Method for preparing zinc cadmium sulfide catalyst by recovering soot of fuming furnace

Abstract

The invention belongs to the technical field of metallurgy, and discloses a method for preparing a zinc cadmium sulfide catalyst by recovering smoke ash of a fuming furnace, which comprises the following steps: carrying out water washing pretreatment on the smoke ash of the fuming furnace; the pretreated smoke ash of the fuming furnace is leached through sulfuric acid, and a leaching solution is obtained after heating and stirring; adjusting the pH value of the leaching solution, adding an impurity removal agent, and fully stirring to obtain a purified solution; adding a surfactant into the purified liquid, and fully stirring to obtain a solution A; preparing a sulfur source solution with a certain concentration, slowly pouring the sulfur source solution into the solution A, and uniformly stirring to obtain a solution B; dropwise adding an ammonia water solution into the solution B until a large amount of white to light yellow sol is generated in the reactor; and carrying out ultrasonic treatment on the obtained sol, washing, filtering and drying to obtain the zinc cadmium sulfide catalyst. According to the technical scheme, the problems that an existing fuming furnace is large in ash recovery difficulty and low in recovery value are solved.

Description

Technical Field

[0001] The invention belongs to the technical field of metallurgy, and in particular relates to a method for preparing a zinc cadmium sulfide catalyst by recycling ash from a fuming furnace. Background Art

[0002] With the development of the metallurgical industry, the output of zinc-containing secondary resources has shown a significant growth trend. In contrast, the serious lack of utilization of this resource not only causes waste of valuable metals, but also poses a potential threat to the environment. Therefore, taking the recovery of secondary zinc-containing resources and increasing product added value as the future development direction is the only way to promote industrial transformation and upgrading and achieve green development. Among the many recycling methods, catalysts have the advantages of low product purity requirements and recyclability. The preparation of catalysts using zinc-containing secondary resources as raw materials is expected to increase the recycling value of such resources and solve the problems of complex composition and low utilization rate of zinc-containing solid waste. Summary of the invention

[0003] In order to solve the problems existing in the prior art, the purpose of the present invention is to provide a method for recovering zinc-cadmium sulfide catalyst from fuming furnace ash. The present invention can effectively recover zinc and cadmium ions in the fuming furnace ash and prepare zinc-cadmium sulfide catalyst, thereby improving the recovery value of zinc-containing solid waste.

[0004] In order to achieve the above objectives, the technical solutions adopted in this paper are as follows: A method for recovering fuming furnace ash to prepare zinc cadmium sulfide catalyst comprises the following steps: The fuming furnace ash is pre-treated by water washing to remove soluble impurities, wherein the soluble impurities include soluble impurities of iron, chlorine and calcium; The pre-treated fuming furnace ash is washed with sulfuric acid to leach out zinc and cadmium ions in the fuming furnace ash, and then solid-liquid separation is performed to obtain a leachate; The leachate is adjusted to be acidic, and then purified by using an impurity removal agent to remove the impurity copper ions in the leachate, and after the purification is completed, solid-liquid separation is performed to obtain a purified liquid; The purified liquid is mixed with a surfactant to obtain a solution A; Adding a sulfur source solution to the solution A and mixing well to obtain a solution B; Adding an aqueous ammonia solution to the solution B until a white to light yellow sol is generated in the reaction system; The sol is subjected to ultrasonic treatment to remove impurities in the sol, and then solid-liquid separation, washing and drying are performed to obtain a zinc cadmium sulfide catalyst.

[0005] Preferably, the water washing pretreatment of the fuming furnace ash comprises: The fuming furnace ash is mixed with deionized water at 70-90 °C at a liquid-to-solid ratio of (4-6):1, and then stirred for 1-3 hours, and then solid-liquid separation is performed. The washed slag obtained by solid-liquid separation is dried at 60-80 °C for 4-6 hours to obtain the fuming furnace ash after water washing pretreatment.

[0006] Preferably, the process of washing the pre-treated fuming furnace ash with sulfuric acid leaching water comprises: The fuming furnace fly ash after water washing pretreatment is added into 250-270 g / L sulfuric acid solution at a liquid-to-solid ratio of (7-9):1, stirred at 70-90 °C for 2-3 h, and then solid-liquid separation is performed to obtain a leachate.

[0007] Preferably, the pH value of the leaching solution is adjusted to 1.5-2.5 using sodium hydroxide solution and sulfuric acid solution.

[0008] Preferably, 0.0005-0.005 mol / L Na2S·9H2O is added to the leaching solution for purification. During purification, the solution is stirred at 25-35°C for 5-15 min, and purification is completed.

