Method for extracting high-value components from waste copper-bismuth catalyst

Abstract

The invention discloses a method for extracting high-value components from a waste copper-bismuth catalyst. The method comprises the following steps: S1, removing volatile components; s2, oxidizing roasting; s3, sulfuric acid leaching; s4, sulfuric acid leaching liquid treatment; s5, hydrochloric acid leaching; and S6, preparing bismuth oxychloride. According to the method for extracting the high-value components from the waste copper-bismuth catalyst, three elements, namely copper, bismuth and silicon, which account for main components in the waste copper-bismuth catalyst can be respectively extracted in a compound form for recycling by adopting a set of technological process, so that the resource utilization rate can be increased, and the consumption of auxiliary materials and energy sources adopted by the process is relatively low; the method is high in treatment capacity, various products can serve as chemical raw materials to be applied to various fields, accordingly, efficient recycling of resources is achieved, and the method can be further suitable for the industry of recycling high-value components of waste copper-bismuth catalysts at the present stage.

Description

Technical Field

[0001] The invention relates to the technical field of hazardous waste disposal and utilization, and in particular to a method for extracting high-value components from waste copper-bismuth catalysts. Background Art

[0002] 1,4-Butynediol (BYD) is an intermediate in the production of 1,4-butanediol (BDO). The current mainstream method for producing BYD is the synthesis of methanol and acetylene under the action of copper-bismuth catalysts. The increase in the demand for BDO indirectly leads to a significant increase in the use of copper-bismuth catalysts. A large amount of carbon-containing byproducts will remain in the copper-bismuth catalyst during the catalytic production process. These substances accumulate on the surface of the copper-bismuth catalyst, blocking the catalyst pores and causing the catalyst to deactivate; and mechanical wear, carrier shedding, and catalytic material loss during the production process will cause catalyst deactivation. When the deactivated copper-bismuth catalyst is regenerated, its catalytic performance decreases significantly with the increase in the number of regenerations. The copper-bismuth catalyst contains high-value-added copper and bismuth elements. For the discarded copper-bismuth catalyst that has lost its regeneration value, the high-value-added components must be extracted before the resource recycling can be realized.

[0003] Among the existing patents, the publication number is CN201910870435 - "Method for treating waste containing acetylide", which includes the following steps: (1) fully mixing the material with the porous structure material and water, and adjusting the pH; (2) removing part of the water; (3) detecting the catalytic performance; (4) if the catalytic performance is greater than 90%, it is returned to production after being roasted at 300-850°C in an incinerator; (5) if the catalytic performance is less than 90%, it is roasted at 300-1500°C in an incinerator to obtain the metal. The patent's description of the extraction of high-value components (Example 5, the remaining examples are regeneration or other non-copper-bismuth catalysts) is flawed. The patent uses copper-bismuth alloy as a product, but does not actually separate the two metal elements with the highest added value in the catalyst. Instead, it uses a mixture as a product; it does not describe what kind of reducing agent is used when roasting at 1200°C. Even if the catalyst contains some carbon, how to ensure that the residual carbon can reduce the metal to a recovery rate of more than 96% is too coincidental; the roasting process is an oxidation process of organic matter and carbon, which will result in a large amount of carbon dioxide emissions, which is contrary to my country's current low-carbon economy; 51% of water is still retained after dehydration. Since a large amount of formaldehyde and 1,4-butynediol remain in the discarded copper-bismuth catalyst, the patent does not describe how to ensure their complete combustion during roasting or how to avoid formaldehyde vapor explosion.

