Recycling method of waste hydrogenation catalyst

Abstract

The invention belongs to the field of secondary resource recovery processing. The invention provides a waste hydrogenation catalyst recovery treatment method, which comprises: mixing a waste hydrogenation catalyst, sodium carbonate and a sodium aluminate solution to obtain a raw slurry, roasting the raw slurry to obtain a clinker, and carrying out water leaching on the clinker to obtain a sodium aluminate-containing leachate and a nickel-rich leachate, sodium salt roasting is carried out on the waste hydrogenation catalyst through combination of sodium carbonate and a sodium aluminate solution, inert aluminum oxide in the waste hydrogenation catalyst is dissociated to release nickel, then elements such as aluminum are leached out through water leaching, a nickel-rich material is obtained, separation and recycling are achieved, and the waste hydrogenation catalyst is recycled. And efficient recovery and resource cyclic utilization of the waste hydrogenation catalyst can be realized under relatively short and relatively mild process conditions.

Description

Technical Field

[0001] The invention belongs to the technical field of comprehensive recovery of secondary resources and relates to a recovery and treatment method of waste hydrogenation catalysts. Background Art

[0002] Hydrogenation catalysts are usually based on alumina as the basic carrier, with catalytic metals such as nickel loaded on it. They are one of the most important alumina-based catalysts in the oil refining process. Hydrogenation catalysts are used to catalyze hydrodesulfurization, denitrogenation, deoxygenation, demetallization, etc., to improve the quality and output of finished oil. In recent years, with the continuous improvement of oil refining capacity, the consumption of hydrogenation catalysts has been growing steadily. However, in order to solve the problem that hydrogenation catalysts are deactivated due to carbon deposition, sintering and other reasons during use, they cannot be used. New catalysts are often replaced, which leads to the generation of a large number of waste hydrogenation catalysts over time.

[0003] Waste hydrogenation catalysts contain a large amount of valuable elements such as aluminum and nickel, and the content is much higher than that of natural minerals. It is a high-value secondary metal resource. Due to some characteristics of the waste hydrogenation catalyst materials themselves, various existing recycling and treatment processes face some urgent problems to be solved. Specifically, the components of waste hydrogenation catalysts are extremely complex, containing a large amount of inert aluminum oxide (corundum, etc.) and a certain amount of silicon dioxide, and inert aluminum oxide is difficult to dissolve by acid and alkali. After the waste hydrogenation catalyst is sintered and deactivated, the valuable metal nickel is embedded or wrapped into the inert aluminum oxide carrier and is difficult to be leached by acid and alkali. In addition, valuable metal elements exist in various forms such as oxides, sulfides, salts, and multi-metal complexes, which makes separation and recovery extremely difficult.

[0004] At present, the main method for industrial recovery of valuable element nickel in waste hydrogenation catalysts is roasting-leaching, but this recovery method has the following disadvantages: (1) when no other additives are added, the roasting temperature is high, the time is long, and the energy consumption is high; (2) when other additives are added, the amount of additives is large and the cost is high.

[0005] For example, CN116751966A discloses a method for separating and recovering molybdenum and nickel from waste hydrogenation catalysts, comprising first placing the waste catalyst in a tubular furnace for air roasting to generate molybdenum trioxide and nickel oxide, and after reaching a certain temperature, the molybdenum trioxide begins to sublimate, and the gasified molybdenum trioxide is recycled through a condenser. Subsequently, the remaining roasted product is placed in a reactor, a certain concentration of chlorine dioxide gas is introduced, and the nickel oxide reacts with it at room temperature to generate nickel chloride and is recycled. CN105709853A discloses a method for recycling waste hydrogenation catalysts, comprising grinding the waste hydrogenation catalyst after degreasing to form a powder, washing it with hydrochloric acid, filtering, washing, drying, introducing chlorine and air under the action of ultrasound, reacting, moving the solid product into a container filled with nitrogen and heating it, volatilizing the chloride or chlorine oxide of metal molybdenum, nickel or cobalt, and vanadium, separating the gas-solid phase, condensing and recovering the metal from the gas phase, and washing the solid residue after separation with water or an acidic solution, and drying. Although the above methods can effectively separate and recover nickel and other metals, they use a large amount of dangerous chlorine and chlorine dioxide gas for treatment, which has high requirements for equipment, complex processes, and is prone to safety problems.

