vanadium-rich extract; in this embodiment, the phosphate ester extraction system is 10% by volume of P204, 15% by volume of triisoamyl phosphate and 75% by volume of sulfonated kerosene;

[0087] (4.2) Centrifuge the vanadium-rich extract, remove the aqueous phase carried by the vanadium-rich extract, wash the vanadium-rich raffinate with water, and back-extract 20 mL of the vanadium-rich extract with 10 mL of a 2 mol / L sulfuric acid aqueous solution at a temperature of 20° C. for 5 min to obtain a vanadyl sulfate solution;

[0088] (5) Preparation of Vanadyl Sulfate

[0089] The vanadyl sulfate solution is evaporated and crystallized to obtain vanadyl sulfate. After testing, the purity of the vanadyl sulfate is 99.4%.

[0090] In this embodiment, the recovery rate of vanadium element from the leaching solution to the stripping process is 99.05%, and the recovery rate of molybdenum element is 99.16%.

[0091] The specific steps of the preparation method of the imidazoline quaternary ammonium salt extractant of the present embodiment are as follows:

[0092] S1: 9.15 g n = 5 alkyl imidazoline, 11.3 g N-(4-butylphenyl)-2-chloro-acetamide and 200 mL acetonitrile were stirred evenly and reacted at 75 ° C for 6 h, and the acetonitrile was removed by rotary evaporation at 80 ° C, and dried to obtain imidazoline quaternary ammonium salt;

[0093] S2: 24.55 g of imidazoline quaternary ammonium salt, 16.12 g of diisooctyl phosphate, 10 mL of 6 mol / L sodium bicarbonate aqueous solution and 100 mL of isopropanol were stirred evenly and reacted at 60°C for 12 h; cooled and filtered to remove sodium chloride, and isopropanol and water were removed by rotary evaporation at 80°C, and dried to obtain an imidazoline quaternary ammonium salt extractant.

[0094] Example 3

[0095] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst in this embodiment has the following specific steps:

[0096] (1) Preparation of leachate

[0097] The waste oil hydrogenation catalyst is placed in a muffle furnace and roasted at 600°C for 6 hours; 50g of the waste oil hydrogenation catalyst after oxidation roasting is evenly mixed with 90g of Na2CO3, ground into 80 meshes with a mortar, transferred to a muffle furnace, and roasted at 900°C for 6 hours; 30g of the waste oil hydrogenation catalyst after roasting is added to 75g of water and dissolved in a beaker, stirred at 70°C for 2 hours, and filtered, the filtrate is the leaching liquid, and the filter residue is recovered;

[0098] (2) Restoration

[0099] The pH value of the leaching solution was adjusted to 2.2 with a 2 mol / L sulfuric acid aqueous solution, and 130% of the theoretical molar amount of sodium bisulfite was added, and the mixture was reacted at 50°C for 1 hour to obtain a pre-extraction solution;

[0100] (3) Molybdenum recovery

[0101] (3.1) Adjust the pH value of 30 mL of pre-extraction solution to 2, add 0.3 g of 3,4,5-trihydroxybenzoic acid and stir evenly, and oscillate and extract with 10 mL of oxazoline quaternary ammonium salt extraction system in an extraction purification oscillator at an extraction temperature of 20° C. for 8 min to obtain a molybdenum-rich extract and a vanadium-rich raffinate; in this embodiment, the oxazoline quaternary ammonium salt extraction system is 6% by volume of an imidazoline quaternary ammonium salt extractant and 94% by volume of sulfonated kerosene;

[0102] (3.2) centrifuging the molybdenum-rich extract, removing the aqueous phase carried by the molybdenum-rich extract, washing the molybdenum-rich extract with water, and back-extracting 40 mL of the molybdenum-rich extract with 10 mL of 3 mol / L ammonia solution at an extraction temperature of 20° C. for an extraction time of 8 min to obtain a molybdenum-containing solution;

[0103] (4) Recovery of vanadium

[0104] (4.1) Adjust the pH value of 10 mL of vanadium-rich raffinate to 2, heat to 50° C. and stir for 25 min, and oscillate and extract with 10 mL of phosphate ester extraction system in an extraction purification oscillator at an extraction temperature of 20° C. for 8 min to obtain a vanadium-rich extract; in this embodiment, the phosphate ester extraction system is 15% by volume of P507, 10% by volume of triisoamyl phosphate and 75% by volume of sulfonated kerosene;

[0105] (4.2) Centrifuge the vanadium-rich extract, remove the aqueous phase carried by the vanadium-rich extract, wash the vanadium-rich raffinate with water, and back-extract 40 mL of the vanadium-rich extract with 10 mL of a 1 mol / L sulfuric acid aqueous solution at a temperature of 20° C. for 8 min to obtain a vanadyl sulfate solution;

[0106] (5) Preparation of Vanadyl Sulfate

[0107] The vanadyl sulfate solution is evaporated and crystallized to obtain vanadyl sulfate. After testing, the purity of the vanadyl sulfate is 99.6%.