[0009] Preferably, when the purified liquid is mixed with the surfactant, a hexadecyltrimethylammonium bromide surfactant is added to the purified liquid to activate the purified liquid, and stirred at room temperature for 25-35 min to obtain the solution A, wherein the addition ratio of hexadecyltrimethylammonium bromide is 0.9-1.1 g / L.

[0010] Preferably, the sulfur source solution is 1.4-1.6 mol / L sodium sulfide solution, thiourea solution or thioacetamide solution; The sulfur source solution is added to the solution A and stirred for 4-6 minutes to obtain the solution B.

[0011] Preferably, a 1+1 ammonia solution is added to solution B until a white to light yellow sol is generated in the reaction system.

[0012] Preferably, the sol is ultrasonicated at an ultrasonic power of 60-100 W for 10-20 min, and then solid-liquid separation is performed, and the separated solid product is repeatedly washed with deionized water and alcohol until neutral, and then dried at 50-70° C. for 4-6 h to obtain the zinc cadmium sulfide catalyst.

[0013] The present invention also provides a zinc cadmium sulfide catalyst, which is prepared by the method of the present invention as described above.

[0014] The technical solution of the present invention has the following beneficial effects: The method for preparing zinc-cadmium sulfide catalyst by recycling fuming furnace ash of the present invention can effectively recycle the valuable metal elements zinc and cadmium in the fuming furnace ash, and use them as raw materials to prepare catalysts. The zinc-cadmium sulfide type I straddle-type heterogeneous structure is designed, the sulfur source is optimized, and the nanomaterial showing agglomeration phenomenon is synthesized by the sol-gel method. At the same time, the higher specific surface area and mesoporous structure can provide more active sites, greatly enhancing the catalytic effect of the material. Its catalytic rate is 13.3 times that of commercial zinc sulfide. It is applied to the catalytic treatment of metallurgical organic mineral processing wastewater, meeting the environmental protection requirement of "treating waste with waste". The utilization value of metallurgical solid waste is improved, and a theoretical reference is provided for the functionalization and resource utilization of complex zinc-containing ash. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a scanning electron microscope image of the zinc cadmium sulfide catalyst obtained in Example 1 of the present invention; Figure 2 This is a scanning electron microscope image of the zinc cadmium sulfide catalyst obtained in Example 2 of the present invention; Figure 3 This is a scanning electron microscope image of the zinc cadmium sulfide catalyst obtained in Example 2 of the present invention. DETAILED DESCRIPTION

[0016] According to the technical solution of the present invention, without changing the essential spirit of the present invention, a person skilled in the art can propose a variety of interchangeable structures and implementations. Therefore, the following specific implementation methods and drawings are only examples of the technical solution of the present invention and should not be regarded as the entirety of the present invention or the limitation of its technical solution.

[0017] The invention provides a method for preparing a zinc cadmium sulfide catalyst by recycling fuming furnace ash. The method comprises the following steps: leaching the fuming furnace ash with sulfuric acid, purifying the leaching liquid, and then adopting a sol-gel method to prepare the zinc cadmium sulfide catalyst, thereby realizing the recovery and resource utilization of valuable metals in zinc-containing solid waste.

[0018] The method for recovering fuming furnace ash to prepare zinc cadmium sulfide catalyst of the present invention specifically comprises the following steps: Step (1): Weigh a certain mass of fuming furnace ash, heat deionized water to 70-90°C, and put the fuming furnace ash into deionized water at a liquid-solid ratio of (4-6):1. After stirring for 1-3 hours, use vacuum filtration equipment to separate the solid and liquid to remove soluble impurities such as iron, chlorine and calcium. Dry the separated washed slag at 60-80°C for 4-6 hours to obtain the fuming furnace ash after water washing pretreatment.

[0019] Step (2): Weigh a certain mass of fumed furnace fly ash after water washing pretreatment and add it to a 250-270 g / L sulfuric acid solution to leach zinc and cadmium ions in the fly ash, wherein the liquid-to-solid ratio of the sulfuric acid solution to the fumed furnace fly ash is (7-9):1, and then stir at 70-90°C for 2-3 hours, then use vacuum filtration equipment to separate the solid and liquid, and dry the separated leaching residue at 60-80°C for 4-6 hours to obtain a leaching solution and leaching residue.

[0020] Step (3): adjusting the pH value of the leaching solution to 1.5-2.5 with a sodium hydroxide solution and a sulfuric acid solution, then adding an impurity remover Na2S·9H2O to the leaching solution at a solid-liquid ratio of 0.0005-0.005 mol / L to remove copper ions, then starting stirring, stirring at 25-35°C for 5-15 min, and then performing liquid-solid separation to obtain a purified liquid and purified slag.