[0004] The publication number is CN201910712564 - "Treatment method and application of waste catalyst containing acetylene copper", which includes the following steps: (1) the catalyst is mixed with a surfactant and water to form a slurry; (2) the slurry is sprayed into a fluidized bed incinerator; (3) the solid obtained after incineration is mixed with water; (4) the solid-liquid mixture is separated by sedimentation, and the solid phase is a metal oxide. The description of the extraction of high-value components in this patent is defective, because the copper-bismuth catalyst is based on silicon dioxide, and the reaction steps of this patent do not remove silicon dioxide, so the final product is mainly silicon dioxide, a small amount of copper-bismuth oxide, and a wet material composed of free water. It is a complex mixture, and the high-value elements are not separated; there is no description of the components contained in the product and the corresponding purity.

[0005] At present, the existing technologies and related patents for the extraction and utilization of high-value components of waste copper-bismuth catalysts all use high-temperature roasting to remove moisture and organic matter to obtain copper-bismuth alloys. This method has low resource utilization efficiency, high energy consumption, and extremely limited application range. It is not suitable for the current industry of recycling high-value components of waste copper-bismuth catalysts. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the existing defects and provide a method for extracting high-value components from waste copper-bismuth catalysts. By adopting a set of process flows, the three elements of copper, bismuth and silicon, which are the main components of the waste copper-bismuth catalysts, can be extracted in the form of compounds for recycling and reuse, which can improve resource utilization. In addition, the auxiliary materials and energy consumption used in this process are low, and the processing capacity is large. Various products can be used as chemical raw materials in various fields, thereby realizing efficient recycling of resources. It can also be applicable to the industry of recycling high-value components of waste copper-bismuth catalysts at this stage, which can effectively solve the problems in the background technology.

[0007] To achieve the above object, the present invention provides the following technical solution: a method for extracting high-value components from waste copper-bismuth catalysts, comprising the following steps: S1. Removing volatiles: heating the waste copper-bismuth catalyst slurry to remove volatiles, condensing and liquefying the volatiles for recovery, and removing the volatiles to form solid slag; S2, oxidative roasting: the solid slag is fully oxidatively roasted in an oxidative roasting furnace to obtain roasted sand; S3, sulfuric acid leaching: roasted sand and dilute sulfuric acid are stirred and heated to react, and the leaching residue and leachate are obtained by filtration; S4, sulfuric acid leaching solution treatment: the filtrate is heated and evaporated to concentrate, naturally cooled and crystallized, and filtered to obtain the copper sulfate pentahydrate product, and the filtrate is returned to leach the next batch of roasted sand; S5, hydrochloric acid leaching: the leaching residue obtained by sulfuric acid leaching is stirred and heated with dilute hydrochloric acid to react, and the leaching residue and leaching liquid are obtained by filtration. The leaching residue is washed with water and then dried to obtain a crude silicon dioxide product; S6. Preparation of bismuth oxychloride: sodium dodecyl sulfate is added to the hydrochloric acid leaching solution and stirred evenly, sodium hydroxide solution is added dropwise, and a filter cake is obtained by filtering. After washing and drying, a nano-grade bismuth oxychloride product is obtained.

[0008] As a preferred technical solution of the present invention, S1, removing volatiles is specifically as follows: take an appropriate amount of waste copper-bismuth catalyst slurry and pour it into a two-mouth flask, place an electric-controlled digital display heater at the bottom of the flask, and place an asbestos net between the heater and the flask to evenly disperse the heat; insert a thermometer into one of the two mouths of the flask to measure the internal gas temperature, and connect the serpentine condenser to the other mouth, and connect the outlet of the condenser to a conical flask to receive the liquid formed after the condensation and liquefaction of the volatiles. Turn on the cooling water of the serpentine condenser, turn on the heater to slowly heat up, the heating rate is 0-9℃ / min, and the thermometer in the flask shows that obvious volatiles begin to be produced at about 90℃. At this time, reduce the heating rate to 0-3℃ / min until there is no obvious volatiles in the flask. At this time, the thermometer in the flask shows about 175℃, then stop heating, and pour out the solid slag.

[0009] As a preferred technical solution of the present invention, S2, oxidation roasting, is specifically as follows: pouring the solid slag into a corundum crucible, placing it into an oxidation roasting furnace, and performing sufficient oxidation roasting at 450-550° C. for 2-8 hours.

