Equipment and method for producing cyclic ketone compound by oxidizing cycloolefin by using adipic acid production waste gas

Abstract

The invention belongs to the field of chemical engineering manufacturing industry, and relates to equipment and a method for producing cyclic ketone compounds by oxidizing cycloolefin by using waste gas produced by adipic acid. Raw material gas A containing nitrous oxide from an adipic acid production process production line can be subjected to oxygen removal, so that the oxygen content is less than 100ppm; the raw material gas A containing nitrous oxide from the adipic acid production line can also be purified into purer gas containing 50-99% of N2O, and the purer gas is used for reacting with the cycloolefin compound; the reaction equation is CnH2n-2 (cycloolefin) + N2O (nitrous oxide)-> CnH2n-2O (a product cyclic ketone compound) + a byproduct + N2 superscript (nitrogen), wherein n is a positive integer from 4 to 24. The device is stable in consumption quota, low in production cost and high in economic benefit compared with the prior art.

Description

Technical Field

[0001] This invention belongs to the field of chemical manufacturing and relates to equipment and methods for producing cyclic ketone compounds by oxidizing cyclic olefins using tail gas containing nitrous oxide emitted from an adipic acid production line. In particular, it relates to equipment and methods for producing cyclic ketone compounds by oxidizing cyclic olefins using waste gas from adipic acid production. Background Technology

[0002] N2O generated by human activities mainly comes from industrial and agricultural production. Since the Industrial Revolution, the concentration of N2O in the atmosphere has been continuously increasing, and it is projected that by 2100, the concentration of N2O in the atmosphere will be 1.5 times its current level. Therefore, the elimination of N2O has gradually become a hot topic of international research. A large amount of N2O is emitted from the Earth every year. Simply eliminating N2O through catalytic decomposition or selective catalytic reduction is not the best method, especially for industrial production with high N2O emissions. For example, the traditional adipic acid production process produces a large number of byproducts, and the waste gas generated by this process can increase the N2O content in the atmosphere by about 10%. Therefore, the recycling and utilization of N2O is of great significance. Domestic and international efforts are focused on further research and treatment to increase its utilization value, thereby achieving the goal of controlling N2O emissions. Research has found that the research field of N2O mainly includes three aspects: one is the purification research of N2O. After purification, N2O can be utilized to achieve the goal of N2O emission reduction. High-purity N2O can often be used in industries such as medical treatment, electronics manufacturing, and food processing aids, improving product quality while reducing production costs. This has led to a series of purification methods. Dolan Williamsb et al. invented a method for separating N2O from a mixture of N2, O2, and N2O using Pressure Swing Adsorption (PSA) technology to selectively adsorb N2O with an adsorbent, achieving purification. However, the mixed gases produced by industrial plants contain not only N2, O2, and N2O, but also large amounts of CO2 and other impurities. In response, Chevalier Gilbert et al. proposed using a selective permeation membrane to recover N2O from gas mixtures, but this is only suitable for recovering N2O from gas mixtures with small emissions. Nagamura Tashi invented a process for recovering N2O, first feeding N2O gas containing N2, O2, and water vapor into a compressor, then distilling it, with pure N2O discharged from the bottom of the distillation column. However, this N2O recovery process is complex to operate, and the lubricating oil in the compressor may cause secondary pollution to the N2O mixture. Therefore, the separation and purification of N2O is often costly and difficult to operate, which limits its further development. On the other hand, research focuses on the decomposition of N2O. Catalytic decomposition is an effective method for eliminating N2O. Based on the different active components of the catalyst, catalysts can be classified into ion-exchange molecular sieves, supported noble metals, and transition metal oxides, among others. L. Yan, R.J. Lu, and M. Tursun, among others, have reported on their applications. The adipic acid production unit of China National Petroleum Corporation's Liaoyang Petrochemical Company has a designed capacity of approximately 50,000 tons of N2O per year as a byproduct. The traditional N2O emission reduction unit uses catalytic decomposition technology from BASF (Germany) and a newly built unit using a process package from STEULER (Germany), aiming to reduce the emission of the inert greenhouse gas N2O.During the production of adipic acid, approximately 5330 kg of N2O gas is generated per hour. After treatment by the N2O emission reduction unit, over 95% of the N2O is decomposed into N2 and O2. The Liaohua Traditional N2O emission reduction unit, initially built in August 2007, mainly consists of an N2O emission reduction reaction unit, a waste heat recovery unit, and an air compressor unit. Completed and put into operation in March 2008, the Liaohua Traditional N2O emission reduction unit is designed to reduce N2O gas emissions by 41,000 tons annually, with a designed operating time of 8000 hours per year. The decomposition method releases the generated N2 and O2 into the atmosphere. Domestic adipic acid production plants produce approximately 1 million tons of N2O as a byproduct annually. While catalysts can decompose N2O into environmentally non-toxic and harmless N2 and O2, the stability of the catalyst and the demanding reaction conditions such as high temperature and high pressure required for the catalytic process pose challenges to the production process, and the effective reuse of N2O has generally not been achieved. The nitrous oxide decomposition method incurs significant costs in terms of labor, electricity, and equipment investment. Although it meets environmental protection requirements and international emission standards, this method only recovers heat. IVANOV.AA et al. reported the use of zeolite and its modified catalysts to catalyze the oxidation of benzene to phenol, with N2O serving as an oxygen carrier for the direct oxidation of benzene to phenol. The main and side reactions occurring in the N2O-involved benzene oxidation to phenol reaction are shown in equations (1) to (3).

[0003]

[0004] From a thermodynamic perspective, the reaction probabilities of equations (1), (2), and (3) are all very high. Due to the occurrence of side reactions, the selectivity of the products is greatly reduced, and greenhouse gas CO2 is also produced, resulting in very poor overall economic efficiency. In the process of N2O oxidation of propane to propylene, researchers have verified the different conversion rates exhibited by different oxidants under the same catalyst conditions. Bulánek R et al. investigated the effects of O2 and N2O as oxidants on the reaction activity of propane oxidation to propylene under the same reaction conditions, but there was a problem of catalyst deactivation. Therefore, for the propane dehydrogenation to propylene process, the research on catalysts is crucial, especially the stability and catalytic efficiency of the catalysts, which restrict its industrial production.

[0005] From a green chemistry perspective, research on using N2O as an oxidant in chemical raw material production is of great significance. It not only solves environmental problems but also brings significant economic benefits to production, representing a green chemical technology that turns waste into treasure. Therefore, new methods for N2O emission reduction are urgently needed. Among these, using N2O as a selective oxygen donor for the catalytic oxidation of hydrocarbons has attracted widespread attention from researchers. Numerous studies have found that N2O can non-catalytically oxidize olefins to produce carbon-based compounds. Panov.GI et al. introduced a highly efficient method for oxidizing olefins to carbon-based compounds, transferring oxygen from N2O to unsaturated carbon atoms with near 100% selectivity. This oxidation method can be applied to a variety of organic compounds, including aliphatic, cyclic, and heterocyclic olefins and their numerous derivatives.

[0006] Cyclohexanone is generally classified into two main categories based on its applications: amide-grade and non-amide-grade. Amide-grade cyclohexanone is primarily used to manufacture caprolactam and adipic acid, both crucial raw materials for producing fiber PA6 and engineering plastic PA66. Simultaneously, cyclohexanone is an important industrial solvent and can also be used in the production of pharmaceutical intermediates. In China, most cyclohexanone plants are downstream caprolactam and adipic acid production facilities, and its market as an organic solvent has not yet been fully developed. With the gradual maturation of the polyamide industry chain, more cyclohexanone production capacity will be released, and its application in high-end inks, additives, adhesives, and other fields will significantly increase. Major domestic manufacturers are as follows:

[0007]

[0008] Currently, the commonly used methods for synthesizing cyclohexanone are: ① phenol hydrogenation, ② cyclohexane oxidation, and ③ cyclohexene synthesis. Among them, the phenol hydrogenation method mainly involves the catalytic hydrogenation of phenol under the action of hydrogen and a catalyst, as shown in reaction formula (4). Compared with other processes, the phenol hydrogenation method for producing cyclohexanone is safer, easier to separate and purify the product, and produces a better quality cyclohexanone. However, the main problems it faces are the design of the catalyst and the substitution of the hydrogen source. In addition, during the reaction, there is an intermediate active substance in the form of an enol before the conversion of phenol to cyclohexanone, resulting in the presence of cyclohexane, cyclohexanol, ethers, and alkane derivatives of phenol as byproducts, leading to a low yield of the target product, cyclohexanone.

[0009]

[0010] Another method is the cyclohexane oxidation method, as shown in reaction formula (5). Cyclohexane is produced by hydrogenating benzene, and then oxidized to obtain cyclohexanone. More than 90% of cyclohexanone products are obtained by this method. There are two oxidation process routes for cyclohexane oxidation: one is a catalytic oxidation process, and the other is a non-catalytic oxidation process. The catalytic oxidation process mainly uses cobalt salts, boric acid, or metaboric acid as catalysts. However, overall, this method has high energy consumption and high pollution, and with the continuous improvement of environmental awareness and requirements, it faces the need for improvement.

[0011]

[0012] Cyclohexene hydration is an important method for producing cyclohexanone, as shown in reaction formula (6). Benzene, as a substrate, undergoes selective hydrogenation under hydrogenation catalysis to prepare a cyclohexene intermediate. This intermediate can then be efficiently hydrated to produce cyclohexanol, which is subsequently dehydrogenated to generate cyclohexanone. However, the cyclohexene hydration process for producing cyclohexanol is relatively complex, with low single-pass conversion and high energy consumption, making it unsuitable for industrial production.

[0013]

[0014] Currently, there are two main caprolactam production processes in China: cyclohexane oxidation and cyclohexene hydration. As of the end of 2020, the total caprolactam production capacity in China was 4.37 million tons. Of this, the cyclohexene hydration process accounted for 2.31 million tons (53% of the total capacity), the cyclohexane oxidation process accounted for 1.66 million tons (38% of the total capacity), and the phenol process accounted for 400,000 tons (9% of the total capacity). New caprolactam projects under construction will add 3 million tons of capacity. Except for the Baling Petrochemical relocation project, which plans to use the cyclohexene esterification process, all other projects will use the cyclohexene hydration process. Both methods involve cyclohexanone intermediates. However, the existing technologies for both processes have high consumption quotas, making it difficult to reduce production costs and economic efficiency. Summary of the Invention

[0015] Purpose of the invention

[0016] To address the problems existing in the aforementioned technical processes, this invention provides an apparatus and method for producing cyclic ketone compounds by oxidizing cyclic olefins using waste gas from adipic acid production. This invention utilizes the waste gas from adipic acid production line, specifically the tail gas containing nitrous oxide emitted during the adipic acid production process, to oxidize cyclic olefins and produce cyclic ketone compounds.

