Harmless treatment system and process for copper-containing rectifying still residues

Abstract

The invention discloses a harmless treatment system and process for copper-containing rectifying still residues. The process comprises the following steps: mixing the rectifying still residues with a dechlorinating agent and a denitrifying agent according to the ratio of 100: 5: 3 for pretreatment; feeding into a micro negative pressure pyrolysis kettle through a hydraulic device, controlling the temperature by stages, heating to 400-500 DEG C at the speed of 20-30 DEG C / h under the anaerobic condition, and pyrolyzing for 13-15 hours; carrying out gas-solid separation on the product to obtain copper-containing light and heavy components, and respectively roasting, cooling and fractionating to obtain a copper-based raw material, toluene-methanol azeotrope and fuel oil; tail gas is subjected to two-stage combustion and alkali liquor spraying dust removal and emission, a two-stage safety device is arranged, and carbon emission reduction is achieved by integrating CO2 concentration monitoring. The disposal system comprises a full-automatic hydraulic feeding machine, a pyrolysis kettle with a double-layer structure, an integrated condensation water tank with a buffering and cooling pipe, a non-condensable gas backdraft system comprising an oil storage tank and a water-sealed tank, a spraying type desulfurization and dust removal tower, a negative pressure deslagging pipeline and a PLC (Programmable Logic Controller) control system. The method is good in environmental protection property, high in resource recovery rate, high in treatment efficiency and capable of achieving harmlessness, reduction and recycling of the copper-containing rectifying still residues.

Description

Technical Field

[0001] The present invention relates to the technical field of hazardous waste treatment, and specifically refers to a harmless treatment process for copper-containing distillation kettle residues and a harmless treatment system for copper-containing distillation kettle residues for realizing this process. This process and system are mainly used to treat copper-containing distillation kettle residues to achieve their harmlessness, reduction, and resource utilization, and can be widely applied to industries such as chemical industry, pesticides, pharmaceuticals, and dyes that generate copper-containing distillation kettle residues. Background Art

[0002] In the production processes of industries such as chemical industry, pesticides, pharmaceuticals, and dyes, a large amount of copper-containing distillation kettle residues are generated as a common type of hazardous waste. These copper-containing distillation kettle residues usually contain copper and other heavy metals, organic high-boiling substances, as well as impurity elements such as chlorine and nitrogen. If not properly treated, it will not only cause serious environmental pollution but also lead to waste of resources.

[0003] Currently, there are many problems with traditional treatment methods for copper-containing distillation kettle residues. Conventional treatment methods use co-incineration with low calorific value hazardous waste. However, due to the complex organic components and impurities in copper-containing distillation kettle residues, highly toxic and harmful substances such as dioxins are easily generated during the incineration process, causing serious pollution to the atmospheric environment. At the same time, CO 2 will also be emitted, the copper content in the ash is very low and has no utilization value. It not only requires an additional landfill fee but also causes waste of copper resources and leaves potential hazards for future water pollution!

[0004] Under the background of increasingly strict environmental protection requirements and resource shortages, there is an urgent need for an efficient, environmentally friendly, and energy-saving harmless treatment process and system for copper-containing distillation kettle residues, which can realize the harmless treatment of copper-containing distillation kettle residues while maximizing the recovery of useful resources therein, reducing treatment costs, and reducing secondary pollution. Summary of the Invention

[0005] The present invention aims to solve the above technical problems and provides a harmless treatment system and process for copper-containing distillation kettle residues.

[0006] To solve the above technical problems, the technical solution provided by the present invention is: a harmless treatment process for copper-containing distillation kettle residues, including the following steps:

[0007] S1: Mix the distillation residue with a dechlorinating agent and a denitrifying agent in a mass ratio of 100:5:3 to form a pretreatment material;

[0008] S2: Transport the pretreatment material to a slightly negative pressure pyrolysis kettle through a hydraulic device, and heat it to 400 - 500 °C at a heating rate of 20 - 30 °C / h under anaerobic conditions for pyrolysis reaction, and the reaction time is 13 - 15 hours;

[0009] S3: The pyrolysis products are separated into light components, heavy components and copper-containing components through gas-solid separation;

[0010] S4: The copper-containing components are calcined at 850 - 950 °C to remove carbon deposits, obtaining copper-based industrial raw materials;

[0011] S5: The light components are cooled to room temperature by a coil condenser to recover the toluene-methanol azeotrope;

[0012] S6: The heavy components are fractionated in two stages to obtain fuel oil products;

[0013] S7: The pyrolysis tail gas is successively treated by combustion at 800 - 900 °C in a primary combustion chamber, catalytic combustion at 1150 °C in a secondary catalytic combustion chamber, and dust removal by alkali liquor spraying before being discharged.