[0010] As a preferred technical solution of the present invention, S3, sulfuric acid leaching is specifically as follows: take out the roasted sand after oxidative roasting, mix it with deionized water at a liquid-to-solid ratio of 3-10:1, add concentrated sulfuric acid until the pH is stabilized at 0-1, then transfer it into a three-necked flask, heat it to 90°C in an oil bath, stir and leach for 2-5h, monitor the pH during the process, if it is higher than 1, then add concentrated sulfuric acid again to return the pH to 0-1, and filter after the leaching to obtain sulfuric acid leaching residue and sulfuric acid leachate.

[0011] As a preferred technical solution of the present invention, S4, sulfuric acid leachate treatment is specifically: the sulfuric acid leachate is poured into a beaker, heated and evaporated to concentrate to 30-50% of the original leachate volume, and then the concentrated sulfuric acid leachate is poured into a polytetrafluoroethylene beaker and naturally cooled to room temperature, filtered to obtain a copper sulfate pentahydrate product, and the filtrate is used as a sulfuric acid leaching mother liquor for leaching the next batch of roasted sand.

[0012] As a preferred technical solution of the present invention, S5, hydrochloric acid leaching is specifically as follows: the sulfuric acid leaching residue is rinsed with deionized water until it is nearly neutral, mixed with a 1.5 mol / L hydrochloric acid solution according to a liquid-to-solid ratio of 3-5:1, stirred evenly and transferred into a three-necked flask, and the pH is monitored to see if it is greater than 0.5. If it is higher than 0.5, concentrated hydrochloric acid is added dropwise to maintain the pH at 0-0.5, and the oil bath is heated to 30-50°C, stirred and leached for 1-6h, and the hydrochloric acid leaching solution and hydrochloric acid leaching residue are filtered to obtain the hydrochloric acid leaching solution and the hydrochloric acid leaching residue, and the hydrochloric acid leaching residue is washed with water and then dried to obtain a crude silicon dioxide product.

[0013] As a preferred technical solution of the present invention, S6, preparing bismuth oxychloride is specifically as follows: pouring the hydrochloric acid leachate into a three-necked flask, adding sodium dodecyl sulfate at 0.1% of the mass of the leachate, stirring evenly at room temperature, slowly adding 0.5 mol / L sodium hydroxide solution while stirring, stopping the dropping after the pH value stabilizes at 1 after real-time monitoring, continuing to stir for 5 minutes and then filtering, washing the filter cake with water, and drying it at 100°C for 5 hours to obtain a nano-scale bismuth oxychloride product.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. The method for extracting high-value components from waste copper-bismuth catalysts exemplified in the present invention only uses one set of production processes, which can extract the three elements of copper, bismuth and silicon, which are the main components of the waste copper-bismuth catalyst, in the form of compounds to form high-purity products, so that more than 95% of the high-value components can be recovered and recycled.

[0015] 2. The method for extracting high-value components from waste copper-bismuth catalysts exemplified in the present invention can directly process the waste copper-bismuth catalyst slurry unloaded from the BYD slurry bed equipment without any pretreatment; and the main steps of the present invention do not involve ultra-high temperature roasting, high temperature and high pressure reaction processes, which can greatly simplify the process flow.

[0016] 3. The method of extracting high-value components from waste copper-bismuth catalysts exemplified in the present invention can safely separate the organic matter remaining in the catalyst and safely decompose the residual copper acetylene without causing an explosion. The process operation is highly safe, thereby avoiding explosion accidents.

[0017] 4. The method for extracting high-value components from waste copper-bismuth catalysts exemplified in the present invention realizes the comprehensive recovery of high-value components of waste copper-bismuth catalysts, and the product quality and recovery rate are high. The purity of copper sulfate pentahydrate (in terms of CuSO 4 •5H 2 O) ≥98%, crude silicon dioxide (SiO 2 The purity of nano bismuth oxychloride (in terms of BiOCl) is ≥94%, and the purity of nano bismuth oxychloride (in terms of BiOCl) is ≥99%, both of which meet the market standards. The auxiliary material and energy consumption are low, the processing capacity is large, and it is suitable for large-scale production.

