CN107164629A - A kind of aluminium scrap base hydrogenation catalyst processing method based on microwave oxygen-enriched air roasting - Google Patents

Abstract

The invention relates to a method for treating waste aluminum-based hydrogenation catalysts based on microwave oxygen-enriched roasting, and belongs to the fields of environmental protection and resource comprehensive recovery and reuse. In the present invention, the waste aluminum-based hydrogenation catalyst is subjected to deoiling treatment to obtain an oil-free waste aluminum-based hydrogenation catalyst, which is finely ground to a particle size of not more than 400 meshes, and is roasted by microwave under oxygen atmosphere conditions to obtain calcined sand and tail gas, and the tail gas is sequentially passed through Oxidizing solution, deionized water, saturated sodium hydroxide solution are processed to obtain dilute sulfuric acid and sodium carbonate solution, and calcined sand is mainly metal oxide, and dilute sulfuric acid and sodium carbonate solution can be used as the leaching agent of this metal oxide; Waste of the present invention The aluminum-based hydrogenation catalyst can fully oxidize, desulfurize and decarburize, produce zero emission of harmful tail gas, and obtain the leaching agent required for subsequent metal recovery, which realizes the efficient and clean recycling of waste aluminum-based rare metal catalysts.

Description

A method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting

technical field

The invention relates to a method for treating waste aluminum-based hydrogenation catalysts based on microwave oxygen-enriched roasting, and belongs to the fields of environmental protection and resource comprehensive recovery and reuse.

Background technique

Aluminum-based catalyst is a catalyst with γ-Al ₂ O ₃ as the carrier and molybdenum, nickel, vanadium, cobalt, tungsten and other valuable metals or their oxides as active components. It is widely used in the hydrogenation of crude oil in the petrochemical industry Desulfurization refining process to improve oil quality. However, after a certain period of use, the catalyst loses its activity due to metal deposition such as vanadium and carbon disulfide poisoning and cannot be regenerated. The deactivated spent catalyst contains about 15-25% sulfur, 6-10% carbon and a large amount of valuable metals, and the presence of valuable metals mainly in the form of sulfide is not conducive to recovery. If it is directly landfilled without treatment, it will not only cause a waste of resources, but also cause serious pollution to the environment due to the heavy metal elements therein.

At present, there are two main ways to deal with this kind of spent catalyst: one is to directly landfill it as solid waste; the other is to pretreat it by high-temperature fire roasting, degreasing, desulfurization and decarburization to obtain metal oxides, and then use wet method Recovery of valuable metals. The former pollutes soil and groundwater sources, and also causes the loss of rare and precious metal resources such as molybdenum, nickel, vanadium, cobalt, and tungsten. Although the latter does not cause waste of resources, it is difficult to accurately control the relevant conditions due to the direct fire roasting method, which inevitably produces difficult-to-handle composite metal oxides and harmful gases.

Patent CN102367520A discloses a method for comprehensively recovering vanadium from waste aluminum-based catalysts. The waste aluminum-based catalyst is mixed with sodium carbonate in a certain proportion, and roasted at a high temperature of 800-1200°C for 30-60 minutes. The temperature of this method is too high, and the generated molybdenum oxide has been sublimated. Although vanadium is recovered, it causes a waste of molybdenum resources, and the sodium salt will cause corrosion to the equipment and shorten the service life of the equipment.

Patent CN 102042388B discloses a method for recovering metals from waste catalysts containing nickel and molybdenum. It is roasted in the air at 300-550°C for 1-10 hours to remove oily substances, sulfur and carbon in the spent catalysts. The roasting time of this method is too long. long, consumes a lot of energy, and pollutes the air. Patent CN 105274344A mentions a method for recovering vanadium and molybdenum from waste petroleum catalysts. The waste catalyst is ignited in the air at a temperature of 500-650°C to achieve the purpose of removing sulfur and carbon in the waste catalyst. However, due to There is a large amount of crude oil attached to the surface of the spent catalyst, and it is difficult to control the calcination temperature when it is ignited in the air, which will lead to the generation of refractory composite metal oxides (CoMoO ₄ , NiMoO ₄ , NiAl ₂ O ₄ , etc.) in the calcine, which will affect the leaching of subsequent metals Recycle.