[0006] Therefore, there is an urgent need for a method to efficiently recover spent hydrogenation catalysts under mild conditions to achieve the recycling of high-value metal secondary resources. Summary of the invention

[0007] In view of the problems existing in the prior art, the object of the present invention is to provide a method for recovering and treating a waste hydrogenation catalyst, which comprises mixing the waste hydrogenation catalyst with sodium carbonate and sodium aluminate solution to obtain a raw material slurry, roasting the raw material slurry to obtain a clinker, and leaching the clinker in water to obtain a sodium aluminate-containing leaching solution and a nickel-rich leaching material; sodium-fermenting and roasting the waste hydrogenation catalyst with a combination of sodium carbonate and sodium aluminate solution to dissociate the inert alumina in the waste hydrogenation catalyst to release nickel, and then leaching aluminum and other elements by water leaching to obtain a nickel-rich material, thereby achieving separation and recovery, and realizing efficient recovery and resource recycling of the waste hydrogenation catalyst under shorter and milder process conditions.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a method for recovering and treating a waste hydrogenation catalyst, the method comprising:

[0010] A waste hydrogenation catalyst is provided, and the waste hydrogenation catalyst is mixed with sodium carbonate and sodium aluminate solution to obtain a raw material slurry, the raw material slurry is roasted to obtain a clinker, and the clinker is soaked in water to obtain a sodium aluminate-containing leaching solution and a nickel-rich leaching material.

[0011] The present invention firstly adopts sodium carbonate and sodium aluminate solution to carry out coordinated sodium calcination on the waste hydrogenation catalyst. The components of the sodium carbonate and sodium aluminate solutions can cooperate with each other, so that the inert aluminum oxide in the waste hydrogenation catalyst is more easily and completely dissociated, and the nickel wrapped therein is released; and then water leaching is performed to obtain a nickel-rich leached material (or nickel-rich material) and a sodium aluminate-containing leaching solution, thereby realizing efficient recovery of nickel in the waste hydrogenation catalyst and recycling of raw materials, and shortening the calcination time at the same time. The calcination conditions are mild, and high temperature and strong acid and strong alkali environment are not required, so that the corrosion of strong acid and strong alkali to the equipment is avoided, and the operation risk is reduced.

[0012] It is worth noting that, compared with the use of sodium bicarbonate or directly using sodium hydroxide for mixing and then roasting, the present invention uses sodium carbonate and sodium aluminate solution to produce a synergistic effect, which is beneficial to improve the nickel recovery rate in the waste hydrogenation catalyst and reduce the recovery cost at the same time. This is because sodium bicarbonate contains less Na2O, and 2 mol of sodium bicarbonate is required to have the same effect as 1 mol of sodium carbonate, so the cost is relatively high, and the thermal stability of sodium bicarbonate is relatively poor. It is easy to decompose under high temperature conditions to produce carbon dioxide and water, which will cause temperature fluctuations during the roasting process and affect the roasting effect; while sodium hydroxide is highly corrosive and easily corrodes equipment, and its price is relatively expensive and the cost is high.

[0013] It should also be noted that those with common technical knowledge in the field or professionals in the field know that the waste hydrogenation catalyst contains NiO and inactive Al2O3 components.