[0021] Step (4): 0.9-1.1 g / L of a surfactant, hexadecyltrimethylammonium bromide, is added to the purified liquid to activate the purified liquid, and then stirring is started at room temperature for 25-35 min.

[0022] Step (5): Slowly pour 1.4-1.6 mol / L sodium sulfide solution, thiourea solution or thioacetamide solution into the liquid obtained in step (4), and stir at room temperature for 4-6 minutes.

[0023] Step (6): Add 1+1 ammonia water dropwise to the mixed solution in step (5) until a large amount of white to light yellow sol is produced.

[0024] Step (7): The sol obtained in step (6) is ultrasonically treated at an ultrasonic power of 60-80 W for 10-20 min, and then solid-liquid separation is performed to fully disperse the sol and the solution to remove impurities in the sol. The separated sol is then washed with deionized water and alcohol for multiple times, and then dried at 50-70 ° C for 4-6 h to obtain a zinc cadmium sulfide catalyst.

[0025] Specifically, the present invention provides an embodiment of a method for recovering fuming furnace ash to prepare zinc cadmium sulfide catalyst as follows: Embodiment 1: The method for preparing zinc cadmium sulfide catalyst by recycling ash from a fuming furnace in this embodiment comprises the following steps: Step (1): weigh 100 g of fuming furnace ash, heat 500 ml of deionized water to 80 °C, add the fuming furnace ash into the deionized water at a liquid-solid ratio of 5:1, stir for 2 h, and then perform solid-liquid separation. Dry the separated washed slag at 70 °C for 5 h to obtain pretreated fuming furnace ash.

[0026] Step (2): weigh 30 g of the pretreated fuming furnace fly ash and add it to 240 ml of 260 g / L sulfuric acid solution, where the liquid-to-solid ratio of the sulfuric acid solution to the fuming furnace fly ash is 8:1; then stir at 80 °C for 2.5 h and perform solid-liquid separation; dry the separated leaching residue at 70 °C for 5 h to obtain a leaching solution and leaching residue.

[0027] Step (3): 150 ml of the leachate obtained in step (2) was taken, and the pH value of the leachate was adjusted to 2.0 using 1+10 sodium hydroxide solution and 1+10 sulfuric acid solution, and 0.00448 mol / L Na2S·9H2O was added to the leachate, and then stirring was started. After stirring at 30°C for 10 min, liquid-solid separation was performed to obtain purified liquid and purified slag.

[0028] Step (4): Measure 150 ml of the purified liquid obtained in step (3), add 1 g / L of hexadecyltrimethylammonium bromide to the purified liquid, and stir at room temperature for 30 minutes.

[0029] Step (5): Prepare 50 ml of 1.5 mol / L thioacetamide solution, slowly pour the thioacetamide solution into 50 ml of the liquid obtained in step (4), and stir at room temperature for 5 min.

[0030] Step (6): adding 1+1 aqueous ammonia dropwise to the solution obtained in step (5) until a large amount of white to light yellow sol is produced, then stop adding; Step (7): The sol obtained in step (6) was ultrasonically treated at an ultrasonic power of 70 W for 15 min, and then solid-liquid separation was performed, and the sol was washed with deionized water and alcohol until neutral, and then dried at 60° C. for 5 h to obtain the zinc cadmium sulfide catalyst of this embodiment.

[0031] Figure 1 This is a scanning electron microscope image of the zinc cadmium sulfide catalyst obtained in Example 1 of the present invention. It can be seen that the zinc cadmium sulfide catalyst morphology shows agglomeration of nanomaterials, and the higher specific surface area and pore structure can provide more active sites.

[0032] 0.06 g of the zinc cadmium sulfide catalyst prepared in this example was added into 100 mL of butyl xanthate wastewater with an initial concentration of 50 mg / L. After 90 min, the butyl xanthate was completely degraded.

[0033] Embodiment 2: The method for preparing zinc cadmium sulfide catalyst by recycling ash from a fuming furnace in this embodiment comprises the following steps: Step (1): weigh 100 g of fuming furnace ash, heat 500 ml of deionized water to 70°C, add the fuming furnace ash into the deionized water at a liquid-solid ratio of 4:1, stir for 1 hour, and then perform solid-liquid separation. Dry the separated washed slag at 60°C for 4 hours to obtain pretreated fuming furnace ash.