Patent CN 105274343A discloses a method for extracting tungsten and nickel from spent petroleum hydrogenation catalysts. Put the spent catalysts that have been ground to a certain particle size in a muffle furnace, and oxidize and roast them at 600-800°C for 3-5 hours , This method takes a long time to roast, consumes a lot of energy, and produces harmful gases that pollute the air.

The above methods for removing sulfur and carbon from spent catalysts have the following disadvantages: a. The treatment time is long, the roasting temperature is high, and the energy consumption is high; b. The treatment temperature is difficult to control, and it is easy to generate complex metal oxides; Roasting equipment requires high corrosion resistance; d. Waste gas is not treated, polluting the environment.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a waste aluminum-based hydrogenation catalyst treatment method based on microwave oxygen-enriched roasting. The formation of metal oxides realizes the harmless comprehensive utilization of roasting tail gas.

The technical scheme of the present invention is: in an oxygen-enriched atmosphere, carry out microwave roasting on the waste aluminum-based hydrogenation catalyst to remove sulfur and carbon in the waste catalyst, realize oxidative desulfurization of valuable metals in the waste catalyst, and obtain easily leached metal Oxides and metal oxides can be recovered by wet leaching, and sulfuric acid and sodium carbonate solutions can be obtained through harmless comprehensive treatment of roasting tail gas. Both sulfuric acid and sodium carbonate solutions can be used as leaching agents for metal oxides.

A method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst;

(2) finely grinding the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is not greater than 400 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain calcined sand and tail gas I;

(4) Tail gas I obtained in step (3) is treated with an oxidative solution to obtain dilute sulfuric acid I and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution and tail gas IV, and tail gas IV is directly discharged;

(7) combining dilute sulfuric acid I obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distilling to obtain concentrated sulfuric acid; evaporating and crystallizing the sodium carbonate solution obtained in step (6) to obtain sodium carbonate crystals;

(8) Add the sodium carbonate crystals obtained in step (7) into deionized water to prepare sodium carbonate solution II with a concentration of 0.5~2.5mol/L, and prepare the concentrated sulfuric acid obtained in step (7) into a dilute solution with a concentration of 1~3mol/L. Sulfuric acid solution III;

(9) Add the calcined sand obtained in step (3) to the sodium carbonate solution II or dilute sulfuric acid solution III obtained in step (8), and react for 2 to 5 hours at a temperature of 75-95°C under stirring conditions to obtain a metal leachate;

In the step (3), the microwave frequency is 2450MHz, the microwave power is 700-2000W, the microwave roasting temperature is 500-700°C, and the roasting time is 15-75min;

The oxidizing solution in the step (4) is hydrogen peroxide or sodium hypochlorite solution, and the mass concentration of the oxidizing solution is 10-30%;

In the step (9), the solid-to-liquid ratio g:ml of calcined sand and sodium carbonate solution II is 1:(5~10), and the solid-liquid ratio g:ml of calcined sand and dilute sulfuric acid solution is 1:(4~9 );

The deoiling treatment method is carried out according to the patent application number 201710033821.9 "A method for removing oily substances on the surface of waste aluminum-based hydrogenation catalyst".

The beneficial effects of the present invention are:

(1) The present invention adopts microwave oxygen-enriched roasting of spent catalysts, which can fully oxidize, desulfurize and decarburize, eliminate harmful exhaust gas, and obtain the leaching agent required for subsequent metal recovery, realizing the efficient, clean and recyclable utilization of waste aluminum-based rare and precious metal catalysts;

(2) The process of the present invention is non-toxic and harmless, low energy consumption, simple process, and low dependence on equipment, and can be completed by a microwave reaction device that can pass through the atmosphere and a corresponding tail gas recovery and treatment device;

(3) The roasted material of this method has been deoiled in advance, and the roasting temperature is easy to control, which effectively avoids the formation of refractory multi-metal composite oxides due to excessive temperature or fluctuations in temperature, and effectively promotes the subsequent leaching of rare and precious metals. Take back;

(4) The method of the present invention realizes the comprehensive recovery and utilization of the roasting tail gas at the same time, reduces the cost and protects the environment.