[0014] Furthermore, in step S2, the pyrolysis kettle maintains a slightly negative pressure of -5 kPa to -1 kPa, and the heating process uses staged temperature control:

[0015] In the first stage, diesel or natural gas is used as fuel, and the temperature is raised to 120 ± 5 °C within 2 hours;

[0016] In the second stage, the self-produced non-condensable gas is used for combustion heating to raise the temperature to 400 - 500 °C.

[0017] Furthermore, the dechlorination agent contains a composite of calcium oxide and sodium carbonate, the denitrification agent is a zinc oxide-calcium oxide composite deoxidizer or a mixture of urea and kaolin, and the total addition amount of the two does not exceed 10% of the total mass of the materials.

[0018] Furthermore, in step S7, the tail gas treatment system is provided with a double-stage safety device, including:

[0019] A water seal flame arrester is provided at the front end, and the working liquid level maintains a water column pressure of 50 - 60 cm;

[0020] A combined device of a gas gun and a blower is provided at the rear end, and the air excess coefficient is controlled at 1.2 - 1.5.

[0021] Furthermore, in step S3, the gas-solid separation adopts a gradient cooling process:

[0022] The primary separation intercepts the light components at 130 °C;

[0023] The secondary separation condenses and recovers the heavy components at 130 - 380 °C;

[0024] The final separation collects the copper-containing slag at room temperature or at a high temperature of 150 °C by using the slag discharging system of the pyrolysis furnace. Furthermore, the fuel oil products meet the GB / T17411 marine fuel oil standard, with a calorific value ≥ 40 MJ / kg and a sulfur content ≤ 0.5 wt%.

[0025] Furthermore, it also includes carbon emission reduction treatment:

[0026] The system integrates an on-line monitoring device for CO 2 concentration;

[0027] The carbon emission reduction amount is calculated by the formula Q = K×(V1×C1 - V2×C2), where K is a correction coefficient of 0.75 - 0.85;

[0028] Generate CCER carbon quota certificates and conduct electronic filing.

[0029] The harmless treatment system for copper-containing distillation kettle residues includes:

[0030] A feeding mechanism, specifically a fully automatic hydraulic feeder;

[0031] A main furnace system, specifically including a pyrolysis kettle. The pyrolysis kettle has a double-layer structure. The inner layer is made of Q345R boiler volume plate, the outer shell is made of refractory material, and anti-smoke leakage devices are provided at both ends of the pyrolysis kettle;

[0032] A cooling system, specifically including an integrated coil condensation water tank, and a buffer pipe and a cooling pipe are arranged inside. The buffer pipe and the cooling pipe are designed in parallel;

[0033] A non-condensable gas re-burning system, specifically including an oil storage tank and multiple water seal tanks. The water seal tanks are connected to the pyrolysis kettle through non-condensable combustible gas pipelines;

[0034] A desulfurization and dust removal system, specifically including a spray desulfurization and dust removal tower. The spray desulfurization and dust removal tower is connected to the pyrolysis kettle through a pipeline;

[0035] A slag discharging system, specifically including a negative pressure slag discharging pipeline. A pulse dust removal device and a cyclone dust removal device are sequentially arranged on the negative pressure slag discharging pipeline.

[0036] In addition, a cracking device for copper-containing hazardous waste proposed above according to the present invention may also have the following additional technical features:

[0037] The pyrolysis kettle of the main furnace system adopts a heating method with a fuel engine and non-condensable gas for combustion support.

[0038] Both ends of the integrated coil condensation water tank in the cooling system are fixed with blind plates.

[0039] A steam drum tank is provided between the main furnace system and the cooling system.

[0040] It also includes an exhaust gas combustion chamber, which is connected to the non-condensable combustible gas pipeline.

[0041] It also includes a PLC control system for controlling the feeding system, the main furnace system, the cooling system, the non-condensable gas re-burning system, the desulfurization and dust removal system, and the slag discharging system, and is internally provided with a real-time monitoring and automatic alarm module.

[0042] The advantages of the present invention compared with the prior art are as follows:

[0043] 1. Good environmental protection performance

[0044] This process and system can effectively remove harmful substances in the copper-containing distillation residue, realizing the harmless treatment of hazardous waste. The generation of dioxins is effectively inhibited during the pyrolysis process. The tail gas meets the discharge standards after multi-stage treatment. The flue gas discharge is white water vapor, odorless, and does not produce other waste emissions. The production site is clean and tidy, meeting the national environmental protection production standards, and reducing environmental pollution. The system operates under slightly negative pressure, reducing the leakage of harmful gases and ensuring the safety and cleanliness of the production environment.