[0018] 5. The method of extracting high-value components from waste copper-bismuth catalysts exemplified in the present invention, and the various products of the invention can be used as chemical raw materials in various fields. In particular, bismuth oxychloride, as a new type of semiconductor photocatalytic material, can be used in sewage treatment, solar power generation, hydrogen production, anti-cancer and sterilization, etc., to achieve efficient recycling of resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] A method for extracting high-value components from waste copper-bismuth catalysts comprises the following steps: S1. Remove volatiles: Take an appropriate amount of waste copper-bismuth catalyst slurry and pour it into a two-necked flask. Place an electric-controlled digital display heater at the bottom of the flask, and place an asbestos mesh between the heater and the flask to evenly disperse the heat. Insert a thermometer into one of the two-necked flask ports to measure the internal gas temperature, and connect the other port to a serpentine condenser. The outlet of the condenser is connected to a conical flask to receive the liquid formed after the volatiles are condensed and liquefied. Open the serpentine condenser cooling water, turn on the heater to slowly heat up, the heating rate is 0-9℃ / min, when the thermometer in the flask shows about 90℃, obvious volatiles begin to be produced, then reduce the heating rate to 0-3℃ / min, until there is no obvious volatiles in the flask, the thermometer in the flask shows about 175℃, then stop heating and pour out the solid slag; the heating rate and material temperature range must be strictly kept within the specified range, the heating rate can ensure that the volatiles are safely and steadily separated from the solid slag, and can ensure that the acetylene copper remaining on the catalyst is slowly decomposed, otherwise if the heating rate is too fast, it will cause the acetylene copper to explode; the main components of the condensate are formaldehyde, 1,4-butynediol and water, which can be returned to the BYD process flow; S2, oxidation roasting: pour the solid slag into a corundum crucible, put it into an oxidation roasting furnace, and perform sufficient oxidation roasting at 450-550°C for 2-8h; S3, sulfuric acid leaching: take out the roasted sand after oxidation roasting, mix it with deionized water at a liquid-to-solid ratio of 3-10:1, add concentrated sulfuric acid until the pH is stable at 0-1, then transfer it to a three-necked flask, heat it to 90°C in an oil bath, stir and leach for 2-5h, monitor the pH during the process, if it is higher than 1, add concentrated sulfuric acid again to return the pH to 0-1, and filter after the leaching to obtain sulfuric acid leaching residue and sulfuric acid leachate; S4, sulfuric acid leachate treatment: pour the sulfuric acid leachate into a beaker, heat and evaporate to concentrate to 30-50% of the original leachate volume, then pour the concentrated sulfuric acid leachate into a polytetrafluoroethylene beaker and naturally cool to room temperature, filter to obtain copper sulfate pentahydrate product, and use the filtrate as sulfuric acid leaching mother liquor for leaching the next batch of roasted sand; S5, hydrochloric acid leaching: rinse the sulfuric acid leaching residue with deionized water until it is nearly neutral, mix it with 1.5 mol / L hydrochloric acid solution at a liquid-to-solid ratio of 3-5:1, stir it evenly and transfer it into a three-necked flask, monitor whether the pH is greater than 0.5, if it is higher than 0.5, add concentrated hydrochloric acid to maintain the pH at 0-0.5, heat it to 30-50°C in an oil bath, stir and leach for 1-6h, filter to obtain the hydrochloric acid leaching solution and hydrochloric acid leaching residue, wash the hydrochloric acid leaching residue with water and then dry it to obtain the crude silicon dioxide product; S6. Preparation of bismuth oxychloride: pour the hydrochloric acid leachate into a three-necked flask, add sodium dodecyl sulfate at 0.1% of the mass of the leachate, stir evenly at room temperature, slowly add 0.5 mol / L sodium hydroxide solution while stirring, stop adding after the pH value is stabilized at 1 after real-time monitoring, continue stirring for 5 minutes and filter, wash the filter cake with water, and dry it at 100°C for 5 hours to obtain the nano-sized bismuth oxychloride product.