[0017] Technical solution

[0018] Production method for producing cyclic ketones by oxidizing cyclic olefins using adipic acid production waste gas:

[0019] In the aziridine production line, the nitrous oxide-containing feed gas A can be deoxygenated to a content of less than 100 ppm, allowing it to react directly with cyclic olefins to produce cyclic ketone compounds and byproducts. The nitrous oxide-containing feed gas A in the aziridine production line can also be purified to a purer gas containing 50-99% N₂O for reaction with cyclic olefin compounds. The reaction equation is as follows:

[0020] C n H 2n-2 (Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24.

[0021] Furthermore, the specific process for the nitrous oxide-containing raw material gas A in the diacid production line to react directly with cyclic olefins to generate cyclic ketone compounds and byproducts after oxygen removal (to reduce the oxygen content to less than 100 ppm) is as follows: The nitrous oxide-containing raw material gas A in the diacid production line enters the raw material gas A storage tank. The raw material gas A storage tank is a floating head gas storage tank. The operating pressure of the raw material gas A storage tank is 0.01–1.0 MPa, and the operating temperature is 0–50°C. The raw material gas A in the raw material gas A storage tank enters a variable... The pressure adsorption deoxygenation device removes oxygen to form gas composition B. Gas composition B can also be purified to a higher N2O concentration, between 50% and 99%. The oxygen content in gas composition B is less than 100 ppm. Gas composition B enters the raw material gas B storage tank, which is a floating head type tank. The operating pressure of the raw material gas B storage tank is 0.01 to 1.0 MPa, and the operating temperature is 37 to 50°C. Gas composition B is pressurized to 1.0 to 5.0 MPa and 37 to 60°C by the first gas booster and then enters the raw material gas B metering tank.

[0022] A large specific surface area metallic material is added inside the fixed-bed reactor. Gas composition B from the feed gas metering tank is metered and pressurized to a pressure of 5–30 MPa, forming gas stream M1. Gas stream M1 is mixed with gas stream M3, a portion of which is returned from the high-pressure separator via a second gas booster. The standard state volume ratio of gas stream M1 to gas stream M3 is controlled at 1:1 to 1:50. Then, the mixture enters a high-pressure heat exchanger to exchange heat with the reaction product stream M4 from the fixed-bed reactor filled with the large specific surface area metallic material. After heat exchange, the mixture of gas streams M1 and M3 flows... The temperature reaches 90–200℃, then enters a high-pressure preheater to be preheated to 210–350℃. After preheating, the mixture of gas streams M1 and M3 enters a fixed-bed reactor packed with a large specific surface area metal material. Cycloolefin or cycloolefin-saturated alkane mixture stream M2, originating from a cycloolefin metering tank, is pressurized and metered before entering a high-pressure heat exchanger to exchange heat with reaction product stream M4 from the fixed-bed reactor packed with a large specific surface area metal material. After heat exchange, the temperature reaches 90–200℃, and then it enters the high-pressure preheater for further preheating, reaching the required temperature of 100℃ for the fixed-bed reactor. At approximately 350°C, gas streams M1 and M3, along with a mixture of cyclic olefins or cyclic olefin-saturated alkane streams M2, enter a fixed-bed reactor packed with a large specific surface area of ​​metal. Within this reactor, they react to produce stream M4, which includes the target product, a cyclic ketone compound, with a selectivity of 93%–99%, and a byproduct, a cyclic enone compound, at a concentration of 0.5%–5%. The light component of the byproduct has a boiling point lower than that of the cyclic ketone compound, which is then separated by distillation. The heavier component of the byproduct, a cyclic enone compound with a boiling point higher than that of the cyclic ketone compound, is further separated by distillation. The cyclic ketone compound is hydrogenated in a hydrogenation fixed-bed reactor to produce a cyclic ketone compound, which is then recovered by a distillation column. The hydrogenation fixed-bed reactor is packed with a palladium-Al₂O₃ catalyst. The operating pressure of the hydrogenation fixed-bed reactor is 0.1–1.0 MPa, and the operating temperature is 0–60 °C. A mixture of cyclic olefins or cyclic olefins and saturated alkanes is continuously fed into the fixed-bed reactor along with feed gas B through a high-pressure heat exchanger and a high-pressure preheater. The molar ratio of nitrous oxide in gas stream M1 to cyclic olefins in gas stream M2 is 0.05–1, and the following reaction occurs: C n H 2n-2 (Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24;

[0023] The reaction temperature in the fixed-bed reactor is controlled at 100–350℃, and the pressure in the fixed-bed reactor is 5–30 MPa. The main target product, cyclic ketone compound, and by-products are generated. The by-products include a light component with a lower boiling point than the cyclic ketone compound, which accounts for 0.5%–3% of the by-products, and a heavy component, cyclohexenone compound, with a higher boiling point than the cyclic ketone compound, which accounts for 0.5%–3% of the cyclohexenone compound. The selectivity for the formation of cyclic ketone compounds from cyclic olefins is greater than 93%–99%, and the conversion rate of nitrous oxide in gas composition B is greater than or equal to 90%–99.9%.

[0024] The inlet stream of the high-pressure separator is called M6. Part of the gas phase is mixed with the gas stream M1 by the stream M3 compressed and returned by the second gas booster of the circulation system, and the other part is called stream M8, which enters the cryogenic gas discharge tank. In the cryogenic gas discharge tank, the liquid phase enters the low-pressure separator for recycling, and the gas phase is called gas stream M9. After treatment and testing, the N2O content is less than 0.1% of the total volume and then discharged.

[0025] The liquid phase in the high-pressure separator enters the low-pressure separator. The liquid phase in the low-pressure separator consists of cyclic ketone compound products and reaction byproducts. The reaction byproducts include low-boiling-point byproducts, light and heavy cyclic ketone compounds, and unreacted cyclic alkenes. Alternatively, the liquid phase in the low-pressure separator consists of cyclic ketone compound products and reaction byproducts, including light and heavy cyclic ketone compounds and a mixture of unreacted cyclic alkenes and saturated alkanes. This is called the cyclic olefin recovery distillation column M7. The bottom of the cyclic olefin recovery distillation column of the cyclic olefin recovery distillation column yields the target product, a mixture of cyclic ketone compounds and byproducts. The unreacted cyclic alkenes and the mixture of cyclic alkenes and saturated alkanes are returned to the cyclic olefin metering tank for recycling.

[0026] The gases from the top of the cryogenic gas emission tank and the top of the low-pressure separator are combined and enter the water washing tower. The function of the cryogenic gas emission tank is to cool the gas stream from the outlet of the cryogenic gas emission tank to the water washing tower to 5-15°C under the action of the coolant. The liquid phase of the water washing tower enters the oil-water separator for oil-water separation. The oil phase of the oil-water separator is recycled back to the olefin metering tank. The gas phase of the water washing tower is discharged after testing and the organic matter content is less than 5 ppm. The water at the bottom of the oil-water separator is pumped into the interior of the top of the water washing tower by a water circulation pump for spraying. The water and trace organic compounds at the bottom of the water washing tower enter the oil-water separator for separation.

[0027] The target product, cyclic ketones, and light components obtained from the bottom of the cyclic olefin recovery distillation column are fed into the recovery distillation column. The light components obtained from the top of the distillation column are stored and utilized. The main product obtained from the bottom of the light component recovery distillation column is fed into the cyclic ketone and cyclic enol recovery distillation column via stream M11. The target product, cyclic ketones, obtained from the top of the column is stored and utilized via stream M12. The bottom of the column yields cyclic enol C.n H 2n-4 O is sent to the pharmaceutical section via logistics M13B for storage and utilization. It is an important intermediate in the pharmaceutical industry. The heavy component byproduct, cyclic ketone compound, is sent to a hydrogenation fixed-bed reactor via logistics M13A for hydrogenation to generate the target cyclic ketone compound. The hydrogenation reaction is carried out in the hydrogenation fixed-bed reactor in the presence of Al2O3 catalyst coated with 3% to 5% palladium, at a reaction pressure of 0.1 to 1.0 MPa, a hydrogenation reaction temperature of 30 to 100°C, and a cyclic ketone to hydrogen molar ratio of 1:400 to 1000. The cyclic ketone compound is then returned to the cyclic ketone and cyclic ketone recovery distillation column for further distillation to obtain the target cyclic ketone compound.

[0028] Furthermore, when the gas composition B needs to be purified, it is purified to a higher purity containing 50-99% N2O by a nitrous oxide purification device and then enters the raw material gas B storage tank for reaction with cyclic olefin compounds.

[0029] Furthermore, after adding a large specific surface area metal material inside the fixed-bed reactor, the entire equipment needs to be purged with N2 gas from a nitrogen tank before the reaction begins. The subsequent reaction is carried out under N2 protection. The gas stream M1 and gas stream M3 mixture, as well as the cyclic olefin or cyclic olefin-saturated alkane mixture stream M2, are mixed and then pass through a high-pressure heat exchanger to reach a temperature of 90-200°C. After passing through a high-pressure preheater, the temperature reaches 210-350°C. The reaction temperature inside the fixed-bed reactor is controlled at 100-350°C, and the pressure inside the fixed-bed reactor is 5-30 MPa. The material entering the high-pressure cooler is cooled to 0-35°C by the high-pressure cooler.

[0030] Furthermore, the fixed-bed reactor is internally equipped with a cage-type heat exchanger. The cage-type heat exchanger is of the type specified in Chinese Patent Publication No. CN209197530U, entitled "A Cage-Type Heat Exchanger in a Catalytic Hydrogenation Reactor." A heat transfer fluid at 100–350°C is introduced into the cage-type heat exchanger within the catalytic hydrogenation reactor to remove the heat released during the reaction of cyclic olefins with nitrous oxide. A large specific surface area metal material is added to the inner cavity of the fixed-bed reactor. The fixed-bed reactor is a tubular fixed-bed reactor with an outer jacket layer. A heat transfer fluid at 100–350°C passes through the jacket, removing the heat released during the reaction of cyclic olefin compounds with nitrous oxide. The tubular fixed-bed reactor can be a single-tube or multi-tube parallel fixed-bed reactor.

[0031] Furthermore, the large specific surface area metal material is one or more of Raschig rings, Sirra rings, and structured corrugated wire mesh fillers, with a specific surface area of ​​200-2000 square meters per cubic meter. The Raschig ring dimensions are 2mm × 2mm × 0.2mm (diameter × height × thickness), 4mm × 4mm × 0.2mm, 6mm × 6mm × 0.2mm, 10mm × 10mm × 0.2mm, 15mm × 15mm × 0.2mm, 25mm × 25mm × 0.2mm, or Sirra rings or structured corrugated wire mesh fillers with the same specific surface area. The metal material is one or more alloys of 304 stainless steel, 316L stainless steel, copper, iron, nickel, chromium, or manganese.