[0045] 2. High resource recovery rate

[0046] Through the pyrolysis, gas-solid separation and subsequent treatment of the copper-containing distillation residue, useful resources such as copper, methanol, toluene, fuel oil, etc. can be effectively recovered and utilized. The copper-containing components can be used as raw materials for copper smelting. The light components can recover the toluene-methanol azeotrope, and the heavy components can obtain fuel oil products meeting the standards, realizing the maximum utilization of resources and reducing resource waste. The non-condensable gas re-burning system re-uses the gases that cannot be cooled, saving fuel costs and improving energy utilization efficiency.

[0047] 3. High treatment efficiency

[0048] The pyrolysis process uses staged temperature control and self-produced non-condensable gas for heating, shortening the heating time and improving the pyrolysis efficiency. The gas-solid separation adopts a gradient cooling process, which can quickly and effectively separate the pyrolysis products into different components for subsequent treatment. The system is controlled by PLC, realizing automated operation and real-time monitoring, and can timely adjust system parameters to ensure the high-efficiency operation of the system and improve the treatment efficiency.

[0049] 4. Low cost

[0050] This process not only eliminates all the drawbacks of the conventional treatment methods. At the same time, through the recycling of resources and the reuse of energy, certain economic benefits are generated, such as the sale of products such as copper-based industrial raw materials, toluene-methanol azeotrope, fuel oil, etc., and the re-burning of non-condensable gas saves fuel costs. The structural design of the equipment is reasonable, such as the double-layer structure and refractory material shell of the pyrolysis kettle, the high-efficiency heat exchange design of the cooling system, etc., reducing the energy consumption and maintenance costs of the equipment.

[0051] 5. Safe and reliable operation

[0052] The feeding mechanism adopts a fully automatic hydraulic feeder, eliminating the need for workers to enter the main furnace, reducing the labor intensity and safety risks of workers. Anti-smoke leakage devices are installed at both ends of the pyrolysis kettle. Blind plates are used to fix both ends of the cooling system. Safety devices such as safety water seals and flame arresters are installed in the non-condensable gas afterburning system, ensuring the sealing and safety of the equipment during operation and preventing accidents such as harmful gas leakage and fires. The real-time monitoring and automatic alarm functions of the PLC control system can promptly detect and handle abnormal situations, ensuring the safe and stable operation of the equipment.

[0053] 6. Have carbon emission reduction benefits

[0054] The system integrates a CO 2 concentration on-line monitoring device. By monitoring the CO 2 concentration and calculating the carbon emission reduction amount, a CCER carbon quota certificate is generated and electronically filed. The emission reduction amount CCER can be traded in the carbon emission trading market, achieving the unity of economic benefits and environmental benefits and meeting the requirements of sustainable development. Description of the drawings

[0055] Figure 1 It is a structural schematic diagram of the harmless treatment system and process of the copper-containing distillation kettle residue of the present invention.

[0056] Figure 2 It is a process flow diagram of the harmless treatment system and process of the copper-containing distillation kettle residue of the present invention.

[0057] As shown in the figure: 1. Fully automatic hydraulic feeder; 2. Pyrolysis kettle; 3. Integrated coil condensation water tank; 301. Buffer pipe; 302. Cooling pipe; 4. Oil storage tank; 401. Oil and gas pipeline; 5. Water seal tank; 6. Non-condensable combustible gas pipeline; 7. Spray type desulfurization and dust removal tower; 701. Flue gas pipeline; 8. Negative pressure slag discharge pipeline; 9. Pulse dust removal equipment; 10. Cyclone dust removal equipment; 11. Steam drum tank; 12. Exhaust gas combustion chamber; 13. PLC control system. Detailed implementation manners

[0058] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0059] I. Working principle of the present invention:

[0060] 1.1 Harmless treatment process of copper-containing distillation kettle residue

[0061] Pretreatment step S1: Mix the distillation residue with a dechlorinating agent and a denitrifying agent in a mass ratio of 100:5:3 to form a pretreated material. The dechlorinating agent comprises a compound of calcium oxide and sodium carbonate, the denitrifying agent is a mixture of urea and kaolin, and the total amount of zinc oxide and calcium oxide composite denitrifying agent or the total amount of the two does not exceed 10% of the total mass of the material. By adding the dechlorinating agent and the denitrifying agent, the chlorine and nitrogen elements in the distillation residue can be effectively removed in the subsequent pyrolysis process to reduce the generation of pollutants.