[0022] Further, in S1, in the process of removing volatiles, before the material is heated to 90°C, the heating rate is controlled at 0-9°C / min; when heated to 90°C, the heating rate is controlled at 0-3°C / min, and the heating end point temperature is 175°C. The decomposition temperature of acetylene copper is 105-110°C. This step can decompose a small amount of acetylene copper generated by the copper-bismuth catalyst during the catalytic reaction to ensure the safety of subsequent material processing.

[0023] Furthermore, in S2, oxidation roasting, since acetylene copper decomposes to generate a small amount of carbon, this part of carbon will be removed during oxidation roasting. In this process, a very small amount of copper oxide may undergo a reduction reaction to generate copper element, so the oxidation roasting here must ensure sufficient temperature (450-550℃) and time (2-8h).

[0024] The main reaction equations involved in the present invention are as follows: The reaction equation of step (1) is as follows: Cu 2 C 2 =2Cu+2C (acetylene copper decomposition) The reaction equation of step (2) is as follows: 2Cu+O 2 =2CuO (elemental copper oxide) 2Cu 2 O+O 2 =4CuO (cuprous oxide) The reaction equation of step (3) is as follows: CuO+H 2 SO 4 =CuSO 4 +H 2 O (sulfuric acid leaching to form copper sulfate) The reaction equation of step (4) is as follows: CuSO 4 +5H 2 O=CuSO 4 •5H 2 O (Copper sulfate crystallizes into copper sulfate pentahydrate) The reaction equation of step (5) is as follows: Bi 2 O 3 +6HCl=2BiCl 3 +3H 2 O (hydrochloric acid leaching to form bismuth chloride) The reaction equation of step (6) is as follows: Bi 3+ +Cl - +2H 2 O=Bi(OH) 2 Cl+2H + Bi(OH) 2 Cl=BiOCl+H 2 O (Bismuth chloride is hydrolyzed to form bismuth oxychloride precipitate) The contents of various substances in the waste copper-bismuth catalyst used in the following embodiments of the present invention are as follows: the average volatile content is 80wt%, and the remaining 20% ​​is dry solid, of which CuO accounts for 53%, Bi2O3 accounts for 3%, SiO2 accounts for 39wt%, and the rest is 500°C burn-out accounting for 5%. Embodiment 1:

[0025] S1. Remove volatiles: Take an appropriate amount of waste copper-bismuth catalyst slurry and pour it into a two-mouth flask. Place an electric-controlled digital display heater at the bottom of the flask. Place an asbestos net between the heater and the flask to evenly disperse the heat. Insert a thermometer into one of the two mouths of the flask to measure the internal gas temperature. Connect the other mouth to a serpentine condenser. The outlet of the condenser is connected to a conical flask to receive the liquid formed after the volatiles are condensed and liquefied. Turn on the cooling water of the serpentine condenser, turn on the heater to slowly heat up, and the heating rate is 9℃ / min. At about 90℃, obvious volatiles begin to be produced. At this time, reduce the heating rate to 3℃ / min until there is no obvious volatiles in the flask. At this time, it is about 175℃, then stop heating, pour out the solid slag, and the main components of the condensate are formaldehyde, 1,4-butynediol and water, which are returned to the BYD process flow for use.

[0026] S2. Oxidation roasting: Pour the solid slag into a corundum crucible, put it into an oxidation roasting furnace, and carry out sufficient oxidation roasting at 550°C for 2h.