[0034] Step (2): weigh 30 g of the pretreated fuming furnace fly ash and add it to 240 ml of 250 g / L sulfuric acid solution, with the liquid-solid ratio of the acid solution to the fuming furnace fly ash being 7:1. Then, stir at 70 °C for 2 h and perform solid-liquid separation. Dry the separated leaching residue at 60 °C for 4 h to obtain a leaching solution and leaching residue.

[0035] Step (3): 150 ml of the leachate obtained in step (2) was measured, and the pH value of the leachate was adjusted to 1.5 using 1+10 sodium hydroxide solution and 1+10 sulfuric acid solution, and 0.0005 mol / L Na2S·9H2O was added to the leachate, and then stirring was started. After stirring at 25°C for 5 min, liquid-solid separation was performed to obtain purified liquid and purified slag.

[0036] Step (4): Measure 150 ml of the purified liquid obtained in step (3), add 0.9 g / L of hexadecyltrimethylammonium bromide to the purified liquid, and stir at room temperature for 25 min.

[0037] Step (5): Slowly pour 50 ml of 1.4 mol / L sodium sulfide solution into 50 ml of the liquid obtained in step (4) and stir at room temperature for 4 min.

[0038] Step (6): adding 1+1 aqueous ammonia dropwise to the solution obtained in step (5) until a large amount of white to light yellow sol is produced, then stop adding; Step (7): The sol obtained in step (6) is ultrasonically treated at an ultrasonic power of 80 W for 10 min, and then solid-liquid separation is performed, and the sol is washed with deionized water and alcohol until neutral, and then dried at 50° C. for 4 h to obtain the zinc cadmium sulfide catalyst of this embodiment.

[0039] Figure 2 This is a scanning electron microscope image of the zinc cadmium sulfide catalyst obtained in Example 2 of the present invention. It can be seen that the zinc cadmium sulfide catalyst exhibits a lamellar structure, has better crystallinity and smaller surface energy than the zinc cadmium sulfide catalyst in Example 1, and has relatively poor adsorption performance for butyl xanthate.

[0040] 0.06 g of the zinc cadmium sulfide catalyst prepared in this example was added to 100 mL of butyl xanthate wastewater with an initial concentration of 50 mg / L. After 4-15 min, the butyl xanthate was completely degraded.

[0041] Embodiment 3: The method for preparing zinc cadmium sulfide catalyst by recycling ash from a fuming furnace in this embodiment comprises the following steps: Step (1): weigh 100 g of fuming furnace ash, heat 500 ml of deionized water to 90 °C, put the fuming furnace ash into the deionized water at a liquid-solid ratio of 6:1, stir for 3 h, and then perform solid-liquid separation. Dry the separated washed slag at 80 °C for 6 h to obtain pretreated fuming furnace ash.

[0042] Step (2): 30 g of the pretreated fuming furnace fly ash is weighed and added into 240 ml of 270 g / L sulfuric acid solution, wherein the liquid-to-solid ratio of the sulfuric acid solution to the fuming furnace fly ash is 9:1. The mixture is then stirred at 90 °C for 3 h and then solid-liquid separation is performed. The separated leaching residue is dried at 80 °C for 6 h to obtain a leaching solution and leaching residue.

[0043] Step (3): 150 ml of the leachate obtained in step (2) was taken, and the pH value of the leachate was adjusted to 2.5 using 1+10 sodium hydroxide solution and 1+10 sulfuric acid solution, and 0.005 mol / L Na2S·9H2O was added to the leachate, and then stirring was started. After stirring at 35°C for 15 min, liquid-solid separation was performed to obtain purified liquid and purified slag.

[0044] Step (4): Measure 150 ml of the purified liquid obtained in step (3), add 1.1 g / L hexadecyltrimethylammonium bromide to the purified liquid, and stir at room temperature for 35 min.

[0045] Step (5): Slowly pour 50 ml of 1.6 mol / L thiourea solution into 50 ml of the liquid obtained in step (4) and stir at room temperature for 6 min.

[0046] Step (6): adding 1+1 aqueous ammonia to the solution obtained in step (5) dropwise until a large amount of white to light yellow sol is produced, then stopping the addition; Step (7): The sol obtained in step (6) was ultrasonically treated at an ultrasonic power of 60 W for 20 min, and then solid-liquid separation was performed, and the sol was washed with deionized water and alcohol until neutral, and then dried at 70° C. for 6 h to obtain the zinc cadmium sulfide catalyst of this embodiment.