[0062] Pyrolysis step S2: The pretreated material is transported to a micro-negative pressure pyrolysis kettle through a hydraulic device, and heated to 400-500°C at a heating rate of 20-30°C / h under anaerobic conditions for pyrolysis reaction, and the reaction time is 13-15 hours. The pyrolysis kettle maintains a micro-negative pressure of -5kPa to -1kPa, and the heating process adopts staged temperature control: the first stage uses diesel or natural gas as fuel, and the temperature is raised to 120±5°C within 2 hours; the second stage uses self-produced non-condensable gas combustion for heating, and the temperature is raised to 400-500°C. During the pyrolysis process, the macromolecular bonds are broken, and isomerization simultaneously decomposes chlorine and nitrogen elements from benzene rings and alkanes, and small molecules are polymerized to achieve the reduction, harmlessness, stabilization and resource utilization of solid waste, while effectively inhibiting the production of dioxins.

[0063] Gas-solid separation step S3: The pyrolysis product is subjected to gas-solid separation to obtain light components, heavy components and copper-containing components. The gas-solid separation adopts a gradient cooling process: the primary separation recovers the light components at -110°C, the secondary separation recovers the heavy components by condensation at 110-380°C; the final separation recovers the copper-containing slag at 80°C to 150°C using the furnace's own slag discharge system. Through this gradient cooling separation process, different components in the pyrolysis product can be effectively separated, which is convenient for subsequent processing and utilization.

[0064] Copper-containing component treatment step S4: The copper-containing component is roasted at 850-950°C to remove carbon deposits, thereby obtaining a copper-based industrial raw material. After testing, the copper-containing component is mainly composed of copper and copper oxides. After the organic matter is cracked at high temperature, the carbon deposits are removed by high-temperature roasting. The main components are copper and copper compounds. It is an industrial semi-finished product with no harmful properties and can be sold as a copper smelting raw material.

[0065] Light component processing step S5: The light component is cooled to room temperature by a coil condenser to recover toluene-methanol azeotrope. The light component at 110°C is mainly methanol-toluene azeotrope, which can be used as a heating source for a cracking furnace and can also be used as a raw material for extracting methanol and toluene.

[0066] Recombinant fraction treatment step S6: The recombinant fraction is fractionated in two stages to obtain fuel oil products. The components of the recombinant fraction at 130°C - 380°C are mainly C and H compounds, containing trace amounts of O and N, and S and P are negligible. The fuel oil products obtained after treatment meet the GB / T 17411 marine fuel oil standard, with a calorific value ≥ 40 MJ / kg and a sulfur content ≤ 0.5 wt%, and can be used as a heating source for the cracking furnace. After pretreatment, it can also be sold as fuel oil and used in the steel, glass, ceramic, and smelting industries.

[0067] Tail gas treatment step S7: The pyrolysis tail gas is successively subjected to combustion in a primary combustion chamber at 800 - 900°C, catalytic combustion treatment in a secondary catalytic combustion chamber in the range of 1150 - 1300°C, and alkali solution spraying for dust removal before being discharged. The tail gas treatment system is equipped with a two-stage safety device. A water seal flame arrester is set at the front end, and the working liquid level maintains a water column pressure of 50 - 60 cm; a combined device of a gas spray gun and a blower is set at the rear end, and the air excess coefficient is controlled within 1.2 - 1.5. Through multi-stage treatment, it is ensured that the tail gas meets the emission standards and reduces environmental pollution.

[0068] Carbon emission reduction treatment: The system integrates an on-line monitoring device for the concentration of CO 2 The carbon emission reduction amount is calculated by the formula Q = K × (V1 × C1 - V2 × C2), where K = 0.75 - 0.85 is the correction coefficient; a CCER carbon quota certificate is generated and electronically filed. Through the monitoring of the CO 2 concentration and the calculation of the carbon emission reduction amount, the quantitative management of carbon emission reduction is realized, and the emission reduction amount CCER can be traded in the carbon emission trading market, achieving the unity of economic benefits and environmental benefits.

[0069] 1.2 Harmless disposal system for copper concentrate kettle residue

[0070] Feeding mechanism: Specifically, it is a fully automatic hydraulic feeder 1, which can be automatically adjusted longitudinally, horizontally, and vertically, making the equipment more user-friendly. There is no need to enter the main furnace, reducing the labor intensity of workers, improving the working environment of workers, and saving time in the traditional feeding method.

[0071] Main furnace system: Specifically, it includes a pyrolysis kettle 2. The pyrolysis kettle 2 has a double-layer structure. The inner layer is made of Q345R boiler volume plate, which is resistant to high temperature and corrosion; the outer shell is made of refractory materials, with a light specific gravity and good heat preservation effect. Leak-proof smoke devices are set at both ends of the pyrolysis kettle, solving the problem of smoke leakage during ignition in the production process. The pyrolysis kettle 1 of the main furnace system adopts a heating method with a fuel engine and non-condensable gas for combustion assistance. The furnace chamber structure is reasonable, reducing heat loss and also ensuring the service life of the main furnace. The heat preservation shell adopts an up-and-down structure, facilitating inspection and maintenance.