[0027] S3, sulfuric acid leaching: take out the roasted sand after oxidation roasting, mix it with deionized water at a liquid-to-solid ratio of 8:1, add concentrated sulfuric acid until the pH stabilizes at 0.1, then transfer it to a three-necked flask, heat it to 90°C in an oil bath, stir and leach for 2 hours, monitor the pH during the process, if it is higher than 1, add concentrated sulfuric acid again to return the pH to 0.1, and filter to obtain sulfuric acid leaching residue and sulfuric acid leaching solution after the leaching is completed.

[0028] S4. Treatment of sulfuric acid leaching solution: Pour the sulfuric acid leaching solution into a beaker, heat and evaporate to concentrate it to 30% of the original leaching solution volume, then pour the concentrated sulfuric acid leaching solution into a polytetrafluoroethylene beaker and naturally cool it to room temperature, filter to obtain copper sulfate pentahydrate product (product purity 98.5%, copper element recovery rate ≥99%), and use the filtrate as sulfuric acid leaching mother liquor to leach the next batch of roasted sand.

[0029] S5. Hydrochloric acid leaching: rinse the sulfuric acid leaching residue with deionized water until it is nearly neutral, mix it with 1.5 mol / L hydrochloric acid solution at a liquid-to-solid ratio of 3:1, stir evenly and transfer it into a three-necked flask, monitor whether the pH is greater than 0.5, if it is higher than 0.5, add concentrated hydrochloric acid to maintain the pH at 0.1, heat it to 30°C in an oil bath, stir and leach for 6 hours, filter to obtain the hydrochloric acid leachate and filter cake, wash the filter cake with water and then dry it to obtain a crude silicon dioxide product (product purity 94.2%, silicon recovery rate ≥99%).

[0030] S6. Preparation of bismuth oxychloride: put the hydrochloric acid leachate into a three-necked flask, add sodium dodecyl sulfate at 0.1% of the mass of the leachate, stir evenly at room temperature, slowly add 0.5 mol / L sodium hydroxide solution while stirring, monitor in real time that the pH value is stable at 1 and then stop, continue stirring for 5 minutes and filter, wash the filter cake with water, dry it at 100°C for 5 hours to obtain a nano-scale bismuth oxychloride product (product purity 99.2%, bismuth element recovery rate ≥98%), and use a Quantachrome NOVA4000e porosity analyzer to detect that the pore size of the bismuth oxychloride material prepared in this process is within 3-60 nm. Embodiment 2:

[0031] S1. Remove volatiles: Take an appropriate amount of waste copper-bismuth catalyst slurry and pour it into a two-necked flask. Place an electric-controlled digital display heater at the bottom of the flask, and place an asbestos mesh between the heater and the flask to evenly disperse the heat. Insert a thermometer into one of the two-necked flask ports to measure the internal gas temperature, and connect the other port to a serpentine condenser. The outlet of the condenser is connected to a conical flask to receive the liquid formed after the volatiles are condensed and liquefied. Open the serpentine condenser cooling water, turn on the heater to slowly heat up, the heating rate is 6℃ / min, obvious volatiles begin to be produced at about 90℃, then reduce the heating rate to 1℃ / min, until no obvious volatiles are produced in the flask, at this time it is about 175℃, then stop heating, pour out the solid slag, the heating rate and material temperature range must be strictly maintained within the specified range, the heating rate can ensure the full separation of volatiles and solid slag, and can also ensure the slow decomposition of acetylene copper remaining on the catalyst, otherwise if the heating rate is too fast, it will cause acetylene copper to explode; the main components of the condensate are formaldehyde, 1,4-butynediol and water, which are returned to the BYD process flow for use.

[0032] S2. Oxidation roasting: Pour the solid slag into a corundum crucible, put it into an oxidation roasting furnace, and carry out sufficient oxidation roasting at 450°C for 8 hours.

