A deep processing system for adiponitrile waste residue oil

Abstract

The utility model provides a kind of deep processing system of adiponitrile waste residue oil belongs to adiponitrile waste residue oil technical field.The utility model's adiponitrile waste residue oil deep processing system includes solid processing unit;Solid processing unit includes the deep extraction device, low-temperature heat treatment device, crushing device, hydrothermal treatment device and filter device connected in turn;Deep extraction device is handled to adiponitrile waste residue oil, and gets crude nitrile and high viscosity residue;Low-temperature heat treatment device is handled to high viscosity residue and gets solid waste residue;Crushing device and hydrothermal treatment device are handled to solid waste residue, and carbon ball is obtained after washing by filter device filtering.The viscosity is big, and it is difficult to divide and transport adiponitrile waste residue oil, and it is efficiently converted into small particle carbon ball with regular shape and stable properties, which significantly improves the convenience and economy of subsequent treatment and disposal.

Description

Technical Field

[0001] This utility model relates to the field of adiponitrile waste oil technology, specifically to a deep treatment system for adiponitrile waste oil. Background Technology

[0002] In the production process of butadiene-based synthesis of adiponitrile (ADN), butadiene is converted into adiponitrile, which has important industrial value, through key steps such as one-step butadiene hydrogenation, carbon chain isomerization, and two-step butadiene hydrogenation.

[0003] After the two-step hydrocyanation of butadiene is completed, the reaction liquid is separated to remove the catalyst, unreacted two-step hydrocyanation feedstock, adiponitrile product, and byproduct 2-methylglutaronitrile (MGN). The remaining portion in the bottom of the reactor is the waste residue oil. This waste residue oil is a key treatment challenge in the current process: it contains incompletely recovered ADN and MGN, which have high industrial value, resulting in resource waste and economic losses; at the same time, it is enriched with various cyano-containing nitrile mixtures, potentially deactivated catalysts / auxiliaries containing heavy metals (such as nickel and phosphorus), and a large amount of recalcitrant coking materials, constituting a serious source of complex pollution.

[0004] Currently, the industry generally lacks efficient, environmentally friendly, and resource-efficient mature treatment technologies. Conventional direct discharge or simple landfill disposal methods not only cause serious and persistent environmental threats to soil and aquatic ecosystems from cyanide compounds, heavy metals, and coke pollutants, but also lead to the waste of valuable chemical raw materials such as ADN and MGN, which seriously violates the principles of green chemistry and sustainable development.

[0005] Therefore, developing a deep treatment system for waste oil generated during the butadiene-based adiponitrile production process, enabling the efficient recovery of key valuable components (ADN, MGN) and the safe and harmless disposal of hazardous substances (cyanonitrile-containing substances, heavy metals, and coke), is of urgent practical significance and important application value for improving process economics, reducing environmental pollution, and promoting the green and sustainable development of the industry. This technical field urgently needs to break through the limitations of traditional treatment models and construct a comprehensive solution that emphasizes both resource recovery and environmental governance. Utility Model Content

[0006] To address the shortcomings of existing technologies, this utility model discloses a deep treatment system for adiponitrile waste oil, which solves the environmental pollution and waste of valuable components ADN and MGN caused by direct discharge or simple landfill disposal of adiponitrile waste oil.

[0007] To address at least one of the aforementioned problems, this utility model proposes a deep treatment system for adiponitrile waste oil, including a solids treatment unit.

[0008] The solid processing unit includes a deep extraction device, a low-temperature heat treatment device, a pulverizing device, a hydrothermal treatment device, and a filtration device connected in sequence.

[0009] The deep extraction device is used to process adiponitrile waste oil to obtain crude nitrile and high-viscosity residue.

[0010] The low-temperature heat treatment device is used to process the high-viscosity slag to obtain solid waste residue;

[0011] The crushing device and the hydrothermal treatment device are used to process the solid waste residue, and carbon balls are obtained after filtration and washing by the filtration device.

