Acetonitrile waste liquid recovery method and recovery equipment

Abstract

The invention discloses a method and equipment for recovering acetonitrile waste liquid. The method comprises the following steps: sequentially carrying out permeation, oxidation, extraction, rectification and adsorption on the acetonitrile waste liquid to obtain recovered acetonitrile. According to the invention, water, salt and acetonitrile can be effectively separated, various trace impurities in acetonitrile are removed, and a high-purity acetonitrile product is obtained through recovery.

Description

Technical Field

[0001] The present invention relates to the field of industrial organic wastewater recovery, and particularly to a method and equipment for recovering acetonitrile waste liquid. Background Art

[0002] Acetonitrile can undergo typical nitrile reactions and can be alkylated, arylated, phthalated, added, and intramolecularly reacted, playing an important role in organic synthesis. The main uses of acetonitrile include extractants in petrochemical production, raw materials or solvents in pharmaceutical and pesticide production, solvents for high-performance liquid chromatography, etc. Among them, the combined use in the pharmaceutical industry and as a solvent for high-performance liquid chromatography accounts for more than 80% of the total consumption, and the demand has still been showing a rapid growth trend in recent years. It is an important organic intermediate.

[0003] With the continuous development of various industries including man-made fibers, petrochemicals, and pharmaceuticals, etc., the amount of wastewater containing acetonitrile compounds is increasing. In addition to containing a large amount of acetonitrile, such wastewater often contains a large amount of salts and cannot be directly discharged. And for incineration treatment, prior concentration treatment is required, which is expensive and very wasteful of resources. Compared with incineration treatment, desalting and recovering the acetonitrile in it is a better choice.

[0004] CN109970290A discloses a method and a special device for zero-emission treatment of high-salt-content acetonitrile wastewater, which uses two designed membrane aeration bioreactor systems with the combined action of a membrane separator and a membrane aeration bioreactor to separate and degrade acetonitrile in high-salt-content acetonitrile wastewater. This method has strong system adaptability and stable operation. However, this device will completely degrade acetonitrile and cannot be recycled anymore. At the same time, this device is not suitable for treating wastewater systems with a high acetonitrile content.

[0005] CN112479929A discloses a comprehensive utilization method for acetonitrile waste solution, which purifies acetonitrile through multi-stage distillation and rectification, and uses a water remover to assist in removing impurities to collect acetonitrile vapor with a higher purity. This method has simple technological steps. However, it has high requirements for the raw material waste acetonitrile. At the same time, this method requires multiple distillation and rectification operations, with high energy consumption and high requirements for various process parameters, and is not suitable for large-scale waste liquid treatment.

[0006] CN 104926690A discloses a method and device for the recovery and refinement of acetonitrile in the synthesis of ceftriaxone sodium. Through the series connection of multi-stage rectification towers, the acetonitrile waste liquid is refined and concentrated, and then enters a pervaporation membrane separation unit for further purification, and finally pure acetonitrile is obtained through the third rectification tower. This process method is reliable and effective, has strong adaptability to acetonitrile raw materials, and is suitable for large-scale treatment. However, this method has high requirements for equipment, requires multiple rectification tower equipment, has a large investment requirement, and at the same time, too many rectification equipment also have high requirements for energy consumption. Summary of the Invention

[0007] The object of the present invention is to overcome the problems existing in the treatment of acetonitrile waste liquid in the prior art, and to provide a recovery method and a recovery device for acetonitrile waste liquid, which can effectively separate water, salt and acetonitrile, remove various trace impurities in acetonitrile, and recover high-purity acetonitrile products.

[0008] To achieve the above object, on the one hand, the present invention provides a recovery method for acetonitrile waste liquid, which includes: sequentially performing osmosis, oxidation, extraction, rectification and adsorption on the acetonitrile waste liquid to obtain recovered acetonitrile.

[0009] On the second aspect, the present invention provides a recovery device for acetonitrile waste liquid, which includes: an osmosis unit, an oxidation unit, an extraction unit, a rectification unit and an adsorption unit connected in series in sequence to realize sequentially performing osmosis, oxidation, extraction, rectification and adsorption on the acetonitrile waste liquid to obtain recovered acetonitrile.