[0014] The following are preferred technical solutions of the present invention, but are not intended to be limitations of the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0015] As a preferred technical solution of the present invention, the recycling method comprises:

[0016] Firstly, a sodium aluminate solution is mixed with sodium carbonate to obtain a mixed solution, and then the mixed solution is mixed with the waste hydrogenation catalyst to obtain the raw material slurry;

[0017] As a preferred technical solution of the present invention, for the mixing, the concentration of the sodium aluminate solution is 2 to 4 mol / L, for example, 2 mol / L, 2.2 mol / L, 2.3 mol / L, 2.7 mol / L, 3 mol / L, 3.3 mol / L, 3.5 mol / L, 3.7 mol / L or 4 mol / L, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0018] The present invention further preferably has a concentration of 2 to 4 mol / L of the sodium aluminate solution, so that sodium carbonate and sodium aluminate can work together to promote the dissociation of inert alumina in the spent hydrogenation catalyst during the roasting process, so as to efficiently recover nickel; and when the concentration of Na2O in the sodium aluminate solution is low, an increase in the amount of sodium carbonate added will result in an increase in the roasting cost.

[0019] As a preferred technical solution of the present invention, the waste hydrogenation catalyst component also includes at least one of Na2O, V2O5, SiO2, P2O5, CoO or MoO3.

[0020] As a preferred technical solution of the present invention, for the mixing, the molar amount of the sodium carbonate is A, the total molar amount of Na2O in the sodium aluminate solution is B, and the molar amount of Al2O3 in the waste hydrogenation catalyst is C, then A:B=(2.5-6):1, for example 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.3:1, 4.5:1, 4.8:1, 5:1, 5.2:1, 5.5:1, 5.8 :1 or 6:1, etc.; (A+B):C=(0.8-1.2):1, for example 0.8:1, 0.83:1, 0.85:1, 0.88:1, 0.9:1, 0.93:1, 0.95:1, 0.98:1, 1:1, 1.05:1, 1.08:1, 1.1:1, 1.12:1, 1.15:1, 1.18:1 or 1.2:1, etc., but are not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable.

[0021] The present invention further preferably prefers (A+B):C=(0.8-1.2):1, so that the inert aluminum oxide in the waste hydrogenation catalyst can be fully converted during the sodium roasting process, and the nickel can be completely released, which is beneficial to the subsequent nickel recovery; when this molar ratio is low, it is easy to cause insufficient Na2O and incomplete reaction; when this molar ratio is high, it is easy to cause excessive sodium to exist in the roasted clinker, affecting subsequent treatment and causing waste of resources.

[0022] As a preferred technical solution of the present invention, the water content of the raw slurry is 35wt% to 40wt%, for example, 35wt%, 35.5wt%, 36wt%, 36.5wt%, 37wt%, 37.5wt%, 38wt%, 38.5wt%, 39wt%, 39.5wt% or 40wt%, etc., but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0023] Excessive increase in the water content in the raw material slurry of the present invention will increase the energy consumption of roasting.

[0024] The present invention preferably controls the dosage by calculating the molar ratio of Na2O in the sodium carbonate to Na2O in the sodium aluminate solution to be (2.5-6):1 (ie A:B) under the conditions that the concentration of the sodium aluminate solution and the moisture content of the raw slurry are determined.

[0025] As a preferred technical solution of the present invention, the roasting temperature is 800-1000°C, for example, 800°C, 820°C, 840°C, 860°C, 880°C, 900°C, 920°C, 940°C, 960°C, 980°C or 1000°C, etc., preferably 860-900°C, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0026] As a preferred technical solution of the present invention, the roasting time is 20 to 60 min, for example, 20 min, 23 min, 25 min, 28 min, 30 min, 33 min, 35 min, 38 min, 40 min, 43 min, 45 min, 48 min, 50 min, 53 min, 55 min, 58 min or 60 min, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0027] The present invention further preferably sets the calcination temperature at 860-900° C. Within this temperature range, the inert alumina in the waste hydrogenation catalyst is completely converted, which is beneficial to improving the nickel recovery rate and the purity of nickel oxide in the nickel-rich leaching material; if the temperature is too low, the inert alumina is difficult to convert and the nickel element is difficult to release, resulting in a decrease in the subsequent nickel recovery rate; if the temperature is too high, the experimental operation risk is high, the equipment requirements are high, and the energy consumption is high.