[0072] Cooling system: Specifically includes an integrated coil condensation water tank 3, with a buffer pipe 301 and a cooling pipe 302 arranged inside. The buffer pipe 301 and the cooling pipe 302 are designed in parallel, having a large heat exchange area and good cooling effect. The design of the double-pipe parallel connection solves the pressure boost of the main furnace during the peak oil output period, greatly improving the quality of the oil product and making the oil output rate higher. Both ends of the integrated coil condensation water tank 3 are fixed with blind plates, which are easy to clean and maintain. There is a steam drum 11 between the main furnace system and the cooling system, which can effectively separate and store steam.

[0073] Non-condensable gas re-burning system: Specifically includes an oil storage tank 4 and multiple water seal tanks 5 connected in sequence. The cooling system is connected to the oil storage tank 4 through an oil and gas pipeline 401, and the water seal tank 5 is connected to the pyrolysis kettle 1 through a non-condensable combustible gas pipeline 6. The gas that cannot be cooled down after passing through the coil condensation water tank enters the system gas purification device through the oil storage tank and then enters the furnace through the pipeline for combustion support, saving fuel. It also includes an exhaust gas combustion chamber 12, which is connected to the non-condensable combustible gas pipeline 6 to further burn the non-condensable gas, ensuring complete combustion of the gas and reducing pollutant emissions.

[0074] Desulfurization and dust removal system: Specifically includes a spray type desulfurization and dust removal tower 7, and the spray type desulfurization and dust removal tower 7 is connected to the pyrolysis kettle 1 through a flue gas pipeline 701. This system can remove harmful substances such as dust, particulate matter, waste oil particles, and NOX in the waste gas, enabling the flue gas formed after combustion to meet the standards after treatment and meeting the environmental protection requirements.

[0075] Slag discharging system: Specifically includes a negative pressure slag discharging pipeline 8, and a pulse dust removal device 9 and a cyclone dust removal device 10 are successively arranged on the negative pressure slag discharging pipeline 8. The self-flowing slag discharging system adopted in this system can also be optionally equipped with pneumatic conveying or scraper, with safe, fast, and clean slag discharging. After pyrolysis is completed, generally when the temperature of the pyrolysis kettle drops to 150 °C, it is recommended to start discharging the copper-containing furnace slag. The process of discharging the copper-containing furnace slag is automatically fully sealed, ensuring a clean production environment. At the same time, with the help of a high-temperature slag discharger, the equipment can discharge the copper-containing furnace slag at a higher temperature to achieve the purpose of saving time.

[0076] PLC control system 13: Used to control the feeding system, main furnace system, cooling system, non-condensable gas re-burning system, desulfurization and dust removal system, and slag discharging system, and is internally equipped with a real-time monitoring and automatic alarm module. Through the PLC control system, the automatic control of the entire disposal system can be realized, the operation status of the system can be monitored in real time. Once an abnormal situation occurs, the automatic alarm module will promptly issue an alarm to remind the operator to handle it, ensuring the safe and stable operation of the equipment.

[0077] 1.3 Technical principle

[0078] Pyrolysis principle

[0079] Under anaerobic conditions, the pretreated distillation residue is heated to 400-500℃ in a slightly negative pressure pyrolysis kettle. In this process, the macromolecular organic matter in the distillation residue undergoes thermal decomposition reaction, the macromolecular bonds are broken, and isomerization simultaneously separates the chlorine and nitrogen elements from the benzene ring and alkane, and small molecules polymerize. The pyrolysis process is divided into two stages. In the first stage, diesel or natural gas is used as fuel to heat the temperature to 120±5℃, at which time non-condensable gas begins to be produced; in the second stage, self-produced non-condensable gas is used for combustion and heating, and the temperature continues to rise to 400-500℃, so that the pyrolysis reaction can be fully carried out, so as to achieve the reduction, harmlessness and resource utilization of solid waste, and effectively inhibit the production of dioxins.

[0080] Gas-solid separation principle

[0081] The pyrolysis products are separated into gas and solid by a gradient cooling process. The primary separation is carried out at -130℃ to condense and recover the light components, the secondary separation is carried out at 130-380℃ to condense and recover the heavy components; the final separation is carried out at 80℃ to recover the copper-containing slag by using the slag discharge system of the cracking furnace. Through this gradient cooling separation process, different components can be effectively separated according to their physical properties (such as boiling point, melting point, etc.).

[0082] Treatment principle of copper-containing components

[0083] The copper-containing components contain copper and copper oxides, as well as some impurities such as carbon deposits. By roasting at a high temperature of 850-950℃, organic matter such as carbon deposits are burned and removed, thereby obtaining a copper-based industrial raw material whose main components are copper and copper compounds, which can be further processed and utilized as a copper smelting raw material.