[0010] Through the above technical solutions, compared with the prior art, the present invention has the following advantages:

[0011] 1. Through technologies such as osmosis, oxidation, combined with extraction, rectification and adsorption, the present invention can effectively separate water, salt and acetonitrile in the acetonitrile waste liquid, remove various trace impurities in acetonitrile, and recover high-purity acetonitrile products.

[0012] 2. The present invention can recover and utilize the effective components in the acetonitrile waste liquid containing salt generated by pharmaceutical synthesis, avoid the pollution of the environment by high-salt organic wastewater, and recover the effective organic components in the wastewater, achieving green circular reuse of resources.

[0013] 3. The recovery device of the present invention adopts a complete set of integrated equipment, and the separation technical principles involved include reverse osmosis, chemical treatment, extraction, rectification, adsorption, etc. This integrated equipment can achieve complete recovery of acetonitrile in the acetonitrile waste liquid containing salt generated by pharmaceutical synthesis, only requires simple auxiliary equipment, has simple operation and high reliability. The whole equipment is of integrated design, with small space, low energy consumption and low material consumption. Brief Description of the Drawings

[0014] Figure 1 is a schematic diagram of a recovery device for acetonitrile waste liquid according to some embodiments of the present invention;

[0015] Figure 2 is a three-dimensional schematic diagram of a recovery device for acetonitrile waste liquid according to some embodiments of the present invention;

[0016] Figure 3 is Figure 1 a schematic diagram of the structure of the osmosis chamber in

[0017] Figure 4Yes Figure 1 Schematic structural diagram of the reaction chamber in

[0018] Figure 5 Yes Figure 1 Schematic structural diagram of the adsorption tower in

[0019] Description of the reference numerals in the drawings

[0020] 2 permeation unit; 3 oxidation unit; 6 rectification unit; 7 adsorption unit; 21 permeation chamber; 28 permeation layer; 31 reaction chamber; 11 ultrasonic generator; 61 rectification column; 71 adsorption tower; 714 upper layer; 715 lower layer; 312 upper material port; 313 lower material port; 716 product collection tank. Detailed description of the specific implementation mode

[0021] The following is a detailed description of the specific implementation mode of the present invention with reference to the accompanying drawings. It should be understood that the specific implementation mode described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0022] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0023] In the present invention, unless otherwise stated, the orientation terms such as "upper, lower, top, bottom" are generally in the direction shown in the drawings or in the vertical, perpendicular or gravitational direction for describing the relative positional relationship of each component.

[0024] The present invention discloses a method for recovering acetonitrile waste liquid on the one hand. The recovery method includes: sequentially subjecting the acetonitrile waste liquid to permeation, oxidation, extraction, rectification and adsorption to obtain recovered acetonitrile.

[0025] In some embodiments of the present invention, the oxidation includes contacting the permeated acetonitrile waste liquid with an oxidant under the irradiation of ultraviolet light or in the presence of ultrasonic waves to remove organic impurities. By permeation, oxidation for impurity removal in the presence of ultrasonic waves or ultraviolet light, combined with technologies such as extraction, rectification and adsorption, the water, salt and acetonitrile in the acetonitrile waste liquid can be effectively separated, and various trace impurities in the acetonitrile can be removed, and a high-purity acetonitrile product can be recovered.

[0026] In some embodiments of the present invention, the permeation includes multi-stage reverse osmosis using a reverse osmosis membrane, and the working pressure is 1-2.5 Mpa; using a multi-stage pressurized permeation membrane to pretreat the acetonitrile waste liquid to remove various solids, particulate impurities and most of the salts therein.

[0027] In some embodiments of the present invention, for better treatment effects, it is preferred that the number of stages of multi-stage permeation is 2 - 5, the pore size of the reverse osmosis membrane is 0.2 - 2 nm, and the material of the reverse osmosis membrane includes one or more of cellulose acetate, polysulfone, polyamide, and chitosan.

[0028] In the present invention, after permeation, the acetonitrile waste liquid first removes various organic impurities in the acetonitrile through ultrasonic waves and an oxidant to generate carbon dioxide and water, then the extractant is brought into contact with the acetonitrile waste liquid to remove most of the water, and then the raffinate phase is extracted.