[0028] It is worth noting that the sodium aluminate solution in the method of the present invention contains sodium hydroxide, which is easier to convert the inert alumina in the waste hydrogenation catalyst than sodium carbonate, and can be used as a seed to promote the formation of sodium aluminate product in the roasted clinker; therefore, compared with the prior art, the method of the present invention requires a lower roasting temperature at the same roasting time, and the roasting time required by the present invention is shorter at the same roasting temperature. In short, the recovery and treatment method of the present invention reduces the roasting temperature, shortens the roasting time, reduces the operating risk and damage to the equipment, and realizes the efficient recovery of nickel in the waste hydrogenation catalyst and the recycling of resources under low temperature conditions.

[0029] As a preferred technical solution of the present invention, for the water immersion, the solid-liquid ratio of the clinker to the water for immersion is 1g:(4-20)mL, for example 1g:4mL, 1g:5mL, 1g:6mL, 1g:7mL, 1g:8mL, 1g:9mL, 1g:10mL, 1g:11mL, 1g:12mL, 1g:13mL, 1g:14mL, 1g:15mL, 1g:16mL, 1g:17mL, 1g:18mL, 1g:19mL or 1g:20mL, etc., preferably 1g:(5-8)mL, but is not limited to the listed values, and other values ​​not listed within the above numerical range are equally applicable.

[0030] The present invention further preferably uses a solid-liquid ratio of clinker to water for leaching of 1 g: (5-8) mL, so that the aluminum element in the roasted clinker is completely leached to obtain a sodium aluminate-containing leaching solution and a nickel-rich leaching material, thereby improving the nickel recovery rate and the purity of nickel oxide in the nickel-rich leaching material; if the water for leaching is too little, the aluminum element in the roasted clinker is incompletely leached; if the water for leaching is too much, there is no obvious improvement in the leaching effect, resulting in waste and increased costs.

[0031] As a preferred technical solution of the present invention, the water immersion temperature is 50-90°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, etc., but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0032] As a preferred technical solution of the present invention, the immersion time is 10 to 40 minutes, for example, 10 minutes, 13 minutes, 15 minutes, 18 minutes, 20 minutes, 23 minutes, 25 minutes, 28 minutes, 30 minutes, 33 minutes, 35 minutes, 38 minutes or 40 minutes, but is not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable.

[0033] As a preferred technical solution of the present invention, the sodium aluminate-containing leachate is reused as the sodium aluminate solution and / or processed as a raw material for aluminum-containing products, and the aluminum-containing products include aluminum hydroxide or pseudo-boehmite.

[0034] A small portion of the sodium aluminate-containing leachate obtained by the present invention can be recycled, which is beneficial to saving the amount of sodium carbonate and saving costs. Most of the sodium aluminate-containing leachate can be used as a raw material to further extract the aluminum element therein to prepare aluminum-containing products such as pseudo-boehmite (γ-AlOOH), thereby realizing the high-value utilization of valuable elements in the waste hydrogenation catalyst.

[0035] As a preferred technical solution of the present invention, the components of the nickel-rich leaching material include nickel oxide.

[0036] As a preferred technical solution of the present invention, the recycling method comprises:

[0037] Provided is a spent hydrogenation catalyst containing NiO and Al2O3, wherein the spent hydrogenation catalyst component further comprises at least one of Na2O, V2O5, SiO2, P2O5, CoO or MoO3.