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

detailed description

The present invention will be described in further detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the content described.

Embodiment 1: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 15.6% and a sulfur content of 6.5%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is no greater than 400 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 700W, the roasting temperature is 500°C, and the roasting time is 15min;

(4) Tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a hydrogen peroxide solution, and the mass concentration of the hydrogen peroxide solution is 30%) to obtain dilute sulfuric acid I and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill and concentrate to obtain concentrated sulfuric acid with a mass concentration of 65%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystal;

(8) adding sodium carbonate crystals obtained in step (7) into deionized water to prepare sodium carbonate solution II with a concentration of 0.5mol/L;

(9) Add the calcined sand obtained in step (3) to the sodium carbonate solution II obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the sodium carbonate solution II is 1: 5, at a temperature of 75 °C, Under the condition of stirring speed of 200r/min, react for 2 h to obtain the leaching solution of metal Mo;

The quality of calcined sand in the present embodiment is 15.248g, and the carbon content rate of calcined sand is 1.23%, and sulfur content rate is 1.63%, and the decarburization rate of oil-removing waste aluminum-based catalyst is calculated as 93.9%, and the desulfurization rate is 83.4%. Sulfuric acid with a mass concentration of 65% and sodium carbonate crystals with a purity of 97.8% can be obtained, and the leaching rate of metal Mo is 96.3%.

Embodiment 2: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 15.6% and a sulfur content of 8.3%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is not greater than 200 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 1200W, the roasting temperature is 550°C, and the roasting time is 30min;

(4) Tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is sodium hypochlorite solution, and the mass concentration of sodium hypochlorite solution is 10%) to obtain dilute sulfuric acid I, dilute hydrochloric acid and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I, dilute hydrochloric acid obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 68%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals;

(8) Add the concentrated sulfuric acid obtained in step (7) to deionized water to prepare dilute sulfuric acid solution III with a concentration of 1 mol/L;

(9) Add the calcined sand obtained in step (3) to the dilute sulfuric acid solution III obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the dilute sulfuric acid solution III is 1: 4, and when the temperature is 80°C, Under the condition of stirring speed of 200 r/min, react for 3 h to obtain the leaching solution of metal Mo, Ni, Co, Al;

The quality of calcined sand in the present embodiment is 14.762g, and the carbon content rate of calcined sand is 1.13%, and sulfur content rate is 1.55%, after calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 94.7%, and the desulfurization rate is 86.2%, Sulfuric acid with a mass concentration of 68% and sodium carbonate crystals with a purity of 95.5% can be obtained. The leaching rates of metals Mo, Ni, Co, and Al are 95.7%, 97.1%, 97.4% and 93.0%, respectively.

Embodiment 3: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 18.2% and a sulfur content of 10.0%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is no greater than 80 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 1700W, the roasting temperature is 700°C, and the roasting time is 45min;

(4) Tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is sodium hypochlorite solution, and the mass concentration of sodium hypochlorite solution is 10%) to obtain dilute sulfuric acid I, dilute hydrochloric acid and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I, dilute hydrochloric acid obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 66%; evaporate and crystallize dilute sulfuric acid solution I obtained in step (6) to obtain sodium carbonate crystals;

(8) Add the concentrated sulfuric acid obtained in step (7) to deionized water to prepare dilute sulfuric acid solution III with a concentration of 2 mol/L;

(9) Add the calcined sand obtained in step (3) to the dilute sulfuric acid solution III obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the dilute sulfuric acid solution III is 1: 7, at a temperature of 95 °C, Under the condition of stirring speed of 200 r/min, react for 4 h to obtain the leaching solution of metal Mo, Ni, Co, Al;

The quality of calcined sand in the present embodiment is 14.436g, and the carbon content rate of calcined sand is 1.07%, and the sulfur content rate is 1.42%. After calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 95.8%, and the desulfurization rate is 89.8%. Sulfuric acid with a mass concentration of 66% can be obtained, sodium carbonate crystals with a purity of 98.2% can be obtained, and the leaching rates of metal Mo, Ni, Co, and Al are 96.9%, 98.7%, 99.1% and 94.6%, respectively.