[0029] In some embodiments of the present invention, the frequency of the ultrasonic waves is 25 - 40 KHz.

[0030] In some embodiments of the present invention, the added mass of the oxidant is 0.1% - 1% of the mass of the acetonitrile waste liquid obtained after permeation.

[0031] In some embodiments of the present invention, the oxidation conditions include: temperature 40 - 70 °C, reaction time 2 - 4 h.

[0032] In some embodiments of the present invention, the oxidant includes one or more of hydrogen peroxide, ferrous oxide, ferrous hydroxide, and ferrous sulfate.

[0033] In some embodiments of the present invention, the extraction conditions include: temperature 15 - 30 °C.

[0034] In some embodiments of the present invention, the added mass of the extractant is 30% - 60% of the mass of the acetonitrile waste liquid obtained after oxidation.

[0035] In some embodiments of the present invention, the extractant includes at least one of ethylene glycol, dimethyl sulfoxide, glycerol, or DMAC.

[0036] For the rectification of the acetonitrile after extraction to remove the extractant, in some embodiments of the present invention, the rectification conditions include: temperature 105 - 130 °C, top reflux ratio 2 - 6, top product discharge temperature controlled at 81 - 82 °C, and top product discharge rate controlled at 50 mL / min - 100 mL / min.

[0037] In some embodiments of the present invention, the adsorption includes sequentially adsorbing the rectified acetonitrile waste liquid with a first adsorbent and a second adsorbent to respectively remove trace organic impurities and trace moisture, wherein,

[0038] The first adsorbent includes one or more of activated carbon fiber, zirconium hydroxide, silicon dioxide, polyethyleneimine, and graphene oxide; the second adsorbent includes one or more of phosphorus pentoxide, calcium hydride, magnesium sulfate, and calcium chloride.

[0039] In some embodiments of the present invention, the acetonitrile waste liquid is a salt-containing acetonitrile waste liquid. The acetonitrile waste liquid includes, by mass percentage: 30-70% acetonitrile, 25-65% water, 1-4% inorganic salts (such as potassium chloride, magnesium sulfate), 0.1-0.5% organic salts (such as sodium acetate, sodium citrate), 0.05-0.2% unsaturated organic impurities (such as various aldehydes, phenols, ketones, etc.), 0.05-0.1% saturated organic impurities (such as n-hexane, ethanol), 0.1-0.5% other inorganic impurities (such as hydrochloric acid, sulfuric acid), and other solids and particles <0.1%; By using the present invention, the effective recovery rate of acetonitrile can be greater than 85%, the mass percentage of the recovered high-purity acetonitrile ≥99.9%, the water content is less than 100 ppm, and the single content of each organic impurity is less than 10 ppm.

[0040] In some embodiments of the present invention, the aforementioned acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated by pharmaceutical synthesis. Using the salt-containing acetonitrile waste liquid generated by pharmaceutical synthesis as a raw material, through multi-stage reverse osmosis, ultrasonic impurity removal, combined with extraction, rectification, adsorption and other technologies, water, salt and acetonitrile can be effectively separated, and various trace impurities in acetonitrile can be removed to obtain a high-purity acetonitrile product.

[0041] On the other hand, the present invention discloses a recovery device for acetonitrile waste liquid. The recovery device includes: a permeation unit 2, an oxidation unit 3, an extraction unit, a rectification unit 6 and an adsorption unit 7 connected in series in sequence to realize permeation, oxidation, extraction, rectification and adsorption of the acetonitrile waste liquid to obtain recovered acetonitrile.

[0042] In some embodiments of the present invention, the permeation unit 2 has a permeation chamber 21, and a plurality of permeation layers 28 are installed in the permeation chamber 21 at intervals in the height direction to perform pretreatment on the acetonitrile waste liquid introduced from the upper part by using multi-stage permeation and remove various solids, particulate impurities and most of the salts therein.

[0043] In some embodiments of the present invention, preferably 2-5 layers of permeation layers are installed at equal intervals in the permeation chamber 21. Each permeation layer 28 includes a reverse osmosis membrane fixed in the permeation chamber to enable 2-5 stages of pressurized permeation treatment of the acetonitrile waste liquid.