[0012] Existing technologies for treating adiponitrile waste oil often lack systematic and comprehensive solutions, focusing primarily on single stages or simple treatments, making it difficult to achieve synergistic optimization of resource recovery and environmental emissions. This invention's solid waste treatment unit significantly improves the resource utilization rate and harmlessness level of adiponitrile waste oil through a multi-stage synergistic treatment approach: First, a deep extraction device efficiently recovers valuable crude nitrile components such as residual adiponitrile and 2-methylglutaronitrile from the waste oil, greatly reducing resource waste. The separated high-viscosity slag then enters a low-temperature heat treatment device, where residual cyanide compounds are effectively decomposed and some volatile substances are removed at a mild temperature, significantly reducing the toxicity and environmental risks of subsequent treatments. The solid waste residue formed after low-temperature heat treatment is refined by a crushing device and then enters a hydrothermal treatment device for deep purification and modification. After filtration and washing, it finally yields a carbon sphere product with a regular shape. The carbon spheres obtained in this application can be used in the fields of fuel, adsorbent, and landfill. Since the preparation process of adiponitrile includes phosphorus-containing catalysts, the waste oil inevitably contains catalysts as well. The carbon spheres obtained after treatment by the technical solution of this application also contain phosphorus and can be used as a better landfill to enrich the soil.

[0013] In some embodiments, a gas processing unit is also included;

[0014] The gas processing unit includes a gas-liquid condensation device. The gas phase outlet of the low-temperature heat treatment device is connected to the inlet of the gas-liquid condensation device, and the condensate outlet of the gas-liquid condensation device is connected to the inlet of the deep extraction device. The gas-liquid condensation device is provided with a non-condensable gas outlet.

[0015] Based on the joint setup of the solid waste treatment unit and the gas treatment unit, the two units work together. The solid waste treatment unit processes the viscous, difficult-to-package and transport adiponitrile waste oil into small carbon pellets, making the transportation and treatment of the adiponitrile plant's "three wastes" (waste gas, wastewater, and solid waste) much simpler. In addition, the condensate from the gas-liquid condensation device in the gas treatment unit contains some adiponitrile (ADN) and 2-methylglutaronitrile (MGN), which can be fed back to the deep extraction device of the solid waste treatment unit to achieve resource recycling. This synergistic effect between the solid waste and gas treatment units makes the entire treatment system an organic whole, with each link cooperating and promoting each other, achieving significant comprehensive results in reducing the emission of "three wastes" and improving the production efficiency of adiponitrile.

[0016] In some embodiments, the gas processing unit is further provided with an SCR treatment-drying device and an ammonia recovery device in sequence after the gas-liquid condensation device;

[0017] The non-condensable gas outlet of the gas-liquid condensation device is connected to the inlet of the SCR treatment-drying device.

[0018] In some embodiments, the vapor phase outlet of the hydrothermal treatment apparatus is connected to the inlet of the SCR treatment-drying apparatus.

[0019] The gaseous substances generated in the solids processing unit can be promptly processed in the gas processing unit, thus avoiding the unorganized emission of harmful gases.

[0020] In some embodiments, the deep extraction device is one or more of a falling film evaporator, a scraped evaporator, and a bi-shaft self-cleaning mixer.

[0021] Existing technologies often fail to completely extract adiponitrile (ADN) and 2-methylglutaronitrile (MGN) from adiponitrile waste oil, resulting in the loss of a significant amount of valuable substances. In the solid processing unit of this invention, a deep extraction device serves as the primary step. Utilizing a falling film evaporator, a scraped evaporator, and a twin-shaft self-cleaning mixer, this deep extraction device maximizes the extraction of ADN and MGN from the waste oil, significantly improving the recovery rate of the target products from the raw material. Compared to existing technologies, it offers higher extraction efficiency and resource utilization.

[0022] In some embodiments, the low-temperature heat treatment apparatus is any one of a high-shear stirring tank, a spray tower, or a planetary mixer with a distributor.

[0023] The high-viscosity waste residue generated after deep extraction is treated with low-temperature heat treatment devices such as high-shear stirring tank, spray tower, and planetary mixer with distributor. The low-temperature environment effectively avoids the decomposition of the target product in the waste residue or unnecessary side reactions that may occur due to high temperature. It also helps the high-viscosity waste residue to become loose and brittle, which is convenient for subsequent crushing and hydrothermal treatment.

[0024] In some embodiments, the hydrothermal treatment apparatus is a mechanically stirred tank or a drum reactor.

[0025] The hydrothermal treatment device is a thermochemical conversion device that uses a high-temperature and high-pressure hydrothermal environment to convert organic waste into carbon-based materials and other products. The waste residue powder after being processed by the crushing device is then processed by a hydrothermal treatment device such as a mechanical stirring kettle or a drum reactor to form a carbon-containing solid (hydrothermal carbon). The adiponitrile waste residue oil with high viscosity and difficult to package and transport is processed into small carbon spheres, making the transportation and treatment of the "three wastes" of the adiponitrile plant more convenient.

[0026] In some embodiments, the SCR processing-drying apparatus includes an SCR processing device and a drying device connected in sequence.