[0033] S3, sulfuric acid leaching: take out the roasted sand after oxidation roasting, mix it with deionized water at a liquid-to-solid ratio of 5:1, add concentrated sulfuric acid until the pH stabilizes at 0.5, then transfer it to a three-necked flask, heat it to 90°C in an oil bath, stir and leach for 5 hours, monitor the pH during the process, if it is higher than 1, add concentrated sulfuric acid again to return the pH to 0.2, filter after the leaching to obtain sulfuric acid leaching residue and sulfuric acid leaching solution.

[0034] S4. Treatment of sulfuric acid leaching solution: Pour the sulfuric acid leaching solution into a beaker, heat and evaporate to concentrate it to 35% of the original leaching solution volume, then pour the concentrated sulfuric acid leaching solution into a polytetrafluoroethylene beaker and naturally cool it to room temperature, filter to obtain copper sulfate pentahydrate product (product purity 98.8%, copper element recovery rate ≥99%), and use the filtrate as sulfuric acid leaching mother liquor to leach the next batch of roasted sand.

[0035] S5. Hydrochloric acid leaching: rinse the sulfuric acid leaching residue with deionized water until it is nearly neutral, mix it with 1.5 mol / L hydrochloric acid solution at a liquid-to-solid ratio of 5:1, stir it evenly and transfer it into a three-necked flask, monitor whether the pH is greater than 0.5, if it is higher than 0.5, add concentrated hydrochloric acid to maintain the pH at 0.2, heat it to 50°C in an oil bath, stir and leach for 3 hours, filter to obtain the hydrochloric acid leachate and filter cake, wash the filter cake with water and then dry it to obtain a crude silicon dioxide product (product purity 94.1%, silicon recovery rate ≥99%).

[0036] S6. Preparation of bismuth oxychloride: put the hydrochloric acid leachate into a three-necked flask, add sodium dodecyl sulfate at 0.1% of the mass of the leachate, stir evenly at room temperature, slowly add 0.5 mol / L sodium hydroxide solution while stirring, monitor in real time that the pH value is stable at 1 and then stop, continue stirring for 5 minutes and filter, wash the filter cake with water, dry it at 100°C for 5 hours to obtain a nano-scale bismuth oxychloride product (product purity 99.3%, bismuth element recovery rate ≥98%), and use Quantachrome NOVA4000e porosity analyzer to detect that the pore size of the bismuth oxychloride material prepared in this process is within 3-60 nm.

[0037] The undisclosed parts in the present invention are all prior art, and their specific structures, materials and working principles are not described in detail. Although the embodiments of the present invention have been shown and described, it is understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for extracting high-value components from waste copper-bismuth catalysts, characterized in that: The following steps are involved: S1. Removing volatiles: heating the waste copper-bismuth catalyst slurry to remove volatiles, condensing and liquefying the volatiles for recovery, and removing the volatiles to form solid slag; S2, oxidative roasting: the solid slag is fully oxidized and roasted in an oxidative roasting furnace to obtain roasted sand; S3, sulfuric acid leaching: roasted sand and dilute sulfuric acid are stirred and heated to react, and the leaching residue and leachate are obtained by filtration; S4, sulfuric acid leaching solution treatment: the filtrate is heated and evaporated to concentrate, naturally cooled and crystallized, and filtered to obtain the copper sulfate pentahydrate product, and the filtrate is returned to leach the next batch of roasted sand; S5, hydrochloric acid leaching: the leaching residue obtained by sulfuric acid leaching is stirred and heated with dilute hydrochloric acid to react, and the leaching residue and leaching liquid are obtained by filtration. The leaching residue is washed with water and then dried to obtain a crude silicon dioxide product; S6. Preparation of bismuth oxychloride: sodium dodecyl sulfate is added to the hydrochloric acid leaching solution and stirred evenly, sodium hydroxide solution is added dropwise, and a filter cake is obtained by filtering. After washing and drying, a nano-grade bismuth oxychloride product is obtained.