[0044] In some embodiments of the present invention, the oxidation unit 3 is equipped with an ultrasonic component or an ultraviolet light emitter to be used for making the permeated acetonitrile waste liquid contact with an oxidant under the irradiation of ultraviolet light or in the presence of ultrasonic waves to remove organic impurities. It should be noted that the present invention has no special requirements for the ultraviolet light emitter, and the present invention will not elaborate on this.

[0045] In some embodiments of the present invention, preferably, the oxidation unit 3 includes a reaction chamber 31 formed by surrounding with a housing. The ultrasonic component includes a plurality of ultrasonic generators 11 distributed on the housing. More preferably, the plurality of ultrasonic generators 11 are distributed at the bottom of the housing. More preferably, the number of the ultrasonic generators 11 is 8 - 16.

[0046] In some embodiments of the present invention, the rectification unit 6 includes a rectification column 61. The present invention has no special requirements for the rectification column, and a conventional rectification column can be used in the present invention, and details thereof will not be described herein again.

[0047] In some embodiments of the present invention, the adsorption unit 7 includes an adsorption tower 71. The top of the adsorption tower 71 is connected to the top of the rectification column. The upper layer 714 of the adsorption tower 71 is filled with a first adsorbent, and the lower layer 715 is filled with a second adsorbent to sequentially remove trace organic impurities and moisture in the acetonitrile waste liquid after rectification. A recovered acetonitrile outlet 716 is provided at the bottom of the adsorption tower. It can be understood that packing inner frames are installed in both the upper layer 714 and the lower layer 715 of the adsorption tower to carry the adsorbent; the top end of the adsorption tower 7 can be opened to take out the inner packing frame for loading, unloading and cleaning; a non - qualified product discharge port 717 is provided in the middle of the lower layer 15 of the adsorption tower for discharging and collecting the non - qualified acetonitrile collected liquid, and the collected liquid will participate in the next recovery as a raw material. The mass of acetonitrile discharged from the non - qualified product discharge port 717 is 10 - 25% of the mass of acetonitrile entering the product collection tank 716.

[0048] To reduce the floor area of the recovery equipment, the recovery equipment of the present invention can be installed to form an integrated equipment. In some embodiments of the present invention, the permeation unit 2 and the rectification unit 6 are installed side by side on the top of the oxidation unit 3, and the discharge port of the permeation chamber 21 and the feed port of the rectification column 61 can be respectively communicated with the top of the reaction chamber 31, and the top of the adsorption tower 71 is connected to the top of the rectification column 61.

[0049] In some embodiments of the present invention, a heating device (such as a heating coil) in the prior art is installed in the reaction chamber 31. A lower material port 313 is provided at the lower part of the reaction chamber 31, an upper material port 312 is provided at the upper part of the reaction chamber, and a left opening 319 and a right opening 310 are provided at the top of the reaction chamber. A control valve can be installed at the left opening to achieve an openable and closable connection with the bottom of the permeation chamber, and a control valve can be installed at the right opening to achieve an openable and closable connection with the bottom of the rectification column. It should be noted that both oxidation and extraction can be carried out in the reaction chamber. Specifically, in the presence of ultrasonic waves, the acetonitrile waste liquid entering the reaction chamber through the left opening 319 contacts the oxidant fed through the lower material port under oxidation conditions, oxidizing the organic impurities in the acetonitrile waste liquid to generate carbon dioxide and water, and the carbon dioxide is discharged from the upper material port 312; an extractant is fed through the lower material port 313 to extract the reacted material in the reaction chamber to remove most of the water. Among them, the raffinate phase containing most of the water is discharged from the upper material port 312. The extraction phase in the reaction chamber is heated to 105 - 130 °C, and the material in the reaction chamber enters the rectification column through the right opening 310 for rectification, and the overhead material of the rectification column enters the adsorption column.

[0050] In some embodiments of the present invention, the permeation chamber 21 is cylindrical, and the height of the permeation chamber 21 is 1000 mm - 1500 mm, and the diameter is 250 - 400 mm.

[0051] In some embodiments of the present invention, the length of the reaction chamber 31 is 800 - 1200 mm, the width is 600 - 900 mm, and the height is 600 mm - 1000 mm.