[0027] The gas phase outlet of the gas-liquid condenser discharges non-condensable gases, including nitrogen, a small amount of oxygen, and ammonia and NO released during the reaction. x The gas enters the SCR treatment-drying unit; the gas phase outlet of the hydrothermal treatment unit discharges a substance containing a small amount of water vapor and NO. x This portion of the gas also enters the SCR treatment-drying unit. The gas discharged from the gas phase outlet of the gas-liquid condenser and the gas discharged from the gas phase outlet of the hydrothermal treatment unit are treated and dehydrated by the SCR treatment-drying unit. The remaining nitrogen, a small amount of oxygen and ammonia are recovered by the ammonia recovery unit, and the remaining harmless tail gas is treated by the tail gas treatment unit before being discharged.

[0028] In some embodiments, the SCR treatment device is an SCR reactor, and the drying device is a dehydration tower.

[0029] In some embodiments, the filtration device is a plate and frame filter press.

[0030] Compared with existing technologies, the beneficial effects of this utility model are as follows: through the solid processing unit, adiponitrile waste oil with high viscosity and difficult to package and transport is efficiently converted into small carbon spheres with regular shape and stable properties. The solid carbon spheres are easy to store safely, package in a standardized manner and transport at low cost, which greatly reduces the difficulty and cost of logistics and management of "three wastes". At the same time, the carbon spheres themselves are resource products and can be used as fuel, adsorbent or especially phosphorus-containing soil amendment and landfill agent for high value utilization. This not only completely eliminates the environmental risks of the original waste oil, but also realizes the resource utilization of waste, which has outstanding environmental protection and economic benefits. Attached Figure Description

[0031] The accompanying drawings, which form part of this application, are used to provide a further understanding of the present invention. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an undue limitation of the present invention. In the drawings:

[0032] Figure 1 This invention illustrates a deep treatment system for adiponitrile waste oil.

[0033] Figure 2 This utility model demonstrates that... Figure 1 A diagram of hydrothermal carbon spheres prepared by an adiponitrile waste oil deep treatment system.

[0034] The above figures include the following reference numerals:

[0035] 1-Deep extraction device; 2-Low temperature heat treatment device; 3-Pulverizing device; 4-Hydrothermal treatment device; 5-Filtration device; 6-Gas-liquid condensation device; 7-SCR treatment-drying device; 8-Ammonia recovery device. Detailed Implementation

[0036] To facilitate understanding of this utility model, a more comprehensive description of it will be provided below, along with preferred embodiments. However, it should be understood that these embodiments are merely for more detailed explanation and should not be construed as limiting the utility model in any way, i.e., not limiting the scope of protection of this utility model.

[0037] In this utility model, unless otherwise explicitly specified and limited, the term "connection" and other such terms should be interpreted broadly. For example, it can refer to a fixed connection, a detachable connection, or an integral part; it can refer to a direct connection or communication, or an indirect connection or communication through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this utility model according to the specific circumstances.

[0038] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which this invention pertains. Unless otherwise specified, the devices used in the following embodiments are commercially available devices purchased by those skilled in the art.

[0039] Example 1

[0040] A deep treatment system for adiponitrile waste oil, such as Figure 1 As shown, it includes a solid processing unit; the solid processing unit includes a deep extraction device 1, a low-temperature heat treatment device 2, a pulverizing device 3, a hydrothermal treatment device 4, and a filtration device 5 connected in sequence.

[0041] The deep extraction device 1 is equipped with a crude nitrile outlet and a high-viscosity waste residue outlet. The high-viscosity waste residue outlet is connected to the inlet of the low-temperature heat treatment device 2. The low-temperature heat treatment device 2 is equipped with a solid waste residue outlet, which is connected to the inlet of the crushing device 3. The outlet of the crushing device 3 is connected to the inlet of the hydrothermal treatment device 4. The hydrothermal treatment device 4 is equipped with a solid-liquid mixture outlet, which is connected to the inlet of the filtration device 5. The filtration device 5 is equipped with a wastewater outlet and a carbon ball outlet.

[0042] The specific equipment of the deep extraction device 1 is not limited. As a further optional option, the deep extraction device 1 can be one or more of the following: falling film evaporator, scraped evaporator, and bi-shaft self-cleaning mixer.

[0043] The specific equipment of the low-temperature heat treatment device 2 is not limited. As a further alternative, the low-temperature heat treatment device 2 can be any one of a high-shear stirring tank, a spray tower, or a planetary mixer with a distributor.

[0044] The specific equipment of the hydrothermal treatment device 4 is not limited. As a further optional option, the hydrothermal treatment device 4 can be either a mechanically stirred tank or a drum reactor.