2. The method for extracting high-value components from waste copper-bismuth catalysts according to claim 1, characterized in that: S1. Remove volatiles specifically as follows: take an appropriate amount of waste copper-bismuth catalyst slurry and pour it into a two-mouth flask, place an electric-controlled digital display heater at the bottom of the flask, and place an asbestos net between the heater and the flask to evenly disperse the heat; insert a thermometer into one of the two mouths of the flask to measure the internal gas temperature, and connect the other mouth to a serpentine condenser, and connect the outlet of the condenser to a conical flask to receive the liquid formed after the condensation and liquefaction of the volatiles. Turn on the cooling water of the serpentine condenser, turn on the heater to slowly heat up, the heating rate is 0-9℃ / min, and the thermometer in the flask shows that obvious volatiles begin to be produced at about 90℃. At this time, reduce the heating rate to 0-3℃ / min until there is no obvious volatiles in the flask. At this time, the thermometer in the flask shows about 175℃, then stop heating and pour out the solid slag.

3. The method for extracting high-value components from waste copper-bismuth catalysts according to claim 1, characterized in that: S2. Oxidation roasting: specifically, pour the solid slag into a corundum crucible, put it into an oxidation roasting furnace, and perform sufficient oxidation roasting at 450-550° C. for 2-8 hours.

4. The method for extracting high-value components from waste copper-bismuth catalysts according to claim 1, characterized in that: S3, sulfuric acid leaching is specifically as follows: take out the roasted sand after oxidation roasting, mix it with deionized water at a liquid-to-solid ratio of 3-10:1, add concentrated sulfuric acid until the pH value stabilizes at 0-1, then transfer it into a three-necked flask, heat it to 90°C in an oil bath, stir and leach for 2-5h, monitor the pH value during the process, if it is higher than 1, add concentrated sulfuric acid again to return the pH value to 0-1, and filter to obtain sulfuric acid leaching residue and sulfuric acid leaching solution after the leaching is completed.

5. The method for extracting high-value components from waste copper-bismuth catalysts according to claim 1, characterized in that: S4. The specific treatment of the sulfuric acid leaching solution is as follows: the sulfuric acid leaching solution is poured into a beaker, heated and evaporated to concentrate to 30-50% of the original leaching solution volume, and then the concentrated sulfuric acid leaching solution is poured into a polytetrafluoroethylene beaker and naturally cooled to room temperature, and filtered to obtain the copper sulfate pentahydrate product, and the filtrate is used as the sulfuric acid leaching mother liquor for leaching the next batch of roasted sand.

6. The method for extracting high-value components from waste copper-bismuth catalysts according to claim 1, characterized in that: S5. Hydrochloric acid leaching is specifically as follows: the sulfuric acid leaching residue is rinsed with deionized water until it is nearly neutral, mixed with 1.5 mol / L hydrochloric acid solution at a liquid-to-solid ratio of 3-5:1, stirred evenly and transferred into a three-necked flask, and the pH is monitored to see if it is greater than 0.

5. If it is higher than 0.5, concentrated hydrochloric acid is added dropwise to maintain the pH at 0-0.5, heated to 30-50°C in an oil bath, stirred and leached for 1-6h, and the hydrochloric acid leaching solution and hydrochloric acid leaching residue are filtered out, and the hydrochloric acid leaching residue is washed with water and then dried to obtain a crude silica product.

7. The method for extracting high-value components from waste copper-bismuth catalysts according to claim 1, characterized in that: S6. Preparation of bismuth oxychloride is specifically as follows: pour the hydrochloric acid leachate into a three-necked flask, add sodium dodecyl sulfate at 0.1% of the mass of the leachate, stir evenly at room temperature, slowly add 0.5 mol / L sodium hydroxide solution while stirring, stop adding after real-time monitoring when the pH value is stable at 1, continue stirring for 5 minutes and then filter, wash the filter cake with water, and dry it at 100°C for 5 hours to obtain the nano-scale bismuth oxychloride product.

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