[0084] Principles of light and heavy component processing

[0085] The light component is cooled to room temperature by a coil condenser, and the methanol-toluene azeotrope therein is condensed and recovered, which can be used as a heating source for a cracking furnace or as a raw material for extracting methanol and toluene. The heavy component is subjected to two-stage fractionation. According to the principle that components with different boiling points evaporate and condense at different temperatures, the heavy component is separated into fuel oil products that meet the GB / T17411 marine fuel oil standard, which can be used in industries such as steel, glass, ceramics, and smelting.

[0086] Exhaust gas treatment principle

[0087] The pyrolysis tail gas contains some unburned organic substances and other pollutants. First, in the primary combustion chamber, through high-temperature combustion at 800 - 900 °C, the macromolecular organic substances in the tail gas are further decomposed; then, in the secondary catalytic combustion chamber, under the action of a temperature of 1150 - 1250 °C and a catalyst, harmful substances such as dioxins in the tail gas are further converted into harmless substances; finally, through alkali liquor spraying for dust removal, impurities such as dust, particulate matter, and acidic gases in the tail gas are removed to ensure that the tail gas meets the emission standards. The double-stage safety device set in the tail gas treatment system, the water seal flame arrester can prevent flame flashback, and the combined device of the gas burner and the blower can ensure the full combustion of non-condensable gases, improving the safety of the system.

[0088] System operation principle

[0089] The harmless treatment system for copper-containing distillation kettle residues transports the pretreated materials to the pyrolysis kettle through a fully automatic hydraulic feeder. The pyrolysis kettle uses a heating method with a fuel engine and non-condensable gas for combustion support to carry out pyrolysis reactions. The oil and gas generated by pyrolysis enter the cooling system through pipelines. After being cooled by an integrated coil condensation water tank, the oil and gas are converted into fuel oil and enter the storage oil tank, while the non-condensable gas enters the non-condensable gas recirculation combustion system. The non-condensable gas enters the furnace for combustion support after purification, and the excess non-condensable gas enters the waste gas combustion chamber for further combustion. The light components and heavy components generated by pyrolysis are separated by a gas-solid separation system and then processed respectively. The pyrolysis tail gas is discharged after being treated to meet the standards by a desulfurization and dust removal system. The slag discharge system automatically and fully seals and discharges the copper-containing components and furnace slag after pyrolysis is completed. The entire system is automatically controlled and monitored in real time by a PLC control system to ensure the safe and stable operation of the system.

[0090] II. Implementation method:

[0091] As Figure 2 shown, the process flow diagram of the pyrolysis equipment:

[0092] (1) After the raw materials enter the pyrolysis kettle through the hydraulic mechanical device, the furnace door is closed, and the pyrolysis kettle starts to be heated for pyrolysis. In the first two hours, diesel (or natural gas) is used as fuel to heat the pyrolysis kettle. When the temperature reaches about 120 °C, reactions occur in the pyrolysis kettle and non-condensable gases are generated. As the temperature rises, the non-condensable gases start to provide heat for the pyrolysis kettle, saving fuel costs. Subsequently, the temperature of the pyrolysis kettle gradually rises, and when it reaches about 400 °C, the pyrolysis is basically completed.

[0093] (2) The oil and gas enter the buffer tank through the pipeline. After preliminary purification, the oil and gas enter the coil condenser. After being fully cooled by the coil condenser, the oil and gas are converted into fuel oil and enter the storage tank. The non-condensable gas (the main chemical components are C1 and C4 alkanes) enters the gas purification device through the condenser and then enters the safety water seal after purification. (After coming out of the safety water seal, it enters the flame arrester to prevent the fire in the furnace from flashing back and ensure the safety of equipment operation. This device is also one of the safety devices in the whole set of equipment). Then, through the second safety device, the gas spray gun, it is burned for its own heating use. Since the main components of the non-condensable gas, C1 and C4 alkanes, can burn fully, it becomes colorless, odorless, pollution-free, energy-saving and environmentally friendly, effectively saving the customer's cost.

[0094] (3) Slag discharging: Generally, when the temperature of the main furnace drops to 150 °C after pyrolysis is completed, it is recommended to start discharging the copper-containing slag. The process of discharging the copper-containing slag is automatically fully sealed. However, with the help of a high-temperature slag discharger, the equipment can discharge the copper-containing slag at a higher temperature to save time.