Embodiment 4: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 20.0% and a sulfur content of 8.3%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is no greater than 150 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 1200W, the roasting temperature is 650°C, and the roasting time is 60min;

(4) Tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a hydrogen peroxide solution, and the mass concentration of the hydrogen peroxide solution is 25%) to obtain dilute sulfuric acid I and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 68%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals ;

(8) Add the sodium carbonate crystals obtained in step (7) into deionized water to prepare sodium carbonate solution II with a concentration of 1.5 mol/L;

(9) Add the calcined sand obtained in step (3) to the sodium carbonate solution II obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the sodium carbonate solution II is 1: 6, at a temperature of 80°C, Under the condition of a stirring speed of 200 r/min, react for 5 h to obtain a leaching solution of metal Mo;

The quality of calcined sand in the present embodiment is 14.538g, and the carbon content rate of calcined sand is 0.83%, and the sulfur content rate is 1.14%, after calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 97.0%, and the desulfurization rate is 90.0%, Can obtain the sulfuric acid that mass concentration is 68%, the sodium carbonate crystal that purity is 97.6%, the leaching rate of metal Mo is 97.2%.

Embodiment 5: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 20.0% and a sulfur content of 6.5%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is not greater than 300 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 700W, the roasting temperature is 700°C, and the roasting time is 75min;

(4) The tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a sodium hypochlorite solution, and the mass concentration of the sodium hypochlorite solution is 10%) to obtain dilute sulfuric acid I, dilute hydrochloric acid and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I, dilute hydrochloric acid obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 68%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals;

(8) Add the sodium carbonate crystals obtained in step (7) into deionized water to prepare sodium carbonate solution II with a concentration of 2.0mol/L;

(9) Add the calcined sand obtained in step (3) to the sodium carbonate solution II obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the sodium carbonate solution II is 1: 8, at a temperature of 85 °C, Under the condition that the stirring speed is 200 r/min, react for 3 hours to obtain the leaching solution of metal Mo;

The quality of calcined sand in the present embodiment is 14.579g, and the carbon content rate of calcined sand is 1.10%, and sulfur content rate is 1.38%. After calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 96.0%, and the desulfurization rate is 84.5%. Sulfuric acid with a mass concentration of 68%, sodium carbonate crystals with a purity of 97.9%, and a leaching rate of metal Mo of 98.4% can be obtained.

Embodiment 6: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 18.2% and a sulfur content of 8.3%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is no greater than 250 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 1500W, the roasting temperature is 650°C, and the roasting time is 30min;

(4) Tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a hydrogen peroxide solution, and the mass concentration of the hydrogen peroxide solution is 25%) to obtain dilute sulfuric acid I and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 69%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals ;

(8) Add the sodium carbonate crystals obtained in step (7) into deionized water to prepare sodium carbonate solution II with a concentration of 1.8mol/L;

(9) Add the calcined sand obtained in step (3) to the sodium carbonate solution II obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the sodium carbonate solution II is 1: 10, and the temperature is 95°C, Under the condition of stirring speed of 200 r/min, react for 4 h to obtain the leaching solution of metal Mo;

The quality of calcined sand in the present embodiment is 14.245g, and the carbon content rate of calcined sand is 0.73%, and the sulfur content rate is 1.16%, after calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 97.1%, and the desulfurization rate is 90.0%, Sulfuric acid with a mass concentration of 69%, sodium carbonate crystals with a purity of 98.4%, and a leaching rate of metal Mo of 93.9% can be obtained.