[0108] In this embodiment, the recovery rate of vanadium element from the leaching solution to the stripping process is 98.96%, and the recovery rate of molybdenum element is 98.79%.

[0109] The specific steps of the preparation method of the imidazoline quaternary ammonium salt extractant of the present embodiment are as follows:

[0110] S1: 9.85 g n = 6 alkyl imidazoline, 16.9 g N-(4-butylphenyl)-2-chloro-acetamide and 200 mL acetonitrile were stirred evenly and reacted at 75 ° C for 6 h, and the acetonitrile was removed by rotary evaporation at 80 ° C, and dried to obtain imidazoline quaternary ammonium salt;

[0111] S2: 33.8 g of imidazoline quaternary ammonium salt, 16.12 g of diisooctyl phosphate, 10 mL of 6 mol / L sodium bicarbonate aqueous solution and 100 mL of isopropanol were stirred evenly and reacted at 50° C. for 11 h; cooled and filtered to remove sodium chloride, and isopropanol and water were removed by rotary evaporation at 80° C., and dried to obtain an imidazoline quaternary ammonium salt extractant.

[0112] Example 4

[0113] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst in this embodiment has the following specific steps:

[0114] (1) Preparation of leachate

[0115] The waste oil hydrogenation catalyst was placed in a muffle furnace and roasted at 550°C for 8h; 50g of the waste oil hydrogenation catalyst after oxidation roasting was mixed with 110g of Na2CO3, ground into 80 meshes with a mortar, transferred to a muffle furnace, and roasted at 700°C for 8h; 30g of the waste oil hydrogenation catalyst after roasting was added to 90g of water in a beaker, stirred at 60°C for 4h, filtered, and the filtrate was the leaching liquid, and the filter residue was recovered;

[0116] (2) Restoration

[0117] The pH value of the leaching solution was adjusted to 1.9 with a 2 mol / L sulfuric acid aqueous solution, and 110% of the theoretical molar amount of sodium bisulfite was added, and the mixture was reacted at 60°C for 1 hour to obtain a pre-extraction solution;

[0118] (3) Molybdenum recovery

[0119] (3.1) The pH value of 40 mL of the pre-extraction solution was adjusted to 1.8, 0.4 g of 3,4,5-trihydroxybenzoic acid was added and stirred evenly, and 10 mL of oxazoline quaternary ammonium salt extraction system was oscillated and extracted in an extraction purification oscillator at an extraction temperature of 30° C. and an extraction time of 10 min to obtain a molybdenum-rich extract and a vanadium-rich raffinate; in this embodiment, the oxazoline quaternary ammonium salt extraction system is 10% by volume of an imidazoline quaternary ammonium salt extractant and 90% by volume of sulfonated kerosene;

[0120] (3.2) centrifuging the molybdenum-rich extract, removing the aqueous phase carried by the molybdenum-rich extract, washing the molybdenum-rich extract with water, and back-extracting 10 mL of the molybdenum-rich extract with 10 mL of 2 mol / L ammonia solution at an extraction temperature of 30° C. for 10 min to obtain a molybdenum-containing solution;

[0121] (4) Recovery of vanadium

[0122] (4.1) 40 mL of vanadium-rich raffinate was adjusted to pH 2, heated to 50° C. and stirred for 15 min, and then oscillated and extracted with 10 mL of a phosphate ester extraction system in an extraction purification oscillator at a temperature of 30° C. for 10 min to obtain a vanadium-rich extract; in this embodiment, the phosphate ester extraction system is 15% by volume of P507, 15% by volume of triisoamyl phosphate, and 70% by volume of sulfonated kerosene;

[0123] (4.2) Centrifuge the vanadium-rich extract, remove the aqueous phase carried by the vanadium-rich extract, wash the vanadium-rich raffinate with water, and back-extract 10 mL of the vanadium-rich extract with 10 mL of a 4 mol / L sulfuric acid aqueous solution at a temperature of 30° C. for 10 min to obtain a vanadyl sulfate solution;

[0124] (5) Preparation of Vanadyl Sulfate

[0125] The vanadyl sulfate solution is evaporated and crystallized to obtain vanadyl sulfate. After testing, the purity of the vanadyl sulfate is 99.6%.