[0047] Figure 3 This is a scanning electron microscope image of the zinc cadmium sulfide catalyst obtained in Example 3 of the present invention. It can be seen that the zinc cadmium sulfide catalyst exhibits a lamellar structure, has better crystallinity and smaller surface energy than the zinc cadmium sulfide catalyst in Example 1, and has poorer adsorption performance for butyl xanthate.

[0048] 0.06 g of the zinc cadmium sulfide catalyst prepared in this example was added into 100 mL of butyl xanthate wastewater with an initial concentration of 50 mg / L. After 1597 min, the butyl xanthate was completely degraded.

[0049] The specific embodiments of the present invention are described in detail above. It should be understood that ordinary technicians in the field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by technicians in the technical field through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection of the claims of the present invention.

Claims

1. A method for recovering fuming furnace ash to prepare zinc cadmium sulfide catalyst, characterized in that: The process includes the following: Pre-treatment of fuming furnace ash by water washing to remove soluble impurities; The fuming furnace ash pre-treated by leaching and washing is carried out with sulfuric acid, and then solid-liquid separation is performed to obtain a leachate; The leachate is adjusted to be acidic, and then purified by using an impurity-removing agent to remove copper ions in the leachate, and after purification, solid-liquid separation is performed to obtain a purified liquid; The purified liquid is mixed with a surfactant to obtain a solution A; Adding a sulfur source solution to the solution A and mixing well to obtain a solution B; Adding an aqueous ammonia solution to the solution B until a white to light yellow sol is generated in the reaction system; The sol is subjected to ultrasonic treatment to remove impurities in the sol, and then solid-liquid separation, washing and drying are performed to obtain a zinc cadmium sulfide catalyst.

2. The method for recovering zinc cadmium sulfide catalyst from fuming furnace ash according to claim 1, characterized in that: The composition of water washing pretreatment of fuming furnace ash includes: The fuming furnace ash is mixed with deionized water at 70-90°C at a liquid-solid ratio of (4-6):1, and then stirred for 1-3 hours, and then solid-liquid separation is performed. The washed slag obtained by solid-liquid separation is dried at 60-80°C for 4-6 hours to obtain the fuming furnace ash after water washing pretreatment.

3. The method for recovering zinc cadmium sulfide catalyst from fuming furnace ash according to claim 1, characterized in that: The process of washing the pre-treated fuming furnace ash with sulfuric acid leaching includes: The fuming furnace fly ash after water washing pretreatment is added into a 250-270 g / L sulfuric acid solution at a liquid-solid ratio of (7-9):1, stirred at 70-90 °C for 2-3 h, and then solid-liquid separation is performed to obtain a leachate.

4. The method for preparing zinc cadmium sulfide catalyst by recycling fuming furnace ash according to claim 1, characterized in that: Sodium hydroxide solution and sulfuric acid solution are used to adjust the pH value of the leaching solution to 1.5-2.

5.

5. The method for recovering fuming furnace ash to prepare zinc cadmium sulfide catalyst according to claim 1, characterized in that: Na2S·9H2O is added to the leaching solution at a solid-liquid ratio of 0.0005-0.005 mol / L for purification. During purification, it is stirred at 25-35°C for 5-15 minutes to complete the purification.

6. The method for preparing zinc cadmium sulfide catalyst by recycling fuming furnace ash according to claim 1, characterized in that: When the purified liquid is mixed with the surfactant, hexadecyltrimethylammonium bromide is added to the purified liquid, and stirred at room temperature for 25-35 minutes to obtain the solution A, wherein the addition ratio of hexadecyltrimethylammonium bromide is 0.9-1.1 g / L.

7. The method for preparing zinc cadmium sulfide catalyst by recycling fuming furnace ash according to claim 1, characterized in that: The sulfur source solution is 1.4-1.6 mol / L sodium sulfide solution, thiourea solution or thioacetamide solution; The sulfur source solution is added to the solution A and stirred for 4-6 minutes to obtain the solution B.

8. The method for preparing zinc cadmium sulfide catalyst by recycling fuming furnace ash according to claim 1, characterized in that: Add 1+1 ammonia solution to solution B until a white to light yellow sol is produced in the reaction system.

9. The method for preparing zinc cadmium sulfide catalyst by recycling fuming furnace ash according to claim 1, characterized in that: The sol is ultrasonicated at an ultrasonic power of 60-80 W for 10-20 min, and then solid-liquid separation is performed. The separated solid product is repeatedly washed with deionized water and alcohol until neutral, and then dried at 50-70° C. for 4-6 h to obtain the zinc cadmium sulfide catalyst.

10. A zinc cadmium sulfide catalyst, characterized in that The zinc cadmium sulfide catalyst is prepared by the method according to any one of claims 1-9.

Images