[0032] Furthermore, the fixed-bed reactor is a vertical fixed-bed reactor. Cycloolefins are continuously injected from the top of the fixed-bed reactor in one go. Nitrous oxide gas streams M1 and M3 are continuously injected from the top of the fixed-bed reactor in one go, or nitrous oxide gas streams M1 and M3 are continuously injected into the fixed-bed reactor in three parts from the top, middle and bottom positions. The top feed position refers to the position from 0.0% to 20% of the fixed-bed reactor from top to bottom, the middle feed position refers to the position from 20% to 40% of the fixed-bed reactor from top to bottom, and the bottom feed position refers to the position from 40% to 70% of the fixed-bed reactor from top to bottom. The proportion of nitrous oxide feed in the three positions accounts for 20% to 40% of the total nitrous oxide feed, respectively. Alternatively, nitrous oxide gas streams M1 and M3 are injected uniformly from the top of the fixed-bed reactor from 0.0% to 70%.

[0033] Furthermore, in the cyclic olefin to saturated alkane mixture, the mol ratio of cyclic olefin to saturated alkane is 1:1 to 1:20, and the saturated alkane refers to straight-chain alkanes, branched alkanes or cycloalkanes from C4 to C20.

[0034] Furthermore, the material M7 first enters the top of the cyclic olefin recovery distillation column as light component and cyclic olefin material M8, which is then recycled back to the cyclic olefin storage tank. The bottom product of the cyclic olefin recovery distillation column is material M9. Material M9 goes to the light component by-product recovery distillation column. After distillation in the light component by-product recovery distillation column, the top component of the light component column, material M10, is distilled off and sent to the storage tank. The bottom component of the light component by-product recovery distillation column is material M11. Material M11 goes to the cyclic ketone and cyclic enene recovery distillation column. After distillation, the top of the distillation column is... The target product, a cyclic ketone compound, becomes stream M12. Stream M12 is sent to the product storage tank. The bottom product of the cyclic ketone and cyclic enone recovery distillation column, containing a mixture of byproducts cyclic enone and cyclic ketone, is called stream M13. After heat exchange, M13 enters the hydrogenation fixed-bed reactor. After hydrogenation, the hydrogenated product is generated as stream M14. Stream M14 is separated by heat exchange, cooling, high pressure, and low pressure to obtain stream M15, which is a cyclic ketone compound. Stream M15 is returned to the cyclic ketone and cyclic enone recovery distillation column for further distillation to obtain the cyclic ketone compound.

[0035] Furthermore, the hydrogenation product of the hydrogenation fixed-bed reactor contains hydrogenated cyclic ketone compounds and hydrogen gas. This product enters the hydrogenation product heat exchanger via stream M14 to reach a temperature of 50–130°C. The cyclic ketone and hydrogen mixture exiting the bottom of the heat exchanger then enters the hydrogenation product high-pressure cooler via stream M16, where it is cooled to 5–30°C. The product then enters the hydrogenation product high-pressure separator via stream M16 for gas-liquid separation. The liquid at the bottom of the high-pressure separator enters the low-pressure separator via stream M18A. The liquid stream separated at the bottom of the low-pressure separator passes through stream M15 and is then distilled in the cyclic ketone and cyclic ketene recovery distillation column to obtain the target cyclic ketone compound. The gaseous portion of the hydrogenation product high-pressure separator, stream M18B, goes to the hydrogenation product cryogenic discharge tank. After cooling to 0–10°C, it enters the hydrogenation tail gas washing tower via stream M20. The cryogenic discharge tank serves as the... The process involves cooling the flow rate of the hydrogenated product from the cryogenic discharge tank to the hydrogenated tail gas scrubbing tower to 5-15°C using a coolant. The gas phase flow M19 from the low-pressure separator of the hydrogenated product enters the hydrogenated tail gas scrubbing tower, where organic compounds contained in the residual gas from the low-pressure separator are removed. If the organic matter content in the gas is ≤5ppm, it is discharged from the top of the hydrogenated tail gas scrubbing tower. Hydrogen is collected from the top of the hydrogenated tail gas scrubbing tower for recycling. The liquid flow M21 from the bottom of the hydrogenated tail gas scrubbing tower goes to the hydrogenated product oil-water separator for oil-water separation. The oil layer is periodically recovered and centrally processed. The water from the bottom of the hydrogenated product oil-water separator is pumped to the interior of the top of the hydrogenated tail gas scrubbing tower for spraying. The water from the bottom of the hydrogenated tail gas scrubbing tower contains trace amounts of organic matter and is circulated into the hydrogenated product oil-water separator. In the hydrogenated product oil-water separator, the trace organic matter is separated from the water layer.

[0036] A production apparatus for a method of producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas, as described above, includes a nitrogen tank, a cyclic olefin metering tank, a feed gas B metering tank, a high-pressure heat exchanger, a high-pressure preheater, a fixed-bed reactor, a high-pressure cooler, a high-pressure separator, a cryogenic gas discharge tank, and a low-pressure separator. The cyclic olefin metering tank is equipped with a cyclic olefin inlet, and its outlet is connected to the inlet of the fixed-bed reactor via a pipeline through the high-pressure heat exchanger and the high-pressure preheater. The outlet of the feed gas B metering tank is connected via a pipeline through the high-pressure heat exchanger and the high-pressure preheater. The inlet and outlet of the fixed-bed reactor are connected to the inlet of the high-pressure separator via pipelines through a high-pressure heat exchanger and a high-pressure cooler. The outlet at the upper end of the high-pressure separator is connected to the inlet of a cryogenic gas emission tank via a pipeline. A nitrogen emission port is located at the upper end of the cryogenic gas emission tank. The outlet at the lower end of the high-pressure separator is connected to the inlet of a low-pressure separator via a pipeline. A product collection port is located at the lower end of the low-pressure separator, and a gas emission port is located at the upper end of the low-pressure separator. The emitted gas goes to a water scrubbing tower to recover organic components. Inorganic gases, after being treated and meeting standards, are emitted at high altitude. The olefin metering tank, feed gas B metering tank, high-pressure heat exchanger, high-pressure preheater, fixed-bed reactor, high-pressure cooler, high-pressure separator, cryogenic gas exhaust tank, and low-pressure separator are all connected to a nitrogen tank via pipelines, and the nitrogen tank is equipped with a nitrogen inlet. The system also includes a cyclic olefin recovery distillation column, a pressure swing adsorption (PSA) deoxygenation unit, a light component by-product recovery distillation column, a first gas booster, and a second gas booster. The cyclic olefin recovery distillation column has an adipic acid feed gas inlet, and its outlet is connected to the inlet of the PSA deoxygenation unit via a pipeline. The PSA deoxygenation unit... The outlet is connected to the inlet of the light component by-product recovery distillation column via a pipeline. The outlet of the light component by-product recovery distillation column is connected to the inlet of the first gas booster via a pipeline. The feed gas B metering tank is equipped with a feed gas B inlet. The outlet of the first gas booster is connected to the feed gas B inlet of the feed gas B metering tank via a pipeline. The outlet of the high-pressure separator is connected to the inlet of the second gas booster via a pipeline that is connected to the pipeline that is connected to the pipeline that is connected to the pipeline that is connected to the pipeline that is connected to the pipeline that is connected to the high-pressure heat exchanger, and then connected to the outlet of the second gas booster.

[0037] Furthermore, the bottom of the cyclic olefin metering tank, the raw material gas B metering tank, the high-pressure heat exchanger, the high-pressure preheater, the high-pressure cooler, the high-pressure separator, the cryogenic gas discharge tank, and the low-pressure separator are provided with low-pressure discharge ports.

[0038] Furthermore, the outlet pipe of the cyclic olefin metering tank is equipped with a high-pressure cyclic olefin feed pump, the outlet pipe of the raw material gas B metering tank is equipped with a first hydrogenation reactor feed pump, the outlet pipe of the fixed bed reactor is equipped with a high-pressure filter, and the inlet pipe of the fixed bed reactor is connected to a nitrogen tank.

[0039] Advantages and effects

[0040] The waste gas containing nitrous oxide from the nitrous oxide production line only undergoes oxygen removal treatment. Other gases it contains do not need to be separated and directly enter a fixed-bed reactor filled with metal material with a large specific surface area. The fixed-bed reactor is equipped with a cage heat exchanger of CN209197530U. In the fixed-bed reactor, the nitrous oxide in the mixed gas reacts with cyclic olefins to generate highly selective target product cyclic ketone compounds.

[0041] Secondly, the gas section of the high-pressure separator in this process unit adopts a certain proportion of reflux. The refluxed gas is mixed with the raw material gas B, which increases the inert gas content in the reactor, enhances the mass and heat transfer effect in the fixed bed reactor, and makes the operation of the fixed bed reactor more stable.

[0042] Third, the consumption quota is stable, and the production cost is lower and the economic benefits are higher than those of existing technologies. Attached Figure Description

[0043] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. The scope of protection of the present invention is not limited to the descriptions below.

[0044] Figure 1 This is a schematic diagram illustrating the production process of cyclic ketone compounds by oxidizing cyclic olefins using waste gas from adipic acid production.

[0045] Figure 2 This is a schematic diagram of the equipment connection structure for oxidizing cyclic olefins to produce cyclic ketone compounds using waste gas from adipic acid production.

[0046] Explanation of reference numerals in the attached diagrams: V101. Nitrogen tank; V102. Feed gas A storage tank; U101. Pressure swing adsorption deoxygenation unit; V103. Feed gas B storage tank; R101. Cycloolefin metering tank; R102. Feed gas B metering tank; E101A. High-pressure heat exchanger; E102A. High-pressure preheater; K101. Fixed-bed reactor; K102. Hydrogenation fixed-bed reactor; R103A. High-pressure cooler; R103B. Hydrogenation product high-pressure cooler; R104A. High-pressure separator; R104B. Hydrogenation product high-pressure separator; R105A. Cryogenic gas exhaust tank; R105B. Hydrogenation product cryogenic exhaust tank; R106A. Low-pressure separator; R106B. Hydrogenation product low-pressure separator; W101A. Water washing tower. W102B. Hydrogenation tail gas scrubbing tower; X101A. Oil-water separator; X102B. Hydrogenation product oil-water separator; T101. Cyclic olefin recovery distillation tower; T102. Light component by-product recovery distillation tower; T103. Cyclic ketone and cyclic enone recovery distillation tower; E101B. Hydrogenation product heat exchanger; C102A / B. Hydrogen compressor; P101A / B. High-pressure cyclic olefin feed pump; P102A / B. First hydrogenation reactor feed pump; P102A / C. Second hydrogenation reactor feed pump; P103. Water circulation pump; P104. Feed pump; H101A / B. First gas booster; H102A / B. Second gas booster; G101. Nitrous oxide purification unit; F101. High-pressure filter. Detailed Implementation

[0047] like Figure 1 and Figure 2 As shown, the production method for producing cyclic ketone compounds by oxidizing cyclic olefins using waste gas from adipic acid production involves using nitrous oxide-containing feed gas A from the adipic acid production line. The oxygen content of the feed gas A can be reduced to less than 100 ppm after deoxygenation, allowing it to react directly with cyclic olefins to produce cyclic ketone compounds and byproducts. Furthermore, nitrous oxide-containing feed gas A from the adipic acid production line can be purified to a purer gas containing 50-99% N₂O for reaction with cyclic olefin compounds. The reaction equation is as follows:

[0048] C n H 2n-2 (Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24.