[0038] First, sodium carbonate and sodium aluminate solution are mixed, wherein the concentration of the sodium aluminate solution is 2-4 mol / L; then the mixed solution is mixed with the waste hydrogenation catalyst, wherein the molar amount of the sodium carbonate in the mixed solution is A, the total molar amount of Na2O in the sodium aluminate solution is B, and the molar amount of Al2O3 in the waste hydrogenation catalyst is C, and A:B=(2.5-6):1, (A+B):C=(0.8-1.2):1 are controlled to obtain a raw slurry having a water content of 35wt%-40wt%;

[0039] The raw material slurry is roasted at 800-1000° C. for 20-60 min under air atmosphere to obtain clinker, and the clinker is then soaked in water, the solid-liquid ratio of the clinker to the soaking water is 1 g: (4-20) mL, the soaking temperature is 50-90° C., the time is 10-40 min, and after solid-liquid separation, a sodium aluminate-containing leachate and a nickel-rich leachate containing nickel oxide are obtained;

[0040] The sodium aluminate-containing leaching solution is divided into two parts, one part of which is reused as the sodium aluminate solution, and the other part is processed as a raw material to obtain an aluminum-containing product including aluminum hydroxide or pseudo-boehmite.

[0041] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0042] Compared with the prior art solutions, the present invention has at least the following beneficial effects:

[0043] (1) The recovery and treatment method provided by the present invention uses a combination of sodium carbonate and sodium aluminate in a liquid phase system to perform sodium calcination on the waste hydrogenation catalyst. The sodium carbonate and sodium aluminate work synergistically to achieve the conversion of the inert aluminum oxide in the waste hydrogenation catalyst under relatively low temperature and isothermal conditions, and the inert aluminum oxide (β-Al2O3 or α-Al2O3) phase is converted into the sodium aluminate (NaAlO2) phase, releasing the nickel element wrapped therein. The entire calcination process does not require strong acid or alkali, the calcination temperature is low, the calcination time is short, and the operation risk and damage to the equipment are reduced. Then, water leaching is used to fully leach the aluminum element in the calcined clinker, and a nickel-rich leached material is obtained after solid-liquid separation, thereby achieving separation and recovery.

[0044] (2) The recovery and treatment method provided by the present invention achieves a nickel oxide content or purity of ≥90% in the nickel-rich material by further controlling the amount and ratio of the materials in each step and matching the preferred temperature and time parameters;

[0045] (3) In the recovery and treatment method of the present invention, the obtained sodium aluminate-containing leaching solution can be returned to the entire process of mixing, roasting and water leaching for recycling, which effectively reduces the cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 It is a schematic flow chart of the method for recovering and treating the waste hydrogenation catalyst of Example 1. DETAILED DESCRIPTION

[0047] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0048] It should be clear to those skilled in the art that the embodiments are only intended to help understand the present invention and should not be considered as specific limitations of the present invention.

[0049] The waste hydrogenation catalyst used in the following examples and comparative examples is derived from a petroleum refining process. The waste hydrogenation catalyst is ground through a 100-mesh sieve, and the material under the sieve is taken as a raw material for the waste hydrogenation catalyst used in the experiment. The main components of the raw material and their mass percentages are measured as shown in Table 1.

[0050] Table 1

[0051] Components <![CDATA[Al2O3]]> NiO <![CDATA[Na2O]]> <![CDATA[V2O5]]> <![CDATA[SiO2]]> <![CDATA[P2O5]]> CoO <![CDATA[MoO3]]> content 75.6wt% 10.9wt% 6.9wt% 2.7wt% 1.8wt% 1.5wt% 0.2wt% 0.4wt%

[0052] Example 1

[0053] This embodiment provides a method for recycling and treating waste hydrogenation catalysts. Figure 1 As shown, the recycling method comprises:

[0054] 80 mL of sodium aluminate solution and 80.6 g of sodium carbonate are uniformly mixed to obtain a mixed solution, wherein the concentration of the sodium aluminate solution is 2 mol / L, and then the mixed solution is mixed with 100 g of the waste hydrogenation catalyst, so that the molar amount of the sodium carbonate is A, the total molar amount of Na2O in the sodium aluminate solution is B, the molar amount of Al2O3 in the waste hydrogenation catalyst is C, A:B=6:1, (A+B):C=1.2:1, and a raw slurry with a water content of 39 wt% is obtained;

[0055] The raw material slurry is roasted at 1000°C for 20 minutes under an air atmosphere to obtain clinker, and then 100g of the clinker is weighed and soaked in pure water at 90°C for 10 minutes, and the solid-liquid ratio of the clinker to the soaking water is 1g:5mL. After filtration, a sodium aluminate-containing leachate and a nickel-rich leachate containing components including nickel oxide are obtained, and part of the obtained sodium aluminate-containing leachate can be reused as the sodium aluminate solution.

[0056] Example 2

[0057] This embodiment provides a method for recovering and treating a waste hydrogenation catalyst. In the method, the calcination temperature is adjusted from 1000°C to 860°C, and the calcination time is adjusted from 20 min to 50 min. Except for the above, other conditions are exactly the same as those in Example 1.

[0058] Example 3

[0059] This embodiment provides a method for recovering and treating a waste hydrogenation catalyst. In the recovery and treating method, the leaching temperature is adjusted from 90° C. to 70° C., and the leaching time is adjusted from 10 min to 30 min. Except for the above, other conditions are exactly the same as those in Example 1.

[0060] Example 4

[0061] This embodiment provides a method for recovering and treating a waste hydrogenation catalyst. In the method, the calcination temperature is adjusted from 1000° C. to 600° C. Except for the above, other conditions are exactly the same as those in Example 1.

[0062] Example 5

[0063] This embodiment provides a method for recovering and treating a waste hydrogenation catalyst. In the method, the calcination time is adjusted from 20 min to 5 min. Except for the above, other conditions are exactly the same as those in Example 1.

[0064] Example 6

[0065] This embodiment provides a method for recycling a waste hydrogenation catalyst, wherein the recycling method controls A:B=6:1 and adjusts the ratio of (A+B):C from 1.2:1 to 0.7:1. Except for the above, other conditions are exactly the same as those in Example 1.

[0066] Example 7

[0067] This embodiment provides a method for recycling a waste hydrogenation catalyst, wherein the recycling method controls A:B=6:1 and adjusts the ratio of (A+B):C from 1.2:1 to 1.4:1. Except for the above, other conditions are exactly the same as those in Example 1.

[0068] Example 8

[0069] This embodiment provides a method for recycling a waste hydrogenation catalyst, wherein the concentration of the sodium aluminate solution is changed to 4 mol / L, so that the ratio of A:B is adjusted from 6:1 to 2.5:1. Except for the above, the other conditions are exactly the same as those in Example 1.

[0070] Example 9

[0071] This embodiment provides a method for recycling a waste hydrogenation catalyst, wherein the ratio of sodium aluminate solution to sodium carbonate is changed so that the ratio of A:B is adjusted from 6:1 to 5.6:1, and the moisture content of the raw slurry is adjusted from 39wt% to 45wt%. Except for the above, other conditions are exactly the same as those in Example 1.

[0072] Example 10

[0073] This embodiment provides a method for recovering and treating a waste hydrogenation catalyst. In the method, the leaching time is adjusted from 10 min to 5 min. Except for the above, other conditions are exactly the same as those in Example 1.

[0074] Comparative Example 1

[0075] This comparative example provides a method for recovering and treating a waste hydrogenation catalyst. The recovery and treatment method does not use a sodium aluminate solution, and the total molar amount of Na2O in the sodium aluminate solution is replaced by an equal molar amount of sodium carbonate. Except for the above, other conditions are exactly the same as those in Example 1.