[0052] In some embodiments of the present invention, as Figure 1 shown, the recovery device of the present invention further includes an acetonitrile waste liquid storage tank 1, an extractant tank 4, and an oxidant tank 5. Among them, the acetonitrile waste liquid storage tank 1 is connected to the top of the permeation chamber 21 through a pipeline, and both the extractant tank 4 and the oxidant tank 5 are connected to the lower material port 313.

[0053] In some embodiments of the present invention, the height of the rectification column 61 is 1200 - 2400 mm, and the diameter is 200 - 400 mm.

[0054] In some embodiments of the present invention, the diameter of the adsorption column 71 is 300 - 500 mm. Among them, the packing heights of both the first adsorbent and the second adsorbent are 500 mm - 1000 mm.

[0055] In some embodiments of the present invention, a product collection tank 716 is connected to the bottom of the adsorption column 71, and the height of the product collection tank 716 is 400 - 600 mm.

[0056] The present invention can recover acetonitrile from the acetonitrile wastewater containing salt generated in the field of pharmaceutical synthesis. The equipment of the present invention has the advantages of simple integrated operation, high purity of the recovered acetonitrile, reaching the level of similar HPLC, and can be reused in pharmaceutical production again.

[0057] In some embodiments of the present invention, the acetonitrile waste liquid is first filled in the acetonitrile waste liquid storage tank 1, and then introduced into the upper inlet of the permeation chamber 21. Under the action of high pressure and the reverse osmosis membrane, various solids, particulate impurities, and most salts in the acetonitrile waste liquid are removed, and enter the reaction chamber 31 through the left opening 319. After all the acetonitrile waste liquid enters the reaction chamber 31, the left opening 319 is closed; the temperature in the reaction chamber 3 is controlled, the oxidant in the oxidant tank 5 is introduced into the reaction chamber 3 through the lower material port 313, and the ultrasonic generator 11 is started to make various organic impurities in the acetonitrile waste liquid react with the oxidant under ultrasonic waves to generate carbon dioxide and water, so as to remove them from the acetonitrile; then the temperature in the reaction chamber 31 is adjusted, the extractant in the extractant tank 4 is introduced into the reaction chamber 31 through the lower material port 13 to contact with the acetonitrile waste liquid, and the raffinate phase is discharged from the upper material port 12; then the reaction chamber 31 is heated, the right opening 310 is opened to connect the distillation column 61 to distill the acetonitrile, and the acetonitrile distilled from the top of the distillation column 61 enters the adsorption column 71; the acetonitrile in the adsorption column 71 passes through the upper adsorption layer 14 and the lower adsorption layer 15 in sequence, removes trace organic impurities and trace moisture respectively, discharges a part of the acetonitrile proportionally through the unqualified product discharge port 717, and collects the product acetonitrile in the product collection tank 716.

[0058] The advantages of the present invention are illustrated below through examples, but the present invention is not limited thereto.

[0059] Example 1

[0060] Adopt as Figure 1The process shown is as follows. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis. Its composition (by mass percentage) is: acetonitrile 45%, water 52%, inorganic salts 2%, organic salts 0.3%, unsaturated organic impurities 0.1%, saturated organic impurities 0.08%, other inorganic impurities 0.3%, and other solids and particles <0.1%. The acetonitrile waste liquid is first filled in waste liquid tank 1 and then fed into the upper inlet of the permeation chamber. The main structure of the permeation chamber has a height of 1200 mm, a diameter of 320 mm, and 4 reverse osmosis membranes inside to form a 4-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore diameter is 0.4 nm, and the material is a composite material of cellulose acetate and polysulfone. The working pressure during reverse osmosis is 2 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure of this reaction chamber has a length of 1000 mm, a width of 800 mm, and a height of 900 mm. The number of ultrasonic generators at the bottom is 12, and the working frequency is 30 KHz. The acetonitrile waste liquid first reacts with an oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous hydroxide (the ratio of the two is 2:3), and the mass of the oxidant is 0.5% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 60°C, and the reaction time is 3 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is dimethyl sulfoxide, and the mass of the extractant is 40% of the acetonitrile waste liquid. The extraction temperature is 20°C. After extraction, the raffinate phase is discharged from the upper and lower inlets and the heated extractant phase is rectified. The main structure of the rectification column has a height of 1800 mm and a diameter of 350 mm. The heating temperature is set at 120°C, the reflux ratio at the top of the column is 4, the outlet temperature at the top of the column is controlled at 82°C, and the outlet speed at the top of the column is controlled at 80 mL / min. The distillate at the top of the column then enters the adsorption column. The main structure of the adsorption column has a diameter of 400 mm, the height of the upper adsorption layer is 600 mm, and the height of the lower adsorption layer is 800 mm. The adsorbent used in the upper adsorption layer is activated carbon fiber and polyethyleneimine (the ratio of the two is 1:1), and the adsorbent used in the lower adsorption layer is magnesium sulfate and calcium chloride (the ratio of the two is 1:1). The acetonitrile discharged from the unqualified product outlet is 15% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0061] Example 2