[0126] In this embodiment, the recovery rate of vanadium element from the leaching solution to the stripping process is 99.11%, and the recovery rate of molybdenum element is 99.21%.

[0127] The specific steps of the preparation method of the imidazoline quaternary ammonium salt extractant of the present embodiment are as follows:

[0128] S1: 11.25 g n = 8 alkyl imidazoline, 14.66 g N-(4-butylphenyl)-2-chloro-acetamide and 200 mL acetonitrile were stirred evenly and reacted at 80 ° C for 8 h, and the acetonitrile was removed by rotary evaporation at 80 ° C, and dried to obtain imidazoline quaternary ammonium salt;

[0129] S2: 27.03 g of imidazoline quaternary ammonium salt, 16.12 g of diisooctyl phosphate, 10 mL of 6 mol / L sodium bicarbonate aqueous solution and 100 mL of isopropanol were stirred evenly, and reacted at 60°C for 11 h; cooled and filtered to remove sodium chloride, and isopropanol and water were removed by rotary evaporation at 80°C, and dried to obtain an imidazoline quaternary ammonium salt extractant.

[0130] Comparative Example 1

[0131] This comparative example investigates the effects of different extractants on the extraction rates of molybdenum and vanadium in step (3.1). The test results are shown in Table 1.

[0132] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst is different from that in Example 1 in that:

[0133] 1A: Substituting the imidazoline quaternary ammonium salt extractant in step (3.1) of Example 1 with an equal amount of the imidazoline quaternary ammonium salt prepared in step S1 of Example 1, and the rest is the same as in Example 1;

[0134] 1B: The imidazoline quaternary ammonium salt extractant in step (3.1) of Example 1 is replaced with an equal amount of n=1 imidazoline quaternary ammonium salt extractant, and the rest is the same as Example 1.

[0135] Table 1 Test results

[0136]

[0137] By comparing 1A in Table 1 with Example 1, it can be seen that under the same amount of extractant, the imidazoline quaternary ammonium salt extractant prepared by the present invention has a stronger extraction ability for molybdenum than the imidazoline quaternary ammonium salt; by comparing 1B in Table 1 with Example 1, it can be seen that when the anions of the imidazoline quaternary ammonium salt extractants are the same, the carbon chain on the imidazole ring of the cationic imidazoline quaternary ammonium salt extractant increases, the hydrophobicity of the quaternary ammonium salt extractant is enhanced, and the extraction rate is increased accordingly; both have little effect on the extraction rate of vanadium.

[0138] Comparative Example 2

[0139] This comparative example investigated the effect of different pH values ​​on the extraction rates of molybdenum and vanadium in step (3.1). The test results are shown in Table 2.

[0140] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst is different from that of Example 1 in that the pH in step (3.1) is different, and the rest is the same as Example 1.

[0141] Table 2 Test results

[0142]

[0143] It can be seen from Table 2 that with the increase of pH, VO 2+ It gradually transforms to vanadium anions and polymerized vanadium anions, and is thus co-extracted with molybdenum. Therefore, the extraction rate of vanadium increases, while the extraction rate of molybdenum decreases.

[0144] Comparative Example 3

[0145] This comparative example investigates the effect of 3,4,5-trihydroxybenzoic acid on the extraction rate of molybdenum and vanadium in step (3.1). The test results are shown in Table 3.

[0146] The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst is different from that in Example 1 in that 3,4,5-trihydroxybenzoic acid is not added in this comparative example, and the rest is the same as in Example 1.

[0147] Table 3 Test results

[0148]

[0149] It can be seen from Table 3 that the addition of 3,4,5-trihydroxybenzoic acid helps to promote the separation of vanadium and molybdenum and improve the extraction rate of molybdenum.

[0150] The above is an exemplary description of the present invention. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or equivalent replacement that can be done by other technicians in this field without expending creative labor falls within the protection scope of the present invention.