[0076] Comparative Example 2

[0077] This comparative example provides a method for recovering and treating a waste hydrogenation catalyst. The method does not use sodium carbonate, but replaces the sodium carbonate with an equimolar amount of sodium bicarbonate. Except for the above, other conditions are exactly the same as those in Example 1.

[0078] Comparative Example 3

[0079] This comparative example provides a method for recovering and treating a waste hydrogenation catalyst. The method does not use sodium carbonate, but replaces the sodium carbonate with an equimolar amount of sodium hydroxide. Except for the above, other conditions are exactly the same as those in Example 1.

[0080] The nickel-rich leaching materials obtained in the examples and comparative examples were tested for nickel oxide content (purity). The detection method was based on HJ751-2015 "Determination of Nickel and Copper in Solid Waste by Flame Atomic Absorption Spectrophotometry". The results are shown in Table 2.

[0081] Table 2

[0082]

[0083]

[0084] It can be seen from Table 2 that:

[0085] (1) Based on Examples 1 to 3, it can be seen that the method of the present invention uses sodium carbonate and sodium aluminate to form a liquid phase system to sodium-treat the waste hydrogenation catalyst, which is beneficial to promote the conversion of inert aluminum oxide in the waste hydrogenation catalyst into a sodium aluminate-containing clinker that is easily leached in water. After solid-liquid separation, a nickel-rich leached material can be obtained to achieve separation and recovery.

[0086] (2) During the recovery and treatment process of the present invention, nickel oxide is solid in the waste hydrogenation catalyst. After the sodium-fermented calcined sodium aluminate clinker and leached with water, the solution is strongly alkaline, and all the nickel enters the leaching residue (nickel-rich leaching material). Therefore, the recovery rate can reach 100%. However, if the aluminum oxide is not completely converted, the inert aluminum oxide is difficult to convert or not completely converted during the calcination process, and eventually enters the leaching residue, resulting in a relatively low nickel oxide content (purity) in the nickel-rich leaching material, that is, there is a difference in content or purity.

[0087] (3) It can be seen from Example 1 and Examples 6 to 7 that the present invention can make sodium carbonate and sodium aluminate play a better synergistic role by further optimizing the ratio of (A+B):C, so that the inert aluminum oxide in the waste hydrogenation catalyst is easier to convert, the leaching of aluminum element is promoted, and the content or purity of nickel oxide in the nickel-rich leaching material is increased; when the ratio value of (A+B):C is outside the scope of the present invention, it will lead to incomplete conversion of the inert aluminum oxide or cause waste of sodium carbonate.

[0088] (4) Based on Example 1 and Example 8, it can be seen that increasing the concentration of the sodium aluminate solution is beneficial to the full conversion of the inert aluminum oxide.

[0089] (5) It can be seen from Example 1 and Example 9 that increasing the moisture content of the raw material slurry will affect the roasting effect and increase the energy consumption. The actual appropriate roasting time should be extended.

[0090] (6) It can be seen from Example 1 and Example 10 that when the leaching time is insufficient, the roasted clinker cannot be completely leached, resulting in a relatively low nickel oxide content in the nickel-rich leached material.

[0091] (7) Based on Example 1 and Comparative Examples 1 to 3, it can be seen that Comparative Example 1 does not add sodium aluminate, and the effect is worse than that of Example 1. If the nickel oxide content needs to be increased, the roasting time needs to be extended; the roasting effect of adding sodium carbonate is better than the roasting effect of using an equal amount of sodium bicarbonate in Comparative Example 2; the use of strong alkali sodium hydroxide in Comparative Example 3 will cause corrosion to the equipment and is costly.

[0092] From the above, it can be seen that the recovery and treatment method of the present invention uses a combination of sodium carbonate and sodium aluminate to sodium-ferment the waste hydrogenation catalyst in a liquid phase, dissociates the inert alumina in the waste hydrogenation catalyst to release nickel, and then leaches out aluminum and other elements through water leaching to obtain a nickel-rich material, thereby achieving separation and recovery, and achieving efficient recovery and resource recycling of the waste hydrogenation catalyst under shorter and milder process conditions.