[0049] The specific process for the nitrous oxide-containing feed gas A in the aziridine production line to react directly with cyclic olefins to generate cyclic ketones and byproducts after oxygen removal (to reduce the oxygen content to less than 100 ppm) is as follows: The nitrous oxide-containing feed gas A in the aziridine production line enters feed gas A storage tank V102. Feed gas A storage tank V102 is a floating head gas storage tank. The operating pressure of feed gas A storage tank V102 is 0.01–1.0 MPa, and the operating temperature is 0–50°C. Feed gas A from feed gas A storage tank V102 then enters the pressure swing adsorption deoxygenation unit U1. 01. Oxygen is removed to form gaseous component B. Gaseous component B can also be purified to a higher N2O concentration, between 50% and 99%. The oxygen content in gaseous component B is less than 100 ppm. Gaseous component B enters the raw material gas B storage tank V103. The raw material gas B storage tank V103 is a floating head tank. The operating pressure of the raw material gas B storage tank V103 is 0.01 to 1.0 MPa, and the operating temperature is 37 to 50°C. Gaseous component B is pressurized to 1.0 to 5.0 MPa and 37 to 60°C by the first gas booster H101A / B, and then enters the raw material gas B metering tank R102.

[0050] A large specific surface area metal material is added inside the fixed-bed reactor K101. Gas composition B from the feed gas metering tank R102 is metered and pressurized to a pressure of 5-30 MPa, forming gas stream M1. Gas stream M1 is mixed with gas stream M3, which is partially returned from the high-pressure separator R104A via the second gas booster H102A / B. The standard state volume ratio of gas stream M1 to gas stream M3 is controlled at 1:1 to 1:50. Then, it enters the high-pressure heat exchanger E101A to exchange heat with the reaction product stream M4 from the fixed-bed reactor K101 filled with the large specific surface area metal material. After heat exchange, gas stream M1 and gas stream M3... The mixture flow reaches a temperature of 90–200℃, then enters the high-pressure preheater E102 for preheating to 210–350℃. After preheating, the mixture flow of gaseous streams M1 and M3 enters the fixed-bed reactor K101 filled with a large specific surface area metal material. The cyclic olefin or cyclic olefin-saturated alkane mixture flow M2 comes from the cyclic olefin metering tank R101. After pressurization and metering, it enters the high-pressure heat exchanger E101A to exchange heat with the reaction product flow M4 from the fixed-bed reactor K101 filled with a large specific surface area metal material. After heat exchange, the temperature reaches 90–200℃, and then enters the high-pressure preheater E102A for preheating. After preheating, it reaches the fixed-bed reactor K101. The required temperature is 100–350℃. The gas stream M1 and gas stream M3 mixture, along with the cyclic olefin or cyclic olefin-saturated alkane mixture M2, react within the fixed-bed reactor K101 to produce stream M4, which includes the target product, a cyclic ketone compound, with a selectivity of 93%–99%. The concentration of the byproduct cyclic enol is 0.5%–5%, and the concentration of the light component of the byproduct is 0.5%–5%. The light component of the byproduct with a boiling point lower than that of the cyclic ketone compound is separated by distillation. The heavy component of the byproduct with a boiling point higher than that of the cyclic ketone compound is further separated by distillation. Ketone compounds are hydrogenated in a hydrogenation fixed-bed reactor K102 to produce cyclic ketones. The cyclic ketones are then recovered in a distillation column T103. The hydrogenation fixed-bed reactor K102 is packed with a palladium-Al₂O₃ catalyst. The operating pressure of the hydrogenation fixed-bed reactor K102 is 0.1–1.0 MPa, and the operating temperature is 0–60 °C. A mixture of cyclic olefins or cyclic olefins and saturated alkanes, along with feed gas B, is continuously fed into the fixed-bed reactor K101 via a high-pressure heat exchanger E101A and a high-pressure preheater E102A. The molar ratio of nitrous oxide in gas stream M1 to cyclic olefins in gas stream M2 is 0.05–1, and the following reaction occurs:

[0051] C n H 2n-2(Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24;

[0052] The reaction temperature in the fixed-bed reactor K101 is controlled at 100–350℃, and the pressure in the fixed-bed reactor K101 is 5–30 MPa. The main target product, cyclic ketone compound, and by-products are generated. The by-products include a light component with a lower boiling point than the cyclic ketone compound, which accounts for 0.5%–3%, and a heavy component, cyclohexenone compound, with a higher boiling point than the cyclic ketone compound, which accounts for 0.5%–3%. The selectivity for the conversion of cyclic olefins to cyclic ketone compounds is greater than 93%–99%, and the conversion rate of nitrous oxide in gas composition B is greater than or equal to 90%–99.9%.

[0053] The inlet stream of the high-pressure separator R104A is called M6. Part of the gas phase is mixed with the gas stream M1 by the compressed and returned stream M3 from the second gas booster H102A / B. The other part is called stream M8, which enters the cryogenic gas discharge tank R105A. In the cryogenic gas discharge tank R105A, the liquid phase enters the low-pressure separator R106A for recycling. The gas phase is called gas stream M9. After treatment and testing, the N2O content is less than 0.1% of the total volume and then discharged.

[0054] The liquid phase in high-pressure separator R104A enters low-pressure separator R106A. The liquid phase in low-pressure separator R106A consists of cyclic ketone compound products and reaction byproducts. The reaction byproducts include low-boiling-point byproducts, light and heavy cyclic ketone compounds, and unreacted cyclic alkenes. Alternatively, the liquid phase in low-pressure separator R106A consists of cyclic ketone compound products and reaction byproducts, including light and heavy cyclic ketone compounds and a mixture of unreacted cyclic alkenes and saturated alkanes, referred to as stream M7 in the decyclic olefin recovery distillation column T101. Stream M7 is distilled and separated in the bottom of the decyclic olefin recovery distillation column T101 to obtain the target product, a mixture of cyclic ketone compounds and byproducts. The unreacted cyclic alkenes and the mixture of cyclic alkenes and saturated alkanes are returned to the cyclic olefin metering tank R101 for recycling.

[0055] The gases from the top of the cryogenic gas vent tank R105A and the top of the low-pressure separator R106A are combined and enter the water scrubbing tower W101A. The function of the cryogenic gas vent tank R105A is to cool the gas stream from the outlet of the cryogenic gas vent tank R105A to the water scrubbing tower W101A to 5-15°C using a mixture of conventional water and ethylene glycol as the coolant. The liquid phase from the water scrubbing tower W101A enters the oil-water separator X101A for oil-water separation. The oil phase from the oil-water separator X101A is then recycled back to the olefin metering tank R101. In operation, the gas phase of the water scrubbing tower W101A is tested and found to have less than 5 ppm of organic matter in its emissions. Water from the bottom of the oil-water separator X101A is circulated by water circulation pump P103 and sprayed into the interior of the top of the water scrubbing tower W101A. Water and trace organic compounds from the bottom of the water scrubbing tower W101A enter the oil-water separator X101A for separation. The gas vent on W101A is only used for maintenance and safety purposes. The gas vent of the water scrubbing tower W101A discharges gas from the top of the cryogenic gas discharge tank R105A and the low-pressure separator.

[0056] Process exhaust gas of R106A.

[0057] The target product, cyclic ketones, and light components obtained from the bottom of the T101 cyclic olefin recovery distillation column enter the T102 recovery distillation column. The light components obtained from the top distillation are stored and utilized. The main product from the bottom of the T102 light component recovery distillation column enters the T103 cyclic ketone and cyclic enene recovery distillation column via stream M11 for distillation. The target product, cyclic ketones, obtained at the top of the T103 column are stored and utilized via stream M12. The bottom of the T103 column yields cyclic enene C. n H 2n-4 O is sent to the pharmaceutical section via logistics M13B for storage and utilization. It is an important intermediate in the pharmaceutical industry. The heavy component byproduct, cyclic ketone compound, is sent to hydrogenation fixed-bed reactor K102 via logistics M13A to generate the target cyclic ketone compound. The hydrogenation reaction is carried out in hydrogenation fixed-bed reactor K102 in the presence of Al2O3 catalyst coated with 3% to 5% palladium, at a reaction pressure of 0.1 to 1.0 MPa, a hydrogenation reaction temperature of 30 to 100°C, and a cyclic ketone to hydrogen molar ratio of 1:400 to 1000. The cyclic ketone compound is then returned to the cyclic ketone and cyclic ketone recovery distillation column T103 for distillation to obtain the target cyclic ketone compound.

[0058] When gas composition B requires purification, it is purified by the nitrous oxide purification unit G101 to a purer gas containing 50-99% N2O, which then enters the raw material gas B storage tank V103 for reaction with cyclic olefin compounds.

[0059] After adding a large specific surface area metal material inside the fixed-bed reactor K101, the entire equipment needs to be purged with N2 gas from nitrogen tank V101 before the reaction begins. The subsequent reaction is carried out under N2 protection. The gas stream M1 and gas stream M3 mixture, as well as the cyclic olefin or cyclic olefin-saturated alkane mixture stream M2, are mixed and then pass through high-pressure heat exchanger E101, where the temperature reaches 90-200℃. After passing through high-pressure preheater E102, the temperature reaches 210-350℃. The reaction temperature inside the fixed-bed reactor K101 is controlled at 100-350℃, and the pressure inside the fixed-bed reactor K101 is 5-30MPa. The material R103 entering the high-pressure cooler is cooled to 0-35℃ by the high-pressure cooler R103.

[0060] The fixed-bed reactor K101 is equipped with a cage-type heat exchanger. The model of the cage-type heat exchanger is Chinese Patent Publication No.: CN209197530U, patent name: A cage-type heat exchanger in a catalytic hydrogenation reactor. A heat carrier at 100-350°C is introduced into the cage-type heat exchanger in the catalytic hydrogenation reactor to remove the heat released during the reaction of cyclic olefins and nitrous oxide. A metal material with a large specific surface area is added to the inner cavity of the fixed-bed reactor K101. The fixed-bed reactor is a tubular fixed-bed reactor with a jacket layer. A heat carrier at 100-350°C passes through the jacket to remove the heat released during the reaction of cyclic olefins and nitrous oxide. The tubular fixed-bed reactor is a single-tube or multi-tube parallel fixed-bed reactor.

[0061] The large specific surface area metal material is one or more of Raschig rings, Sirra rings, and structured corrugated wire mesh fillers. The specific surface area of ​​the large specific surface area metal material is 200 to 2000 square meters per cubic meter. The Raschig ring dimensions are 2mm × 2mm × 0.2mm (diameter × height × thickness), 4mm × 4mm × 0.2mm, 6mm × 6mm × 0.2mm, 10mm × 10mm × 0.2mm, 15mm × 15mm × 0.2mm, 25mm × 25mm × 0.2mm, or Sirra rings or structured corrugated wire mesh fillers with the same specific surface area. The metal material is one or more of 304 stainless steel, 316L stainless steel, copper, iron, nickel, chromium, or manganese, or an alloy of other metals.