[0062] Adopt as Figure 1The process shown is as follows. The acetonitrile waste liquid comes from the saline acetonitrile waste liquid generated in pharmaceutical synthesis, and its composition (by mass percentage) is: acetonitrile 60%, water 36%, inorganic salts 2.6%, organic salts 0.4%, unsaturated organic impurities 0.15%, saturated organic impurities 0.1%, other inorganic impurities 0.4%, and other solids and particles <0.05%. The acetonitrile waste liquid is first filled in the waste liquid tank 1 and then fed into the upper inlet of the osmosis chamber. The main structure height of the osmosis chamber is 1400 mm, the diameter is 360 mm, and the number of internal reverse osmosis membranes is 5 to form a 5-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore size is 0.25 nm, and the material is a composite material of polyamide and chitosan. The working pressure during reverse osmosis is 2.4 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure length of the reaction chamber is 1200 mm, the width is 800 mm, and the height is 800 mm. The number of ultrasonic generators at the bottom is 15, and the working frequency is 35 KHz. The acetonitrile waste liquid first reacts with the oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous oxide (the ratio of the two is 1:1), and the added mass of the oxidant is 1% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 65 °C, and the reaction time is 4 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is DMAC, and the mass of the extractant is 40% of the acetonitrile waste liquid. The extraction temperature is 16 °C. After extraction, the raffinate phase is discharged from the upper and lower inlets and the heated extraction phase is rectified. The main structure height of the rectification column is 2000 mm, and the diameter is 400 mm. The heating temperature is set at 125 °C, the reflux ratio at the top of the column is 5, the outlet temperature at the top of the column is controlled at 81.5 °C, and the outlet speed at the top of the column is controlled at 70 mL / min. The overhead distillate then enters the adsorption column. The main structure diameter of the adsorption column is 500 mm, the height of the upper adsorption layer is 750 mm, and the height of the lower adsorption layer is 850 mm. The adsorbent used in the upper adsorption layer is zirconium hydroxide and silica (the ratio of the two is 1:2), and the adsorbent used in the lower adsorption layer is phosphorus pentoxide and calcium hydride (the ratio of the two is 1:2). The acetonitrile discharged from the unqualified product outlet is 20% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0063] Example 3