Embodiment 7: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 18.2% and a sulfur content of 8.3%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is not greater than 100 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 1500W, the roasting temperature is 650°C, and the roasting time is 75min;

(4) The tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a sodium hypochlorite solution, and the mass concentration of the sodium hypochlorite solution is 10%) to obtain dilute sulfuric acid I, dilute hydrochloric acid and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I, dilute hydrochloric acid obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 70%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals;

(8) Add the concentrated sulfuric acid obtained in step (7) into deionized water to prepare dilute sulfuric acid solution III with a concentration of 2.5mol/L;

(9) Add the calcined sand obtained in step (3) to the dilute sulfuric acid solution III obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the dilute sulfuric acid solution III is 1:8, at a temperature of 80°C, Under the condition of stirring speed of 200r/min, react for 3.5h to obtain the leaching solution of metal Mo, Ni, Co, Al;

The quality of calcined sand in the present embodiment is 13.726g, and the carbon content rate of calcined sand is 0.52%, and sulfur content rate is 0.78%, after calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 98.0%, and the desulfurization rate is 91.7%, Sulfuric acid with a mass concentration of 70% can be obtained, and sodium carbonate crystals with a purity of 97.8% can be obtained. The leaching rate of Mo is 98.6%, the leaching rate of Al is 97.4%, the leaching rate of Co is 99.2%, and the leaching rate of Ni is 99.1%. .

Embodiment 8: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 18.2% and a sulfur content of 6.5%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is no greater than 150 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain calcined sand and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 2000W, the roasting temperature is 600°C, and the roasting time is 45min;

(4) The tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a sodium hypochlorite solution, and the mass concentration of the sodium hypochlorite solution is 10%) to obtain dilute sulfuric acid I, dilute hydrochloric acid and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I, dilute hydrochloric acid obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 69%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals;

(8) adding sodium carbonate crystals obtained in step (7) into deionized water to prepare sodium carbonate solution II with a concentration of 2.5mol/L;

(9) Add the calcined sand obtained in step (3) to the sodium carbonate solution II obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the sodium carbonate solution II is 1:9, at a temperature of 90°C, Under the condition of stirring speed of 200r/min, react for 3.5h to obtain the leaching solution of metal Mo;

The quality of calcined sand in the present embodiment is 13.838g, and the carbon content rate of calcined sand is 0.66%, and sulfur content rate is 0.98%, after calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 97.7%, and the desulfurization rate is 93.2%, Sulfuric acid with a mass concentration of 69% and sodium carbonate crystals with a purity of 98.1% can be obtained; the leaching rate of metal Mo is 92.3%.

Embodiment 9: As shown in Figure 1, a method for treating waste aluminum-based hydrogenation catalyst based on microwave oxygen-enriched roasting, the specific steps are as follows:

(1) Deoiling the waste aluminum-based hydrogenation catalyst to obtain an oil-free waste aluminum-based hydrogenation catalyst, wherein the oil-free waste aluminum-based hydrogenation catalyst has a carbon content of 15.6% and a sulfur content of 10.0%;

(2) Finely grind 20 g of the oil-free waste aluminum-based hydrogenation catalyst obtained in step (1) until the particle size is not greater than 200 mesh;

(3) Under the condition of oxygen atmosphere, the product obtained in step (2) is subjected to microwave roasting to obtain metal oxide and tail gas I, wherein the microwave frequency is 2450MHz, the microwave power is 1200W, the roasting temperature is 700°C, and the roasting time is 60min;

(4) Tail gas I obtained in step (3) is treated with an oxidizing solution (the oxidizing solution is a hydrogen peroxide solution, and the mass concentration of the hydrogen peroxide solution is 20%) to obtain dilute sulfuric acid I and tail gas II;

(5) Tail gas II obtained in step (4) is treated with deionized water to obtain dilute sulfuric acid II and tail gas III;

(6) Tail gas III obtained in step (5) is treated with saturated sodium hydroxide solution to obtain sodium carbonate solution I and tail gas IV, and tail gas IV is directly discharged;

(7) Combine dilute sulfuric acid I obtained in step (4) and dilute sulfuric acid II obtained in step (5), and distill to obtain concentrated sulfuric acid with a mass concentration of 70%; evaporate and crystallize sodium carbonate solution I obtained in step (6) to obtain sodium carbonate crystals ;