[0062] Fixed-bed reactor K101 is a vertical fixed-bed reactor. Cycloolefins are continuously injected from the top of fixed-bed reactor K101 in one go. Nitrous oxide gas streams M1 and M3 are also continuously injected from the top of fixed-bed reactor K101 in one go, or nitrous oxide gas streams M1 and M3 are injected in three parts from the top, middle, and bottom of fixed-bed reactor K101. The top feed position refers to the feed position starting from the top of fixed-bed reactor K101. The feed amounts of nitrous oxide are 0.0% to 20% from top to bottom, the feed amounts of the middle feed positions refer to the 20% to 40% positions from top to bottom of the fixed bed reactor K101, and the feed amounts of the lower feed positions refer to the 40% to 70% positions from top to bottom of the fixed bed reactor K101. The proportion of nitrous oxide feed amounts in these three positions is 20% to 40% of the total nitrous oxide feed amount, respectively. Alternatively, gaseous streams M1 and M3 containing nitrous oxide are uniformly injected from the top of the fixed bed reactor K101 at positions ranging from 0.0% to 70%.

[0063] In a mixture of cyclic olefins and saturated alkanes, the molar ratio of cyclic olefins to saturated alkanes is 1:1 to 1:20. Saturated alkanes refer to straight-chain alkanes, branched alkanes, or cycloalkanes with carbons 4 to 20. A common example of a mixture of cyclic olefins and saturated alkanes is cyclohexene-cyclohexane.

[0064] Stream M7 first enters the top of the cyclic olefin recovery distillation column T101, where the light component and cyclic olefin stream M8 are recycled back to the cyclic olefin storage tank. The bottom of the cyclic olefin recovery distillation column T101 is stream M9. Stream M9 is sent to the light component by-product recovery distillation column T102. After distillation in the light component by-product recovery distillation column T102, the top component of the light component, stream M10, is distilled off and sent to the storage tank. The bottom component of the light component by-product recovery distillation column T102 is stream M11. Stream M11 is sent to the cyclic ketone and cyclic enol recovery distillation column T103. After distillation in the distillation column… The top of the column contains the target product, a cyclic ketone compound, which becomes stream M12. Stream M12 goes to the product storage tank. The bottom product of the cyclic ketone and cyclic enone recovery distillation column T103 contains a mixture of byproducts, cyclic enones, and cyclic ketones, which is called stream M13. After heat exchange, M13 enters the hydrogenation fixed-bed reactor K102. After hydrogenation, it generates hydrogenation product stream M14. Stream M14 undergoes heat exchange, cooling, high-pressure, and low-pressure separation to obtain stream M15, which is a cyclic ketone compound. Stream M15 is returned to the cyclic ketone and cyclic enone recovery distillation column T103 for distillation to obtain the cyclic ketone compound.

[0065] The hydrogenation product of the fixed-bed hydrogenation reactor K102 is a mixture of hydrogenated cyclic ketones and hydrogen gas. This mixture enters the hydrogenation product heat exchanger E101B via stream M14, where it is heated to 50–130°C. The cyclic ketone and hydrogen mixture exiting from the bottom of heat exchanger E101B then enters the hydrogenation product high-pressure cooler R103B via stream M16, where it is cooled to 5–30°C. The product then enters the hydrogenation product high-pressure separator R104B via stream M16 for gas-liquid separation. The liquid at the bottom of the high-pressure separator R104B is then separated into gas and liquid components. Stream M18A enters the low-pressure separator R106B for hydrogenation products. The liquid stream separated at the bottom of R106B passes through stream M15 and is then distilled in the cyclic ketone and cyclic enone recovery distillation column T103 to obtain the target cyclic ketone compound. The gaseous portion of stream M18B from the high-pressure separator R104B for hydrogenation products goes to the cryogenic discharge tank R105B for hydrogenation products. After being cooled to 0-10°C, it enters the hydrogenation tail gas washing tower W102B via stream M20. The function of the cryogenic discharge tank R105B for hydrogenation products is to cool the hydrogenation products under the action of the coolant. The temperature of the material flowing from the cryogenic discharge tank R105B to the hydrogenation tail gas scrubbing tower W102B is cooled to 5-15°C. The gaseous portion M19 of the hydrogenation product low-pressure separator R106B enters the hydrogenation tail gas scrubbing tower W102B. The hydrogenation tail gas scrubbing tower W102B removes organic compounds from the residual gas in the hydrogenation product low-pressure separator R106B. If the organic matter content in the gas is ≤5ppm, it is discharged from the top of the hydrogenation tail gas scrubbing tower W102B. Hydrogen is collected from the top of the hydrogenation tail gas scrubbing tower W102B and recycled in a hydrogen tank. The liquid stream M21 at the bottom of the hydrogenation tail gas washing tower W102B goes to the hydrogenation product oil-water separator X102B for oil-water separation. The oil layer is periodically recovered and centrally processed. The water at the bottom of the hydrogenation product oil-water separator X102B is transported by the feed pump P104 to the interior of the top of the hydrogenation tail gas washing tower W102B for spraying. The water at the bottom of the hydrogenation tail gas washing tower W102B contains trace amounts of organic matter and is circulated into the hydrogenation product oil-water separator X102B. In the hydrogenation product oil-water separator X102B, the trace amounts of organic matter are separated from the water layer.

[0066] A production equipment for a method of producing cyclic ketone compounds by oxidizing cyclic olefins using waste gas from adipic acid production:

[0067] The system includes a nitrogen tank V101, a cyclic olefin metering tank R101, a feed gas B metering tank R102, a high-pressure heat exchanger E101A, a high-pressure preheater E102A, a fixed-bed reactor K101, a high-pressure cooler R103A, a high-pressure separator R104A, a cryogenic gas exhaust tank R105A, and a low-pressure separator R106A. The cyclic olefin metering tank R101 has a cyclic olefin inlet. The outlet of the cyclic olefin metering tank R101 is connected to the inlet of the fixed-bed reactor K101 via a pipeline through the high-pressure heat exchanger E101A and the high-pressure preheater E102A. The outlet of the feed gas B metering tank R102 is connected via a pipeline through the high-pressure heat exchanger E101A and the high-pressure preheater... Unit E102A is connected to the inlet of fixed-bed reactor K101. The outlet of fixed-bed reactor K101 is connected to the inlet of high-pressure separator R104A via a pipeline through high-pressure heat exchanger E101A and high-pressure cooler R103A. The outlet at the upper end of high-pressure separator R104A is connected to the inlet of cryogenic gas exhaust tank R105A via a pipeline. A nitrogen exhaust port is provided at the upper end of cryogenic gas exhaust tank R105A. The outlet at the lower end of high-pressure separator R104A is connected to the inlet of low-pressure separator R106A via a pipeline. A product collection port is provided at the lower end of low-pressure separator R106A, and a gas exhaust port is provided at the upper end of low-pressure separator R106A. The water washing tower W101A recovers organic components, and inorganic gases are treated and discharged at high altitude after passing the test. The cyclohexene metering tank R101, the raw material gas B metering tank R102, the high-pressure heat exchanger E101A, the high-pressure preheater E102A, the fixed-bed reactor K101, the high-pressure cooler R103A, the high-pressure separator R104A, the cryogenic gas emission tank R105A, and the low-pressure separator R106A are all connected to the nitrogen tank V101 via pipelines. The nitrogen tank V101 is equipped with a nitrogen inlet. The system also includes a cycloolefin recovery distillation tower T101, a pressure swing adsorption deoxygenation unit U101, a light component by-product recovery distillation tower T102, and a first gas booster H101A. / B and the second gas booster H102A / B, the cyclic olefin recovery distillation tower T101 is provided with an adipic acid feed gas inlet, the outlet of the cyclic olefin recovery distillation tower T101 is connected to the inlet of the pressure swing adsorption deoxygenation device U101 through a pipeline, the outlet of the pressure swing adsorption deoxygenation device U101 is connected to the inlet of the light component by-product recovery distillation tower T102 through a pipeline, the outlet of the light component by-product recovery distillation tower T102 is connected to the inlet of the first gas booster H101A / B through a pipeline, the feed gas B metering tank R102 is provided with a feed gas B inlet, the outlet of the first gas booster H101A / B is connected to the feed gas B inlet of the feed gas B metering tank R102 through a pipeline;The outlet of high-pressure separator R104A, before entering cryogenic gas discharge tank R105A, is connected to the inlet of the second gas booster H102A / B. The outlet of cyclohexene metering tank R101, before entering high-pressure heat exchanger E101A, is connected to the outlet of the second gas booster H102A / B. Low-pressure discharge ports are provided at the bottom of cycloolefin metering tank R101, feed gas B metering tank R102, high-pressure heat exchanger E101, high-pressure preheater E102, high-pressure cooler R103, high-pressure separator R104, cryogenic gas discharge tank R105, and low-pressure separator R106A. The outlet pipe of the cyclic olefin metering tank R101 is equipped with a high-pressure cyclic olefin feed pump P101A / B; the outlet pipe of the feed gas metering tank R102 (B) is equipped with a feed pump P102A / B for the first hydrogenation reactor; the outlet pipe of the fixed-bed reactor K101 is equipped with a high-pressure filter F101; and the inlet pipe of the fixed-bed reactor K101 is connected to a nitrogen tank V101. This equipment can utilize adipic acid production waste gas to oxidize cyclic olefins to produce cyclic ketone compounds. The equipment has multiple maintenance interfaces.

[0068] Example 1

[0069] Taking cyclohexene as an example, such as Figure 2 As shown in the diagram, L represents a level gauge, T represents a temperature transmitter, and P represents a pressure transmitter. The reaction equation for cyclohexene with N₂O is:

[0070] Cyclohexene + N₂O → Cyclohexanone + Cyclohexenone + Cyclopentylformaldehyde + N₂↑

[0071] C n H 2n-2 +N₂O→C n H 2n-2 O+CnH 2n-4 O+C n H 2n-2 O+N2↑

[0072] C6H 10 +N₂O→C₆H 10 O+C6H8O+C6H 10 O+N2↑

[0073] When n is 6, the corresponding chemical structural formula is:

[0074]

[0075] The process begins with cyclohexene + N₂O → cyclohexanone + heavy component (byproduct: cyclohexenone) + light component (byproduct: cyclopentylformaldehyde) + N₂↑. In the diacid production line, nitrous oxide-containing raw material gas A enters raw material gas storage tank V102. Tank V102 is a floating head gas storage tank with an operating pressure of 0.01–1.0 MPa and an operating temperature of 0–50°C. The raw material gas A from storage tank T101 then enters the pressure swing adsorption deoxygenation unit U101 to remove oxygen. The oxygen content in the gas is reduced to less than 10 ppm. The qualified gas after oxygen removal by the pressure swing adsorption deoxygenation device U101 is gas composition B. Gas composition B enters the raw material gas B storage tank V103. The raw material gas B storage tank V103 is a floating head tank. The operating pressure of the raw material gas B storage tank V103 is 0.01~1.0Mpa, and the operating temperature is 0~50℃. Gas composition B is pressurized to 1.0~5.0Mpa and 37~60℃ by the first gas booster H101 and then enters the raw material gas B metering tank R102.