[0045] The specific equipment of the filter device 5 is not limited; as a further alternative, the filter device 5 is a plate and frame filter press.

[0046] Example 2

[0047] Based on the adiponitrile waste oil deep treatment system described in Example 1, this embodiment also includes a gas treatment unit;

[0048] The gas processing unit includes a gas-liquid condensation device 6; wherein, the gas phase outlet of the low-temperature heat treatment device 2 is connected to the inlet of the gas-liquid condensation device 6, and the condensate outlet of the gas-liquid condensation device 6 is connected to the inlet of the deep extraction device 1; the gas-liquid condensation device 6 is provided with a non-condensable gas outlet. The condensate of the gas processing unit after being processed by the gas-liquid condensation device 6 contains some adiponitrile (ADN) and 2-methylglutaronitrile (MGN), which can be fed back to the deep extraction device 1 of the solid processing unit to realize the recycling of resources.

[0049] Example 3

[0050] Based on the adiponitrile waste oil deep treatment system described in Example 2, the gas treatment unit of this embodiment also includes an SCR treatment-drying device 7 and an ammonia recovery device 8 to achieve efficient removal of nitrogen oxides (NOx), moisture removal, and recycling of ammonia resources in the exhaust gas.

[0051] The gas processing unit is equipped with an SCR treatment-drying device 7 and an ammonia recovery device 8 in sequence after the gas-liquid condensation device 6; the non-condensable gas outlet of the gas-liquid condensation device 6 is connected to the inlet of the SCR treatment-drying device 7.

[0052] The gas phase outlet of the hydrothermal treatment unit 4 is connected to the inlet of the SCR treatment-drying unit 7.

[0053] It should be noted that the SCR treatment-drying device 7 includes an SCR treatment device and a drying device connected in sequence.

[0054] The specific equipment 7 of the SCR treatment-drying unit is not limited. As a further optional option, the SCR treatment-drying unit 7 can be used in conjunction with the SCR treatment unit and the dehydration tower.

[0055] Example 4

[0056] A method for deep treatment of adiponitrile waste oil, wherein the method of this embodiment operates using the system described in Example 1, includes the following steps:

[0057] (1) Deep extraction: The adiponitrile waste oil is sent into the deep extraction device 1 and deep extraction is carried out at a temperature of 171.2℃ and a pressure of 750Pa for 4 days. The incompletely extracted ADN and MGN in the adiponitrile waste oil are deeply extracted. The liquid phase after extraction is crude nitrile, which is sent back to the adiponitrile plant for refining. The solid phase after extraction is high viscosity slag.

[0058] (2) Low temperature heat treatment: The high viscosity slag after deep extraction enters the low temperature heat treatment device 2. Oxygen-deficient air containing 4% oxygen is introduced at a gas flow rate of 20SLM. The high viscosity slag is treated at 184.4℃ for 8 hours. The solid phase after low temperature heat treatment is solid waste residue. The gas phase after low temperature heat treatment is input into the gas-liquid condensation device 6. After gas-liquid condensation, the condensate is returned to the deep extraction device 1 for deep extraction.

[0059] (3) Hydrothermal carbonization: After the solid waste residue is heat-treated at low temperature, it becomes a blocky solid after cooling. At this time, the waste residue oil has turned into black blocky coke. The solid waste residue powder after being crushed by the crushing device 3 is mixed with water at a liquid-solid ratio of 20:1 and enters the hydrothermal treatment device 4. The hydrothermal temperature is 207.8℃, the time is 6.5h, and the stirring speed is 400rpm. The solid-liquid mixture after hydrothermal carbonization is filtered and washed by the filtration device 5 to obtain carbon balls.

[0060] Example 5

[0061] A method for deep treatment of adiponitrile waste oil, wherein the method in this embodiment operates using the system described in Example 3, includes the following steps:

[0062] (1) Deep extraction: The adiponitrile waste oil is sent into the deep extraction device 1 and deep extraction is carried out at a temperature of 186.2℃ and a pressure of 1150Pa for 5 days. The incompletely extracted ADN and MGN in the adiponitrile waste oil are deeply extracted. The liquid phase after extraction is crude nitrile, which is sent back to the adiponitrile plant for refining. The solid phase after extraction is high viscosity slag.