(8) Add the concentrated sulfuric acid obtained in step (7) to deionized water to prepare dilute sulfuric acid solution III with a concentration of 3.0 mol/L;

(9) Add the calcined sand obtained in step (3) to the dilute sulfuric acid solution III obtained in step (8), wherein the solid-to-liquid ratio g:ml of the calcined sand to the dilute sulfuric acid solution III is 1:9, at a temperature of 85 °C, Under the condition of stirring speed of 200 r/min, react for 2 h to obtain the leaching solution of metal Mo, Ni, Co, Al;

The quality of calcined sand in the present embodiment is 13.838g, and the carbon content rate of calcined sand is 0.66%, and sulfur content rate is 0.98%, after calculation, the decarburization rate of deoiled waste aluminum-based catalyst is 97.7%, and the desulfurization rate is 93.2%, Sulfuric acid with a mass concentration of 70%, sodium carbonate crystals with a purity of 98.1% can be obtained, and the leaching rates of metals Mo, Ni, Co, and Al are 95.3%, 97.6%, 98.1% and 94.5%, respectively.

Claims (4)

1. a kind of aluminium scrap base hydrogenation catalyst processing method based on microwave oxygen-enriched air roasting, it is characterised in that comprise the following steps that：

（1）Aluminium scrap base hydrogenation catalyst progress deoiling treatment is obtained into oil-free aluminium scrap base hydrogenation catalyst；

（2）By step（1）Gained oil-free aluminium scrap base hydrogenation catalyst is finely ground to particle diameter and is not more than 400 mesh；

（3）Under oxygen ambient conditions, by step（2）Products therefrom carries out microwave calcining and obtains calcining and tail gas I；

（4）Step（3）The oxidized property solution processing of gained tail gas I obtains dilute sulfuric acid I and tail gas II；

（5）Step（4）Gained tail gas II handles through deionized water and obtains dilute sulfuric acid II and tail gas III；

（6）Step（5）Gained tail gas III handles through saturation sodium hydroxide solution and obtains sodium carbonate liquor I and tail gas IV, tail gas IV It is expelled directly out；

（7）By step（4）Gained dilute sulfuric acid I and step（5）Gained dilute sulfuric acid II merges, and distillation obtains the concentrated sulfuric acid；By step（6） The evaporative crystallization of gained sodium carbonate liquor I obtains crystals of sodium carbonate；

（8）By step（7）Gained crystals of sodium carbonate is added to the sodium carbonate that 0.5 ~ 2.5mol/L of concentration is configured in deionized water Solution II, by step（7）The gained concentrated sulfuric acid is configured to 1 ~ 3mol/L of concentration dilution heat of sulfuric acid III；

（9）By step（3）Gained calcining is added to step（8）In gained sodium carbonate liquor II or dilution heat of sulfuric acid III, in temperature For under 75 ~ 95 DEG C, stirring condition, 2 ~ 5h of reaction obtains metal leachate.

2. the aluminium scrap base hydrogenation catalyst processing method based on microwave oxygen-enriched air roasting according to claim 1, it is characterised in that： Step（3）Middle microwave frequency is 2450MHz, and microwave power is 700 ~ 2000W, and microwave calcining temperature is 500 ~ 700 DEG C, during roasting Between be 15 ~ 75min.

3. the aluminium scrap base hydrogenation catalyst processing method based on microwave oxygen-enriched air roasting according to claim 1, it is characterised in that： Step（4）Middle oxidizing solution is hydrogen peroxide or liquor natrii hypochloritis, and the mass concentration of oxidizing solution is 10 ~ 30%.

4. the aluminium scrap base hydrogenation catalyst processing method based on microwave oxygen-enriched air roasting according to claim 1, it is characterised in that： Step（9）The solid-to-liquid ratio g of middle calcining and sodium carbonate liquor II:Ml is 1:(5 ~ 10), the solid-to-liquid ratio of calcining and dilution heat of sulfuric acid III g:Ml is 1: (4~9).