[0093] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0094] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0095] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for recovering and treating a waste hydrogenation catalyst, characterized in that: The recycling method comprises: A waste hydrogenation catalyst is provided, the waste hydrogenation catalyst, sodium carbonate and sodium aluminate solution are mixed to obtain a raw material slurry, the raw material slurry is roasted to obtain a clinker, and the clinker is soaked in water to obtain a sodium aluminate-containing leaching solution and a nickel-rich leaching material.

2. The method for recycling waste hydrogenation catalyst according to claim 1, characterized in that: The recycling method comprises: Firstly, a sodium aluminate solution is mixed with sodium carbonate to obtain a mixed solution, and then the mixed solution is mixed with the waste hydrogenation catalyst to obtain the raw material slurry; Preferably, for the mixing, the concentration of the sodium aluminate solution is 2 to 4 mol / L.

3. The method for recycling waste hydrogenation catalyst according to claim 2, characterized in that: The waste hydrogenation catalyst component also includes at least one of Na2O, V2O5, SiO2, P2O5, CoO or MoO3.

4. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 3, characterized in that: For the mixing, the molar amount of the sodium carbonate is A, the total molar amount of Na2O in the sodium aluminate solution is B, and the molar amount of Al2O3 in the waste hydrogenation catalyst is C, then A:B=(2.5-6):1, (A+B):C=(0.8-1.2):

1.

5. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 4, characterized in that: The water content of the raw material slurry is 35wt% to 40wt%.

6. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 5, characterized in that: The calcination temperature is 800-1000°C, preferably 860-900°C; Preferably, the calcination time is 20 to 60 minutes.

7. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 6, characterized in that: For the water soaking, the solid-liquid ratio of the clinker to the water for soaking is 1 g: (4-20) mL, preferably 1 g: (5-8) mL; Preferably, the water immersion temperature is 50-90°C; Preferably, the immersion time is 10 to 40 minutes.

8. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 7, characterized in that: The sodium aluminate-containing leachate is recycled as the sodium aluminate solution and / or processed as a raw material for aluminum-containing products, and the aluminum-containing products include aluminum hydroxide or pseudo-boehmite.

9. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 8, characterized in that: The components of the nickel-rich leaching material include nickel oxide.

10. The method for recovering and treating a waste hydrogenation catalyst according to any one of claims 1 to 9, characterized in that: The recycling method comprises: Providing a waste hydrogenation catalyst containing NiO and Al2O3, wherein the waste hydrogenation catalyst component also includes at least one of Na2O, V2O5, SiO2, P2O5, CoO or MoO3; First, sodium carbonate and sodium aluminate solution are prepared into a mixed solution, wherein the concentration of the sodium aluminate solution is 2-4 mol / L; then the mixed solution is mixed with the waste hydrogenation catalyst, wherein the molar amount of the sodium carbonate is A, the total molar amount of Na2O in the sodium aluminate solution is B, and the molar amount of Al2O3 in the waste hydrogenation catalyst is C, and A:B=(2.5-6):1, (A+B):C=(0.8-1.2):1 are controlled to obtain a raw slurry with a water content of 35wt%-40wt%; The raw material slurry is roasted at 800-1000° C. for 20-60 min under air atmosphere to obtain clinker, and the clinker is then soaked in water, the solid-liquid ratio of the clinker to the soaking water is 1 g: (4-20) mL, the soaking temperature is 50-90° C., the time is 10-40 min, and after solid-liquid separation, a sodium aluminate-containing leachate and a nickel-rich leachate containing nickel oxide are obtained; The sodium aluminate-containing leaching solution is divided into two parts, one part of which is reused as the sodium aluminate solution, and the other part is processed as a raw material to obtain an aluminum-containing product including aluminum hydroxide or pseudo-boehmite.

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