[0064] Adopt as Figure 1The process shown is as follows. The acetonitrile waste liquid comes from the saline acetonitrile waste liquid generated in pharmaceutical synthesis. Its composition (by mass percentage) is: acetonitrile 34%, water 61%, inorganic salts 3.5%, organic salts 0.3%, unsaturated organic impurities 0.12%, saturated organic impurities 0.08%, other inorganic impurities 0.3%, and other solids and particles <0.1%. The acetonitrile waste liquid is first filled in waste liquid tank 1 and then fed into the upper inlet of the permeation chamber. The main structure of the permeation chamber has a height of 1100 mm, a diameter of 280 mm, and 3 reverse osmosis membranes inside to form a three-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore size is 1.2 nm, the material is cellulose acetate, and the working pressure during reverse osmosis is 1.5 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure of this reaction chamber has a length of 900 mm, a width of 700 mm, and a height of 600 mm. The number of ultrasonic generators at the bottom is 15, and the working frequency is 35 KHz. The acetonitrile waste liquid first reacts with an oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous sulfate (the ratio of the two is 1:1). The mass of the oxidant added is 0.4% of the mass of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 50 °C, and the reaction time is 2.5 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is ethylene glycol. The mass of the extractant is 32% of the acetonitrile waste liquid, and the extraction temperature is 28 °C. After extraction, the raffinate phase is discharged from the upper and lower inlets, and the heated extractant phase is rectified. The main structure of the rectification column has a height of 1500 mm and a diameter of 220 mm. The heating temperature is set at 118 °C, the reflux ratio at the top of the column is 2.5, the outlet temperature at the top of the column is controlled at 81 °C, and the outlet speed at the top of the column is controlled at 90 mL / min. The distillate at the top of the column then enters the adsorption column. The main structure of the adsorption column has a diameter of 360 mm. The height of the upper adsorption layer is 600 mm, and the height of the lower adsorption layer is 600 mm. The adsorbent used in the upper adsorption layer is polyethyleneimine and graphene oxide (the ratio of the two is 1:1), and the adsorbent used in the lower adsorption layer is calcium chloride. The acetonitrile discharged from the unqualified product outlet is 10% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0065] Example 4

[0066] Adopt as Figure 1The process shown is as follows. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis. Its composition (by mass percentage) is: acetonitrile 52%, water 44%, inorganic salts 2.8%, organic salts 0.5%, unsaturated organic impurities 0.15%, saturated organic impurities 0.1%, other inorganic impurities 0.2%, and other solids and particles <0.05%. The acetonitrile waste liquid is first filled in the waste liquid tank 1 and then fed into the upper inlet of the osmosis chamber. The main structure of the osmosis chamber has a height of 1000 mm, a diameter of 370 mm, and 4 reverse osmosis membranes inside to form a 4-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore size is 0.9 nm, the material is polysulfone, and the working pressure during reverse osmosis is 2.2 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure of this reaction chamber has a length of 1100 mm, a width of 800 mm, and a height of 850 mm. The number of ultrasonic generators at the bottom is 9, and the working frequency is 40 KHz. The acetonitrile waste liquid first reacts with an oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous hydroxide (the ratio of the two is 1:3), and the mass of the oxidant added is 0.8% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 60 °C, and the reaction time is 3 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is glycerol, and the mass of the extractant is 45% of the acetonitrile waste liquid. The extraction temperature is 22 °C. After extraction, the raffinate phase is discharged from the upper and lower inlets, and the heated extract phase is rectified. The main structure of the rectification column has a height of 2000 mm and a diameter of 300 mm. The heating temperature is set at 124 °C, the reflux ratio at the top of the column is 3.5, the discharge temperature at the top of the column is controlled at 82 °C, and the discharge speed at the top of the column is controlled at 65 mL / min. The distillate at the top of the column then enters the adsorption column. The main structure of the adsorption column has a diameter of 450 mm, the height of the upper adsorption layer is 500 mm, and the height of the lower adsorption layer is 500 mm. The adsorbent used in the upper adsorption layer is silica and graphene oxide (the ratio of the two is 1:1), and the adsorbent used in the lower adsorption layer is phosphorus pentoxide and magnesium sulfate (the ratio of the two is 1:1). The acetonitrile discharged from the unqualified product outlet is 18% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0067] Example 5