[0095] (4) Dust removal: When the non-condensable gas is pre-heated, the gas spray gun and the blower are used to make it burn fully. During the combustion process of the gas, the harmful substances in the gas have been burned. In order to meet the environmental protection emission standards, the burned gas is further purified. The cracked tube condensation is used to cool it down, and then it goes through two-stage spray dust removal and then enters the gas-liquid separation (to separate water and gas), and finally enters the activated carbon adsorption to completely eliminate harmful substances and meet the emission standards.

[0096] As Figure 1 shown: Process description of the pyrolysis equipment:

[0097] (1) Feeding system: The feeding method adopted by this equipment is a fully automatic hydraulic feeder, which can be adjusted longitudinally, horizontally and vertically, making the equipment more user-friendly. There is no need to enter the main furnace, reducing the labor intensity of workers, improving the working environment of workers, and saving the time of the traditional feeding method.

[0098] (2) Main furnace system: The inner liner of the main reaction kettle is made of Q345R boiler volume plate, which is resistant to high temperature and corrosion. The main furnace insulation shell uses a new type of refractory material, which has the advantages of light specific gravity and good heat preservation effect. The insulation shell adopts an up-and-down structure, which is convenient for maintenance and repair. Anti-smoke leakage devices are installed at both ends to solve the problem of smoke leakage during ignition in the production process.

[0099] (3) Heating system: This system adopts the heating method of a fuel engine (+ non-condensable gas combustion support). The furnace structure is reasonable, reducing heat loss and ensuring the service life of the main furnace at the same time.

[0100] (4) Cooling system: This system uses an integrated coil condensing water tank with built-in buffer pipes and cooling pipes. It has a large heat exchange area and good cooling effect. The double-pipe parallel design solves the problem of the main furnace pressure increase during the peak oil production period, greatly improving the quality of the oil and making the oil output rate higher. The two ends of the water tank are fixed with blind plates, which are easy to clean and maintain.

[0101] (5) Non-condensable gas backfire system: The gas that cannot be cooled down after passing through the coil condensation water tank enters the system gas purification device through the oil storage tank and then enters the furnace through the pipeline to assist combustion, saving fuel.

[0102] (6) Desulfurization and dust removal system: This system uses a spray-type desulfurization and dust removal tower to remove dust, particulate matter, waste oil particles, NOX,

[0103] (7) Slag discharge system: This system adopts a gravity-flow slag discharge system, which is safe, fast and clean (you can also choose air delivery or scraper)

[0104] (8) Control system: This system adopts PLC control, digital display, real-time monitoring and automatic alarm.

[0105] This pyrolysis kettle is a micro-negative pressure pyrolysis equipment. The raw material medium is tires, waste plastics, sludge and other solids. The feeding method is automatic feeding by a hydraulic fully automatic feeder. The heating method uses fuel oil and natural gas as the starting fuel. The cooling method uses a water-cooled integrated coil cooling box. The non-condensable gas uses a double purification system. The flue gas treatment uses a multi-stage desulfurization and dust removal purification system. After the hydraulic feeder is used for automatic feeding, the furnace door is closed and ignited for heating. The heating time is about 2 hours. The material in the pyrolysis kettle begins to gasify, and the gas enters the gas distribution bag through the gas outlet, and then enters the cooling system for cooling. After cooling, the gas is liquefied into oil. The non-condensable gas enters the furnace to assist combustion after passing through the water seal and flame arrester. At this time, the burner can be turned off. The flue gas formed after combustion enters the desulfurization and dust removal system through the pipeline and meets the emission standards.

[0106] After the entire pyrolysis process is completed, turn off the flame and wait for the pyrolysis kettle to cool down to a temperature where slag can be discharged before slag can be discharged.

[0107] This equipment operates under normal pressure and sealing condition, without pollution and leakage. The smoke emission is white water vapor, without odor, and does not produce other waste emission. The production site is clean and tidy, the production process is safe and low energy consumption, and meets national production standards.

[0108] The present invention and its embodiments are described above, and such description is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. In short, if ordinary technicians in the field are inspired by it, without departing from the purpose of the invention, they can design a structure and embodiment similar to the technical solution without creativity, which should belong to the protection scope of the present invention.

Claims

1. A harmless treatment process for copper-containing distillation still residues, characterized in that: The following steps are involved: S1: Mixing the distillation residue with a dechlorinating agent and a denitrifying agent in a mass ratio of 100:5:3 to form a pretreated material; S2: The pretreated material is transported to a slightly negative pressure pyrolysis kettle through a hydraulic device, and heated to 400-500°C at a heating rate of 20-30°C / min under anaerobic conditions for pyrolysis reaction, and the reaction time is 13-15 hours; S3: The pyrolysis products are separated by gas-solid separation to obtain light components, heavy components and copper-containing components; S4: The copper-containing component is calcined at 850-950° C. to remove carbon deposits, thereby obtaining a copper-based industrial raw material; S5: The light component is cooled to room temperature via a coil condenser to recover toluene-methanol azeotrope; S6: The heavy component is subjected to two-stage fractionation to obtain a fuel oil product; S7: The pyrolysis tail gas is discharged after being burned in the first combustion chamber at 800-900℃, catalytic combustion treatment at ≥1150℃ in the second catalytic combustion chamber, and dust removal by alkaline solution spraying.