[0076] A large specific surface area metal material is added inside the fixed-bed reactor K101. Gas composition B from the feed gas metering tank R102 is metered and pressurized to a pressure of 5-30 MPa, forming gas stream M1. Gas stream M1 is mixed with gas stream M3, which is partially returned from the high-pressure separator R104A via the second gas booster H102A / B. The standard state volume ratio of gas stream M1 to gas stream M3 is controlled at 1:1 to 1:50. Then, it enters the high-pressure heat exchanger E101A to exchange heat with the reaction product stream M4 from the fixed-bed reactor K101 filled with the large specific surface area metal material. After heat exchange, gas stream M1 and gas stream M3... The mixture flow reaches a temperature of 90–200℃, then enters the high-pressure preheater E102 for preheating to 210–350℃. After preheating, the mixture flow of gaseous streams M1 and M3 enters the fixed-bed reactor K101 filled with a large specific surface area metal material. The cyclic olefin or cyclic olefin-saturated alkane mixture flow M2 comes from the cyclic olefin metering tank R101. After pressurization and metering, it enters the high-pressure heat exchanger E101A to exchange heat with the reaction product flow M4 from the fixed-bed reactor K101 filled with a large specific surface area metal material. After heat exchange, the temperature reaches 90–200℃, and then enters the high-pressure preheater E102A for preheating. After preheating, it reaches the fixed-bed reactor K101. The required temperature is 100–350℃. The gas stream M1 and gas stream M3 mixture, along with the cyclic olefin or cyclic olefin-saturated alkane mixture M2, react within the fixed-bed reactor K101 to produce stream M4, which includes the target product, a cyclic ketone compound, with a selectivity of 93%–99%. The concentration of the byproduct cyclic enol is 0.5%–5%, and the concentration of the light component of the byproduct is 0.5%–5%. The light component of the byproduct with a boiling point lower than that of the cyclic ketone compound is separated by distillation. The heavy component of the byproduct with a boiling point higher than that of the cyclic ketone compound is further separated by distillation. Ketone compounds are hydrogenated in a hydrogenation fixed-bed reactor K102 to produce cyclic ketones. The cyclic ketones are then recovered in a distillation column T103. The hydrogenation fixed-bed reactor K102 is packed with a palladium-Al₂O₃ catalyst. The operating pressure of the hydrogenation fixed-bed reactor K102 is 0.1–1.0 MPa, and the operating temperature is 0–60 °C. A mixture of cyclic olefins or cyclic olefins and saturated alkanes, along with feed gas B, is continuously fed into the fixed-bed reactor K101 via a high-pressure heat exchanger E101A and a high-pressure preheater E102A. The molar ratio of nitrous oxide in gas stream M1 to cyclic olefins in gas stream M2 is 0.05–1, and the following reaction occurs:

[0077] C n H 2n-2(Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24;

[0078] The reaction temperature in the fixed-bed reactor K101 is controlled at 100–350℃, and the pressure in the fixed-bed reactor K101 is 5–30 MPa. The main target product, cyclic ketone compound, and by-products are generated. The by-products include a light component with a lower boiling point than the cyclic ketone compound, which accounts for 0.5%–3%, and a heavy component, cyclohexenone compound, with a higher boiling point than the cyclic ketone compound, which accounts for 0.5%–3%. The selectivity for the conversion of cyclic olefins to cyclic ketone compounds is greater than 93%–99%, and the conversion rate of nitrous oxide in gas composition B is greater than or equal to 90%–99.9%.

[0079] The inlet stream of the high-pressure separator R104A is called M6. Part of the gas phase is mixed with the gas stream M1 by the compressed and returned stream M3 from the second gas booster H102A / B. The other part is called stream M8, which enters the cryogenic gas discharge tank R105A. In the cryogenic gas discharge tank R105A, the liquid phase enters the low-pressure separator R106A for recycling. The gas phase is called gas stream M9. After treatment and testing, the N2O content is less than 0.1% of the total volume and then discharged.

[0080] The liquid phase in high-pressure separator R104A enters low-pressure separator R106A. The liquid phase in low-pressure separator R106A consists of cyclic ketone compound products and reaction byproducts. The reaction byproducts include low-boiling-point byproducts, light and heavy cyclic ketone compounds, and unreacted cyclic alkenes. Alternatively, the liquid phase in low-pressure separator R106A consists of cyclic ketone compound products and reaction byproducts, including light and heavy cyclic ketone compounds and a mixture of unreacted cyclic alkenes and saturated alkanes, referred to as stream M7 in the decyclic olefin recovery distillation column T101. Stream M7 is distilled and separated in the bottom of the decyclic olefin recovery distillation column T101 to obtain the target product, a mixture of cyclic ketone compounds and byproducts. The unreacted cyclic alkenes and the mixture of cyclic alkenes and saturated alkanes are returned to the cyclic olefin metering tank R101 for recycling.

[0081] Example 2

[0082] The method is the same as in Example 1. This example uses cyclopentene as an example. The reaction equation is as follows:

[0083] Cyclopentene + N₂O → Cyclopentanone + Byproducts + N₂↑

[0084] C5H8 + N2O → C5H8O + light component byproducts + N2↑

[0085] The selectivity for the formation of cyclopentene from cyclopentene was 99.34%, with light component byproducts accounting for 0.66% and no heavy component byproducts.

[0086]

[0087] In summary:

[0088] First, this invention is based on the Kelvin equation.

[0089]

[0090] Where P 凹 P represents the saturated vapor pressure of the liquid film. 0 The saturated vapor pressure representing the vapor in the liquid plane state;

[0091] r 凹 The radius represents the aperture; T represents the thermodynamic temperature; M represents the molecular weight of cyclohexene; and R represents the thermodynamic constant.

[0092]

[0093] σ can be viewed as the free enthalpy per unit surface area at a specified temperature and pressure, also known as surface free enthalpy. ρ represents the density of the liquid; n j It represents the composition of the liquid.

[0094] The formula shows that for metallic materials with a large specific surface area, r... 凹 The smaller the value, the better for the same T and n. j Under the condition, P 凹 <P 0 This forms a liquid film; in other words, the presence of a large specific surface area metallic material reduces the reaction pressure between cyclohexene and nitrous oxide.

[0095] Second, the large specific surface area of ​​the metal material allows cyclohexene to be adsorbed on the material surface, forming a large surface area liquid film. This provides sufficient opportunity for nitrous oxide and cyclohexene to collide and react to form cyclohexanone. The presence of the large specific surface area of ​​the metal material gives the cyclohexene liquid film a large surface activation energy, which provides sufficient activation energy for the reaction between cyclohexene and nitrous oxide.

[0096] Third, metallic materials with large specific surface areas can eliminate branched free radicals generated during the reaction of cyclohexene and nitrous oxide, thus preventing explosive reactions.

[0097] Combining the above three advantages, the monopolymer conversion rate of the reaction between cyclohexene and nitrous oxide is higher than the conventional level of existing technologies.

[0098] Material unit conversion rate definition:

[0099] Material conversion rate (%) is defined as (AB) / A*100%.

[0100] A: Under stable operating conditions in a fixed-bed reactor, the temperature, pressure, flow rate, and composition of each bed in the reactor remain constant per unit time. The number of mol of cyclohexene entering the reactor per unit time is A, and the number of mol of unreacted cyclohexene at the reactor outlet is B. The number of mol of the target compound cyclohexanone generated at the reactor outlet is C.

[0101] Selective definition:

[0102] The selectivity (%) for generating the target compound cyclohexanone = C / (AB)*100%.

[0103] Table 1: Gas composition of mixed gas A containing nitrous oxide emitted during the oxidation of nitric acid to produce adipic acid.

[0104]

[0105] Table 2: Gas composition of gas mixture B

[0106] Gas composition Content, %V / V <![CDATA[N2O]]> 36.65～44.68 <![CDATA[N2]]> 47.12～53.19 NOX 0.021～0.043 <![CDATA[O2]]> Less than or equal to 10 ppm CO 0.16～0.32 <![CDATA[CO2]]> 5.86～6.70 Moisture 1.88～2.66

[0107] The composition of raw material gas A is shown in Table 1. The source of raw material gas A is limited by the unstable production process of the adipic acid production line; its composition varies with hourly flow rate, pressure, and temperature. Raw material gas A is stored in raw material gas A storage tank T101, where it undergoes mixing and balancing to stabilize the process. After stabilization, the raw material gas A, with its temperature, pressure, and flow rate, is deoxygenated by the pressure swing adsorption deoxygenation unit U101. The composition of the raw material gas B supplied to the first gas booster H101 is shown in Table 2.

[0108] This patented method for producing cyclic ketone compounds by oxidizing cyclic olefins using nitrous oxide does not require a larger investment than the decomposition method. The heat obtained is recovered and used to provide a heat source for later products. Furthermore, while solving environmental problems, nitrous oxide is used as an oxidant in the oxidation of cyclic olefins into cyclic ketone compounds, reducing costs and achieving the goal of reuse.

[0109] A comparison of the current mainstream caprolactam production processes in China—cyclohexane oxidation, cyclohexene hydration, and the nitrous oxide process of this patented method—is as follows:

[0110] 1) Cyclohexane oxidation method: using benzene and hydrogen as raw materials, benzene is hydrogenated to produce cyclohexane, cyclohexane is oxidized with air to produce a mixture of cyclohexanone and cyclohexanol (KA oil), and cyclohexanol is dehydrogenated to produce cyclohexanone.

[0111] 2) Cyclohexene hydration method: using benzene and hydrogen as raw materials, benzene is selectively hydrogenated to produce cyclohexene (cyclohexane as a byproduct), cyclohexene undergoes a hydration reaction to produce cyclohexanol, and cyclohexanol undergoes a dehydrogenation reaction to produce cyclohexanone.

[0112] 3) Nitrous oxide method: This patented method uses nitrous oxide to oxidize cyclohexene, generating cyclohexanone in one step with high selectivity.

[0113] a) A comparison of the consumption quotas for the three methods is as follows:

[0114]

[0115] b) A comparison of production costs and economic benefits is as follows:

[0116]

[0117] Among the three processes for producing cyclohexanone, the nitrous oxide method has the lowest cost. In summary, the nitrous oxide method for producing cyclohexanone is highly competitive due to its rational process flow, low material consumption, ability to solve the air pollution problem caused by nitrous oxide, and low production cost.