Claims

1. A method for preparing vanadyl sulfate using a waste residue oil hydrogenation catalyst, characterized in that: The steps include: (1) Preparation of leachate Pre-treating the waste oil hydrogenation catalyst to obtain a leaching solution; (2) Restoration The pH value of the leaching solution is adjusted to 1.5-2.2, and a reducing agent is added to react to obtain a pre-extraction solution; (3) Molybdenum recovery (3.1) adjusting the pH value of the pre-extraction liquid to 1.5-2, adding 3,4,5-trihydroxybenzoic acid and mixing evenly, extracting with an imidazoline quaternary ammonium salt extraction system to obtain a molybdenum-rich extract and a vanadium-rich raffinate; the imidazoline quaternary ammonium salt extraction system comprises an imidazoline quaternary ammonium salt extractant and sulfonated kerosene; (3.2) centrifuging and washing the molybdenum-rich extract, and stripping the molybdenum-rich extract with an alkaline solution to obtain a molybdenum-containing solution; (4) Recovery of vanadium (4.1) adjusting the pH value of the vanadium-rich raffinate to 1-2, heating the solution to 40-50° C. and mixing the solution evenly, extracting the solution using a phosphate ester extraction system to obtain a vanadium-rich extract; the phosphate ester extraction system comprises a phosphate ester extractant, triisoamyl phosphate and sulfonated kerosene; (4.2) centrifuging and washing the vanadium-rich extract, and stripping the vanadium-rich extract with a sulfuric acid solution to obtain a vanadyl sulfate solution; (5) Preparation of Vanadyl Sulfate The vanadyl sulfate solution is evaporated and crystallized to obtain vanadyl sulfate; The preparation method of the imidazoline quaternary ammonium salt extractant comprises the following steps: S1: uniformly mixing alkyl imidazoline, N-(4-butylphenyl)-2-chloro-acetamide and acetonitrile to react, removing acetonitrile by rotary evaporation, and drying to obtain imidazoline quaternary ammonium salt; S2: Evenly mix imidazoline quaternary ammonium salt, diisooctyl phosphate, sodium bicarbonate aqueous solution and isopropanol, heat and stir; cool and filter to remove sodium chloride, rotary evaporate to remove isopropanol and water, and dry to obtain imidazoline quaternary ammonium salt extractant.

2. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the S1, the molar ratio of alkyl imidazoline to N-(4-butylphenyl)-2-chloro-acetamide is 1:(1-1.5); the reaction temperature is 70-80° C., and the reaction time is 6-8 hours.

3. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In S2, the molar ratio of imidazoline quaternary ammonium salt to diisooctyl phosphate is (1.2-2):1; the reaction temperature is 50-60°C, and the reaction time is 10-12h.

4. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the above (1), the pretreatment is oxidation roasting-sodium roasting-leaching; The temperature of the oxidation roasting is 500-600°C, and the time of the oxidation roasting is 3-8h; The sodium calcination is to mix the waste oil hydrogenation catalyst after oxidation calcination with Na2CO3, grind and calcine; the mass ratio of Na2CO3 to the waste oil hydrogenation catalyst after oxidation calcination is (1.5-2.5):1; the temperature of the sodium calcination is 500-900°C, and the time of the sodium calcination is 3-8h; The leaching is performed by adding 2.5-5 times the mass parts of water to the waste oil hydrogenation catalyst after sodium roasting, the leaching temperature is 60-90° C., and the leaching time is 1-4 hours.

5. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the above (2), the reducing agent is one of sodium sulfite and sodium bisulfite; the reaction temperature is 25-60°C, and the reaction time is 1-2h.

6. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the above (3.1), the volume ratio of the imidazoline quaternary ammonium salt extraction system to the pre-extraction solution is 1:(1-4).

7. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the above (3.2), the alkaline solution is an ammonia solution with a concentration of 1-3 mol / L, and the volume ratio of the molybdenum-rich extract to the alkaline solution is (1-4):

1.

8. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the above (4.1), the phosphate extractant is one of P204 and P507; the volume ratio of the phosphate extraction system to the vanadium-rich raffinate is 1:(1-3).

9. The method for preparing vanadyl sulfate using waste residue oil hydrogenation catalyst according to claim 1, characterized in that: In the above (4.2), the sulfuric acid solution is a sulfuric acid aqueous solution with a concentration of 0.5-4 mol / L, and the volume ratio of the vanadium-rich raffinate to the sulfuric acid aqueous solution is (1-6):1.

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