2. The harmless disposal process for copper-containing distillation still residues according to claim 1, characterized in that: The pyrolysis kettle in step S2 is maintained at a slight negative pressure of -5kPa to -1kPa, and the heating process is temperature-controlled in stages: In the first stage, diesel or natural gas is used as fuel and the temperature is raised to 120±5℃ within 2 hours; In the second stage, self-produced non-condensable gas is used for combustion heating to raise the temperature to 400-500℃.

3. The harmless disposal process for copper-containing distillation still residues according to claim 1, characterized in that: The dechlorinating agent comprises a compound of calcium oxide and sodium carbonate, and the denitrifying agent is a zinc oxide-calcium oxide composite denitrifying agent or a mixture of urea and kaolin, and the total addition amount of the two does not exceed 10% of the total mass of the materials.

4. The harmless disposal process for copper-containing distillation still residues according to claim 1, characterized in that: In step S7, the tail gas treatment system is provided with a two-stage safety device, including: A water-sealed flame arrester is set at the front end, and the working liquid level maintains a water column pressure of 50-60cm; A gas spray gun and blower combination device is set at the rear end, and the air excess coefficient is controlled at 1.2-1.

5.

5. The harmless disposal process for copper-containing distillation still residues according to claim 1, characterized in that: In step S3, the gas-solid separation adopts a gradient cooling process: The primary separation intercepts the light components at 130°C; Secondary separation: condensation at 130-380°C to recover heavy components; After the final separation, when the furnace temperature drops to 150°C, the copper-containing slag is collected using a mechanical reverse rotating separation device (the cracking furnace has its own slag discharge system).

6. The harmless disposal process for copper-containing distillation still residues according to claim 1, characterized in that: The fuel oil product meets the GB / T17411 marine fuel oil standard, with a calorific value of ≥40MJ / kg and a sulfur content of ≤0.5wt%.

7. The harmless disposal process for copper-containing distillation still residues according to claim 1, characterized in that: Also includes carbon reduction treatments: System IntegrationCO 2 Concentration online monitoring device; Carbon reduction is calculated by the formula Q = K × (V1 × C1-V2 × C2), where K = 0.75-0.85 correction factor; Generate CCER carbon quota certificate and file it electronically.

8. A harmless disposal system for copper-containing distillation kettle residues, characterized by: A feeding mechanism, specifically a fully automatic hydraulic feeding machine (1); The main furnace system specifically comprises a pyrolysis kettle (2), wherein the pyrolysis kettle (2) is a double-layer structure, the inner layer is made of Q345R boiler volume plate, the outer shell is made of refractory material, and smoke leakage prevention devices are arranged at both ends of the pyrolysis kettle. The pyrolysis kettle (1) of the main furnace system adopts a heating method of a fuel engine and non-condensable gas combustion-assisted heating; A cooling system, specifically comprising an integrated coil condensing water tank (3), wherein a buffer tube (301) and a cooling tube (302) are arranged inside, wherein the buffer tube (301) and the cooling tube (302) are designed in parallel, and both ends of the integrated coil condensing water tank (3) in the cooling system are fixed by blind plates; The non-condensable gas backfire system specifically comprises an oil storage tank (4) and a plurality of water seal tanks (5) connected in sequence, wherein the cooling system is connected to the oil storage tank (4) via an oil and gas pipeline (401), and the water seal tank (5) is connected to a pyrolysis kettle (1) via a non-condensable combustible gas pipeline (6); The desulfurization and dust removal system specifically comprises a spray-type desulfurization and dust removal tower (7), wherein the spray-type desulfurization and dust removal tower (7) is connected to the pyrolysis kettle (1) via a flue gas pipeline (701); The slag discharge system specifically comprises a negative pressure slag discharge pipeline (8), on which a pulse dust removal device (9) and a cyclone dust removal device (10) are sequentially arranged.

9. The harmless disposal system for copper-containing distillation still residues according to claim 8, characterized in that: A drum tank (11) is provided between the main furnace system and the cooling system; It also includes an exhaust gas combustion chamber (12) connected to a non-condensable combustible gas pipeline (6); It also includes a PLC control system (13) for controlling the feeding system, the main furnace system, the cooling system, the non-condensable gas backfire system, the desulfurization and dust removal system, and the slag discharge system, and is internally provided with a real-time monitoring and automatic alarm module.

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