[0063] (2) Low-temperature heat treatment: The high-viscosity slag after deep extraction enters the low-temperature heat treatment device 2. Oxygen-deficient air containing 1% oxygen is introduced at a flow rate of 430 SLM, and the high-viscosity slag is treated at 238.8℃ for 3 hours. The solid phase after low-temperature heat treatment is solid waste residue. The gas phase after low-temperature heat treatment is input into the gas-liquid condensation device 6. After gas-liquid condensation, the condensate is returned to the deep extraction device 1 for deep extraction. The gas phase after low-temperature heat treatment is input into the gas-liquid condensation device 6. The non-condensable gas after gas-liquid condensation is sequentially sent to the SCR treatment-drying device 7 for selective catalytic reduction and dehydration to remove NO. x The ammonia is recovered by the ammonia recovery device 8, and the remaining harmless tail gas is treated by the tail gas treatment device before being discharged. The selective catalytic reduction reaction temperature is 285℃, and the ammonia-to-nitrogen ratio is 1.33:1.

[0064] (3) Hydrothermal carbonization: After low-temperature heat treatment, the solid waste residue cools into a blocky solid. At this time, the waste residue oil has turned into black blocky coke. The solid waste residue powder, after being crushed by the crushing device 6, is mixed with water at a liquid-to-solid ratio of 82:1 and enters the hydrothermal treatment device 4. The hydrothermal temperature is 217.9℃, the time is 4 hours, and the stirring speed is 335 rpm. The gas phase after hydrothermal carbonization is sequentially sent to the SCR treatment-drying device 7 for selective catalytic reduction and dehydration to remove NO. x The ammonia recovery device 8 recovers residual ammonia, and the remaining harmless tail gas is treated by the tail gas treatment device before being discharged. The solid-liquid mixture after hydrothermal carbonization is filtered and washed by the filter device 5 to obtain carbon balls.

[0065] It should be noted that the above description is a further detailed explanation of the present invention in conjunction with specific embodiments, and should not be construed as limiting the specific implementation of the present invention to these descriptions. For those skilled in the art, various simple improvements and modifications can be made without departing from the concept of the present invention, and all such improvements and modifications should be considered to fall within the scope of protection of the present invention.

Claims

1. A system for deep processing of adiponitrile spent sludge oil, characterized in that, Includes solids processing units; The solid processing unit includes a deep extraction device, a low-temperature heat treatment device, a pulverizing device, a hydrothermal treatment device, and a filtration device connected in sequence. The deep extraction device is used to process adiponitrile waste oil to obtain crude nitrile and high-viscosity residue. The low-temperature heat treatment device is used to process the high-viscosity slag to obtain solid waste residue; The crushing device and the hydrothermal treatment device are used to process the solid waste residue, and carbon balls are obtained after filtration and washing by the filtration device.

2. The system for deep processing of adiponitrile spent slop oil according to claim 1, characterized in that, It also includes a gas processing unit; The gas processing unit includes a gas-liquid condensation device. The gas phase outlet of the low-temperature heat treatment device is connected to the inlet of the gas-liquid condensation device, and the condensate outlet of the gas-liquid condensation device is connected to the inlet of the deep extraction device. The gas-liquid condensation device is provided with a non-condensable gas outlet.

3. The system for deep processing of adiponitrile spent slop oil according to claim 2, characterized in that, The gas processing unit is further provided with an SCR treatment-drying device and an ammonia recovery device in sequence after the gas-liquid condensation device. The non-condensable gas outlet of the gas-liquid condensation device is connected to the inlet of the SCR treatment-drying device.

4. The system for deep processing of adiponitrile spent slop oil according to claim 3, characterized in that, The vapor phase outlet of the hydrothermal treatment device is connected to the inlet of the SCR treatment-drying device.

5. The system for deep processing of adiponitrile spent slop oil according to claim 1, characterized in that, The deep extraction device is one or more of the following: falling film evaporator, scraped evaporator, and bi-shaft self-cleaning mixer.

6. The deep treatment system for adiponitrile waste oil according to claim 1, characterized in that, The low-temperature heat treatment device is any one of a high-shear stirring tank, a spray tower, or a planetary mixer with a distributor.

7. The system for deep processing of adiponitrile spent slop oil according to claim 1, characterized in that, The hydrothermal treatment device is a mechanically stirred tank or a drum-type reactor.

8. The system for deep processing of adiponitrile spent slop oil according to claim 3, characterized in that, The SCR treatment-drying device includes an SCR treatment device and a drying device connected in sequence.

9. The system for deep processing of adiponitrile spent slop oil according to claim 8, characterized in that, The SCR treatment device is an SCR reactor, and the drying device is a dehydration tower.

10. The system for deep processing of adiponitrile spent slop oil of claim 1, wherein, The filtration device is a plate and frame filter press.

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