[0118] In conclusion, the oxidation of cyclohexene with N₂O to produce cyclohexanone has significant practical implications. BASF has already built and put into operation a 30,000-ton-per-year cycloolefin oxidation production facility in Europe using this theory, although detailed process flow information has not been reported. Therefore, the use of N₂O to produce cyclohexanone, while bringing certain economic benefits, will also inevitably promote research on N₂O emission reduction and utilization, thereby meeting the needs of sustainable development. Transforming N₂O from an atmospheric pollutant into an important industrial raw material not only solves the environmental problems associated with N₂O but also provides a new technological route for the industrial production of cyclohexanone. Therefore, this research has significant social and economic value.

[0119] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all embodiments here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A method for producing cyclic ketone compounds by oxidizing cyclic olefins using waste gas from adipic acid production, characterized in that: In the aziridine production line, the nitrous oxide-containing feed gas A can be deoxygenated to a content of less than 100 ppm, allowing it to react directly with cyclic olefins to produce cyclic ketone compounds and byproducts. The nitrous oxide-containing feed gas A in the aziridine production line can also be purified to a purer gas containing 50-99% N₂O for reaction with cyclic olefin compounds. The reaction equation is as follows: C n H 2n-2 (Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24.

2. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 1, characterized in that: The specific process for the feed gas A containing nitrous oxide in the diacid production line to react directly with cyclic olefins to generate cyclic ketone compounds and byproducts after deoxygenation, reducing the oxygen content to less than 100 ppm, is as follows: Feed gas A containing nitrous oxide enters feed gas A storage tank (V102). Feed gas A storage tank (V102) is a floating head gas storage tank. The operating pressure of feed gas A storage tank (V102) is 0.01–1.0 MPa, and the operating temperature is 0–50°C. Feed gas A from feed gas A storage tank (V102) then enters the pressure swing adsorption deoxygenation unit (U1). 01) Oxygen is removed to form gaseous component B. Gaseous component B can also be purified to a higher N2O concentration, between 50% and 99%. The oxygen content in gaseous component B is less than 100 ppm. Gaseous component B enters the raw material gas B storage tank (V103). The raw material gas B storage tank (V103) is a floating head type tank. The operating pressure of the raw material gas B storage tank (V103) is 0.01 to 1.0 MPa, and the operating temperature is 37 to 50°C. Gaseous component B is pressurized to 1.0 to 5.0 MPa and 37 to 60°C by the first gas booster (H101A / B) and then enters the raw material gas B metering tank (R102). A large specific surface area metal material is added inside the fixed-bed reactor (K101). Gas composition B from the feed gas metering tank (R102) is metered and pressurized to a pressure of 5–30 MPa, forming gas stream M1. Gas stream M1 is mixed with gas stream M3, partially discharged from the high-pressure separator (R104A) and returned by the second gas booster (H102A / B). The standard state volume ratio of gas stream M1 to gas stream M3 is controlled at 1:1 to 1:

50. Then, the mixture enters the high-pressure heat exchanger (E101A) and exchanges heat with the reaction product stream M4 from the fixed-bed reactor (K101) filled with the large specific surface area metal material. After heat exchange, gas stream M1 and gas stream M4... The M3 mixture reaches a temperature of 90–200°C and then enters the high-pressure preheater (E102) for preheating to 210–350°C. After preheating, the gaseous stream M1 and the gaseous stream M3 mixture enter the fixed-bed reactor (K101) packed with a large specific surface area metal material. The cyclic olefin or cyclic olefin-saturated alkane mixture stream M2 comes from the cyclic olefin metering tank (R101). After pressurization and metering, it enters the high-pressure heat exchanger (E101A) to exchange heat with the reaction product stream M4 from the fixed-bed reactor (K101) packed with a large specific surface area metal material. After heat exchange, the temperature reaches 90–200°C, and then it enters the high-pressure preheater (E102A) for preheating. After preheating, it reaches the fixed-bed reactor. The required temperature (K101) is 100–350°C. The gas stream M1 and gas stream M3 mixture, along with the cyclic olefin or cyclic olefin-saturated alkane mixture M2, react within the fixed-bed reactor (K101) to produce stream M4, which includes the target product, a cyclic ketone compound, with a selectivity of 93%–99%, and a byproduct, a cyclic enone compound, with a concentration of 0.5%–5%. The light component of the byproduct has a boiling point lower than that of the cyclic ketone compound, which is separated by distillation. The heavier component of the byproduct, a cyclic enone compound with a boiling point higher than that of the cyclic ketone compound, is further distilled. The product is hydrogenated in a hydrogenation fixed-bed reactor (K102) to produce cyclic ketones. The cyclic ketones are then recovered in a distillation column (T103) for recycling. The hydrogenation fixed-bed reactor (K102) is packed with a palladium-Al2O3 catalyst. The operating pressure of the hydrogenation fixed-bed reactor (K102) is 0.1–1.0 MPa, and the operating temperature is 0–60 °C. A mixture of cyclic olefins or cyclic olefins and saturated alkanes, along with feed gas B, is continuously fed into the fixed-bed reactor (K101) via a high-pressure heat exchanger (E101A) and a high-pressure preheater (E102A). The molar ratio of nitrous oxide in gas stream M1 to cyclic olefins in gas stream M2 is 0.05–1, and the following reaction occurs: C n H 2n-2 (Cycloolefin) + N₂O (nitrous oxide) → C n H 2n-2 O (product: cyclic ketone compound) + byproduct + N2↑ (nitrogen gas) where: n is a positive integer from 4 to 24; The reaction temperature in the fixed-bed reactor (K101) is controlled at 100–350℃, and the pressure in the fixed-bed reactor (K101) is 5–30 MPa. The main target product, cyclic ketone compound, and byproducts are generated. The byproducts include a light component with a lower boiling point than the cyclic ketone compound, which accounts for 0.5%–3% of the byproducts, and a heavy component, cyclohexenone compound, with a higher boiling point than the cyclic ketone compound, which accounts for 0.5%–3% of the cyclohexenone compound. The selectivity for the conversion of cyclic olefins to cyclic ketone compounds is greater than 93%–99%, and the conversion rate of nitrous oxide in gas composition B is greater than or equal to 90%–99.9%. The inlet stream of the high-pressure separator (R104A) is called M6. Part of the gas phase is mixed with the gas stream M1 by the compressed and returned stream M3 from the second circulating gas booster (H102A / B). The other part is called stream M8, which enters the cryogenic gas discharge tank (R105A). In the cryogenic gas discharge tank (R105A), the liquid phase enters the low-pressure separator (R106A) for recycling. The gas phase is called gas stream M9. After treatment and testing, the N2O content is less than 0.1% of the total volume and then discharged. The liquid phase in the high-pressure separator (R104A) enters the low-pressure separator (R106A). The liquid phase in the low-pressure separator (R106A) consists of cyclic ketone compound products and reaction byproducts. The reaction byproducts include low-boiling-point byproducts, light and heavy cyclic ketone compounds, and unreacted cyclic olefins. Alternatively, the liquid phase in the low-pressure separator (R106A) consists of cyclic ketone compound products and reaction byproducts, including light and heavy cyclic ketone compounds and a mixture of unreacted cyclic olefins and saturated alkanes. This mixture is called stream M7, the decyclic olefin recovery distillation column (T101). Stream M7 is distilled and separated in the cyclic olefin recovery distillation column (T101) to obtain the target product, a mixture of cyclic ketone compounds and byproducts, at the bottom. The unreacted cyclic olefins and the mixture of cyclic olefins and saturated alkanes are returned to the cyclic olefin metering tank (R101) for recycling. The gases from the top of the cryogenic gas vent tank (R105A) and the top of the low-pressure separator (R106A) are combined and enter the water scrubbing tower (W101A). The function of the cryogenic gas vent tank (R105A) is to cool the gas stream from its outlet to the water scrubbing tower (W101A) to 5–15°C under the action of the coolant. The liquid phase from the water scrubbing tower (W101A) enters the oil-water separator (X101A) for oil-water separation. The oil phase of the separator (X101A) is recycled in the cyclic olefin metering tank (R101). The gas phase of the water washing tower (W101A) is discharged after testing and the organic matter content is less than 5 ppm. The water at the bottom of the oil-water separator (X101A) is pumped into the interior of the top of the water washing tower (W101A) by the water circulation pump (P103) for spraying. The water and trace organic compounds at the bottom of the water washing tower (W101A) enter the oil-water separator (X101A) for separation. The target product, cyclic ketones, and light component byproducts obtained from the bottom of the cyclic olefin recovery distillation column (T101) enter the recovery distillation column (T102). The light component byproduct obtained from the top distillation of the light component byproduct recovery distillation column (T102) is stored and utilized. The main product obtained from the bottom of the light component byproduct recovery distillation column (T102) enters the cyclic ketone and cyclic enene recovery distillation column (T103) via stream M11 for distillation. The target product, cyclic ketones, obtained from the top of the column is stored and utilized via stream M12. The cyclic enene C is obtained from the bottom of the column. n H 2n-4 O is sent to the pharmaceutical section via logistics M13B for storage and utilization. It is an important intermediate in the pharmaceutical industry. The heavy component byproduct, cyclic ketone compound, is sent to the hydrogenation fixed-bed reactor (K102) via logistics M13A for hydrogenation to generate the target product cyclic ketone compound. The hydrogenation reaction is carried out in the hydrogenation fixed-bed reactor (K102) in the presence of Al2O3 catalyst coated with 3% to 5% palladium, the reaction pressure is 0.1 to 1.0 MPa, the hydrogenation reaction temperature is 30 to 100℃, and the cyclic ketone to hydrogen molar ratio is 1:400 to 1000. The cyclic ketone compound is then returned to the cyclic ketone and cyclic ketone recovery distillation column (T103) for distillation to obtain the target cyclic ketone compound.

3. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: When the gas composition B needs to be purified, it is purified to a purer gas containing 50-99% N2O through a nitrous oxide purification device (G101) and then enters the raw material gas B storage tank (V103) for reaction with cyclic olefin compounds.

4. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: After adding a large specific surface area metallic material inside the fixed-bed reactor (K101), the entire equipment needs to be purged with N2 gas from the nitrogen tank (V101) before the reaction begins. The subsequent reaction proceeds under N2 protection. The mixture of gas streams M1 and M3, along with the cyclic olefin or cyclic olefin-saturated alkane mixture stream M2, is then passed through a high-pressure heat exchanger (E101) to reach a temperature of 90–200°C. After passing through a high-pressure preheater (E102), the temperature reaches 210–350°C. The reaction temperature within the fixed-bed reactor (K101) is controlled at 100–350°C, and the pressure within the fixed-bed reactor (K101) is maintained at 5–50°C. Operating at 30MPa, the material entering the high-pressure cooler (R103) is cooled to 0-35℃ by the high-pressure cooler (R103).

5. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: The fixed-bed reactor (K101) is equipped with a cage-type heat exchanger. The model of the cage-type heat exchanger is Chinese Patent Publication No.: CN209197530U, patent title: A cage-type heat exchanger in a catalytic hydrogenation reactor. A heat carrier at 100-350°C is introduced into the cage-type heat exchanger in the catalytic hydrogenation reactor to remove the heat released during the reaction of cyclic olefins and nitrous oxide. A metal material with a large specific surface area is added to the inner cavity of the fixed-bed reactor (K101). The fixed-bed reactor is a tubular fixed-bed reactor with a jacket layer. A heat carrier at 100-350°C passes through the jacket to remove the heat released during the reaction of cyclic olefins and nitrous oxide. The tubular fixed-bed reactor is a single-tube or multi-tube parallel fixed-bed reactor.

6. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: The large specific surface area metal material is one or more of Raschig rings, Sirra rings, and structured corrugated wire mesh fillers. The specific surface area of ​​the large specific surface area metal material is 200 to 2000 square meters per cubic meter. The Raschig ring dimensions are 2mm × 2mm × 0.2mm (diameter × height × thickness), 4mm × 4mm × 0.2mm, 6mm × 6mm × 0.2mm, 10mm × 10mm × 0.2mm, 15mm × 15mm × 0.2mm, 25mm × 25mm × 0.2mm, or Sirra rings or structured corrugated wire mesh fillers with the same specific surface area. The metal material is one or more alloy materials selected from 304 stainless steel, 316L stainless steel, copper, iron, nickel, chromium, or manganese.

7. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: The fixed-bed reactor (K101) is a vertical fixed-bed reactor. Cycloolefins are continuously injected from the top of the fixed-bed reactor (K101) in one go. Nitrous oxide gas streams M1 and M3 are also continuously injected from the top of the fixed-bed reactor (K101) in one go, or the nitrous oxide gas streams M1 and M3 are injected into the fixed-bed reactor (K101) in three parts from the top, middle, and bottom positions. The top feed position refers to the top of the fixed-bed reactor (K101). The feed amounts of nitrous oxide are 0.0% to 20% from top to bottom in the first three parts, 20% to 40% from top to bottom in the middle part, and 40% to 70% from top to bottom in the lower part. The proportion of nitrous oxide feed amounts in these three parts is 20% to 40% of the total nitrous oxide feed amount, respectively. Alternatively, gaseous streams M1 and M3 containing nitrous oxide are uniformly injected from the top of the fixed bed reactor (K101) at positions ranging from 0.0% to 70%.

8. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: In the cyclic olefin-saturated alkane mixture, the mol ratio of cyclic olefin to saturated alkane is 1:1 to 1:20, and the saturated alkane refers to straight-chain alkanes, branched alkanes or cycloalkanes from C4 to C20.

9. The method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: The first stream, M7, enters the top of the cyclic olefin recovery distillation column (T101), where the light component and cyclic olefin stream M8 are recycled back to the cyclic olefin storage tank. The bottom stream of the cyclic olefin recovery distillation column (T101) is stream M9. Stream M9 is then sent to the light component by-product recovery distillation column (T102). After distillation in the light component by-product recovery distillation column (T102), the top light component stream M10 is distilled off and sent to the storage tank. The bottom stream of the light component by-product recovery distillation column (T102) is stream M11. Stream M11 is then sent to the cyclic ketone and cyclic enone recovery distillation column (T103). After distillation... The top product, a cyclic ketone compound, is the target product at the top of the distillation column, becoming stream M12. Stream M12 goes to the product storage tank. The bottom product of the cyclic ketone and cyclic enkemone recovery distillation column (T103), containing a mixture of byproducts cyclic enkemone and cyclic ketone, is called stream M13. After heat exchange, M13 enters the hydrogenation fixed-bed reactor (K102), where it undergoes hydrogenation to produce a hydrogenated product, stream M14. Stream M14 undergoes heat exchange, cooling, high-pressure, and low-pressure separation to obtain stream M15, which is a cyclic ketone compound. Stream M15 is returned to the cyclic ketone and cyclic enkemone recovery distillation column (T103) for distillation to obtain the cyclic ketone compound.

10. The production method for producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas according to claim 2, characterized in that: The hydrogenation product of the hydrogenation fixed-bed reactor (K102) is a mixture of hydrogenated cyclic ketone compounds and hydrogen gas. This mixture enters the hydrogenation product heat exchanger (E101B) via stream M14 for heat exchange to 50–130°C. The cyclic ketone and hydrogen mixture exiting from the bottom of the hydrogenation product heat exchanger (E101B) then enters the hydrogenation product high-pressure cooler (R103B) via stream M16, where it is cooled to 5–30°C. The product then enters the hydrogenation product high-pressure separator (R104B) via stream M16 for gas-liquid separation. The liquid at the bottom of the hydrogenation product high-pressure separator (R104B) is then... Stream M18A enters the low-pressure separator for hydrogenation products (R106B). The liquid stream separated at the bottom of the low-pressure separator (R106B) passes through stream M15 and is then distilled in the cyclic ketone and cyclic enone recovery distillation column (T103) to obtain the target cyclic ketone compound. The gaseous portion of stream M18B from the high-pressure separator (R104B) of hydrogenation products goes to the cryogenic discharge tank (R105B) of hydrogenation products. After being cooled to 0-10°C, it enters the hydrogenation tail gas washing tower (W102B) via stream M20. The function of the cryogenic discharge tank (R105B) of hydrogenation products is to cool the hydrogenation products under the action of the coolant. The temperature of the stream from the cryogenic discharge tank (R105B) to the hydrogenation tail gas scrubbing tower (W102B) is cooled to 5-15°C. The gaseous portion M19 from the low-pressure separator (R106B) of the hydrogenation products enters the hydrogenation tail gas scrubbing tower (W102B). The hydrogenation tail gas scrubbing tower (W102B) removes organic compounds from the residual gas in the low-pressure separator (R106B). If the organic matter content in the gas is ≤5ppm, it is discharged from the top of the hydrogenation tail gas scrubbing tower (W102B). Hydrogen is collected from the top of the hydrogenation tail gas scrubbing tower (W102B) for recycling. The liquid stream M21 at the bottom of the hydrogen tail gas washing tower (W102B) goes to the hydrogenation product oil-water separator (X102B) for oil-water separation. The oil layer is periodically recovered and centrally processed. The water at the bottom of the hydrogenation product oil-water separator (X102B) is transported by the feed pump (P104) to the interior of the top of the hydrogenation tail gas washing tower (W102B) for spraying. The water at the bottom of the hydrogenation tail gas washing tower (W102B) contains trace amounts of organic matter and is circulated into the hydrogenation product oil-water separator (X102B). In the hydrogenation product oil-water separator (X102B), the trace amounts of organic matter are separated from the water layer.

11. A production apparatus for the production method of producing cyclic ketone compounds by oxidizing cyclic olefins using adipic acid production waste gas as described in claim 2, characterized in that: It includes a nitrogen tank (V101), a cyclic olefin metering tank (R101), a feed gas B metering tank (R102), a high-pressure heat exchanger (E101A), a high-pressure preheater (E102A), a fixed-bed reactor (K101), a high-pressure cooler (R103A), a high-pressure separator (R104A), a cryogenic gas exhaust tank (R105A), and a low-pressure separator (R106A); the cyclic olefin metering tank (R101) is equipped with a cyclic olefin inlet, and the outlet of the cyclic olefin metering tank (R101) is connected to a pipeline via... The inlet of the fixed-bed reactor (K101) is connected via a high-pressure heat exchanger (E101A) and a high-pressure preheater (E102A). The outlet of the feed gas metering tank B (R102) is connected via a pipeline through the high-pressure heat exchanger (E101A) and the high-pressure preheater (E102A) to the inlet of the fixed-bed reactor (K101). The outlet of the fixed-bed reactor (K101) is connected via a pipeline through the high-pressure heat exchanger (E101A) and the high-pressure cooler (R103A) to the inlet of the high-pressure separator (R104A). The outlet at the upper end of the high-pressure separator (R104A) is connected to the inlet of the cryogenic gas discharge tank (R105A) via a pipeline. The upper end of the cryogenic gas discharge tank (R105A) is equipped with a nitrogen discharge port. The outlet at the lower end of the high-pressure separator (R104A) is connected to the inlet of the low-pressure separator (R106A) via a pipeline. The lower end of the low-pressure separator (R106A) is equipped with a product collection port, and the upper end of the low-pressure separator (R106A) is equipped with a gas discharge port. The discharged gas goes to the water scrubbing tower (W101A), and the recovered gas... In the unit, inorganic gases are treated to meet standards and then discharged at high altitude. The cyclohexene metering tank (R101), raw material gas B metering tank (R102), high-pressure heat exchanger (E101A), high-pressure preheater (E102A), fixed-bed reactor (K101), high-pressure cooler (R103A), high-pressure separator (R104A), cryogenic gas discharge tank (R105A), and low-pressure separator (R106A) are all connected to the nitrogen tank (V101) through pipelines. The nitrogen tank (V101) is equipped with a nitrogen inlet.It also includes a cyclic olefin recovery distillation column (T101), a pressure swing adsorption (PSA) deoxygenation unit (U101), a light component by-product recovery distillation column (T102), a first gas booster (H101A / B), and a second gas booster (H102A / B). The cyclic olefin recovery distillation column (T101) is equipped with an adipic acid feed gas inlet. The outlet of the cyclic olefin recovery distillation column (T101) is connected to the inlet of the PSA deoxygenation unit (U101) via a pipeline. The outlet of the PSA deoxygenation unit (U101) is connected to the inlet of the light component by-product recovery distillation column (T102) via a pipeline. The outlet of the light component by-product recovery distillation column (T102) is connected to the inlet of the light component by-product recovery distillation column (T102) via a pipeline. The inlet of the first gas booster (H101A / B) is connected to the raw material gas B metering tank (R102), which has a raw material gas B inlet. The outlet of the first gas booster (H101A / B) is connected to the raw material gas B inlet of the raw material gas B metering tank (R102) via a pipeline. The pipeline connected to the outlet of the high-pressure separator (R104A) before entering the cryogenic gas discharge tank (R105A) is connected to the inlet of the second gas booster (H102A / B). The pipeline connected to the outlet of the cyclohexene metering tank (R101) before entering the high-pressure heat exchanger (E101A) is connected to the outlet of the second gas booster (H102A / B).

12. The production equipment according to claim 11, characterized in that: The bottom of the cyclic olefin metering tank (R101), the raw material gas B metering tank (R102), the high-pressure heat exchanger (E101), the high-pressure preheater (E102), the high-pressure cooler (R103), the high-pressure separator (R104), the cryogenic gas discharge tank (R105), and the low-pressure separator (R106A) are provided with low discharge ports.

13. The production equipment according to claim 11, characterized in that: The outlet pipe of the cyclic olefin metering tank (R101) is equipped with a high-pressure cyclic olefin feed pump (P101A / B), the outlet pipe of the raw material gas B metering tank (R102) is equipped with a first hydrogenation reactor feed pump (P102A / B), the outlet pipe of the fixed bed reactor (K101) is equipped with a high-pressure filter (F101), and the inlet pipe of the fixed bed reactor (K101) is connected to a nitrogen tank (V101).

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