[0068] Different from Example 1, the acetonitrile waste liquid comes from the mobile phase waste liquid generated by high performance liquid chromatography, in which the mass fraction of acetonitrile is 52%, water is 45%, protein is 2%, unsaturated organic impurities are 0.4%, saturated organic impurities are 0.3%, inorganic impurities are 0.2%, and other solid substances are <0.1%. The acetonitrile waste liquid is first filled in the waste liquid tank 1, and then introduced into the upper inlet of the osmosis chamber. The main structure height of the osmosis chamber is 1200 mm, the diameter is 300 mm, and the number of internal reverse osmosis membranes is 4 to form a four-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore size is 1 nm, and the material is a composite material of polyamide and chitosan. The working pressure during reverse osmosis is 2 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure of the reaction chamber has a length of 1000 mm, a width of 900 mm, and a height of 700 mm. The number of ultrasonic generators at the bottom is 10, and the working frequency is 38 KHz. The acetonitrile waste liquid first reacts with the oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous hydroxide (the ratio of the two is 1:2). The mass of the oxidant added is 0.6% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 55 °C, and the reaction time is 3.5 h. After the reaction, an extractant is introduced into the reaction chamber. The extractant used is ethylene glycol. The mass of the extractant is 40% of the acetonitrile waste liquid, and the extraction temperature is 24 °C. After extraction, the raffinate phase is discharged from the upper and lower inlets and the heated extract phase is rectified. The main structure height of the rectification column is 1700 mm, and the diameter is 260 mm. The heating temperature is set at 130 °C, the reflux ratio at the top of the column is 3, the discharge temperature at the top of the column is controlled at 82 °C, and the discharge speed at the top of the column is controlled at 70 mL / min. The distillate at the top of the column then enters the adsorption column. The main structure diameter of the adsorption column is 400 mm. The height of the upper adsorption layer is 540 mm, and the height of the lower adsorption layer is 540 mm. The adsorbent used in the upper adsorption layer is silica and graphene oxide (the ratio of the two is 1:2). The adsorbent used in the lower adsorption layer is calcium chloride. The acetonitrile discharged from the unqualified product outlet is 15% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0069] Comparative Example 1

[0070] Adopt as Figure 1The process shown below is used, but the permeation chamber is not used. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis, and its composition (by mass percentage) is as follows: acetonitrile 54%, water 40%, inorganic salts 3.9%, organic salts 0.4%, unsaturated organic impurities 0.16%, saturated organic impurities 0.1%, other inorganic impurities 0.4%, other solids and particles <0.1%. The acetonitrile waste liquid is first filled in the waste liquid tank 1 and then directly enters the reaction chamber. The main structure of the reaction chamber has a length of 1000 mm, a width of 750 mm, and a height of 800 mm. The number of ultrasonic generators at the bottom is 8, and the working frequency is 28 KHz. The acetonitrile waste liquid first reacts with the oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous hydroxide (the ratio of the two is 1:1). The mass of the oxidant added is 1% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 60 °C, and the reaction time is 3 h. After the reaction is completed, an extractant is introduced into the reaction chamber. The extractant used is DMAC, and the mass of the extractant is 55% of the acetonitrile waste liquid. The extraction temperature is 25 °C. After the extraction is completed, the raffinate phase is discharged from the upper inlet and outlet, and the heated extraction phase is rectified. The main structure height of the rectification column is 2200 mm, and the diameter is 300 mm. The heating temperature is set at 125 °C, the reflux ratio at the top of the column is 5, the outlet temperature at the top of the column is controlled at 81.5 °C, and the outlet speed at the top of the column is controlled at 75 mL / min. The distillate at the top of the column then enters the adsorption column. The main structure diameter of the adsorption column is 400 mm. The height of the upper adsorption layer is 750 mm, and the height of the lower adsorption layer is 850 mm. The adsorbent used in the upper adsorption layer is polyethyleneimine and graphene oxide (the ratio of the two is 2:1), and the adsorbent used in the lower adsorption layer is phosphorus pentoxide and magnesium sulfate (the ratio of the two is 1:2). The acetonitrile discharged from the unqualified product outlet is 15% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0071] Comparative Example 2

[0072] Adopt as Figure 1The process shown, but without using an ultrasonic generator and an oxidant in the reaction chamber. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis. The composition (by mass percentage) is as follows: acetonitrile 38%, water 58%, inorganic salts 3.2%, organic salts 0.4%, unsaturated organic impurities 0.18%, saturated organic impurities 0.04%, other inorganic impurities 0.4%, and other solids and particles <0.1%. The salt-containing acetonitrile waste liquid is first filled in the waste liquid tank 1 and then introduced into the upper inlet of the osmosis chamber. The main structure height of the osmosis chamber is 1250 mm, the diameter is 260 mm, and the number of internal reverse osmosis membranes is 5 to form a 5-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, the pore diameter is 0.4 nm, and the material is a composite material of polyamide and chitosan. The working pressure during reverse osmosis is 1.8 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure length of the reaction chamber is 1200 mm, the width is 700 mm, and the height is 900 mm. An extractant is introduced into the reaction chamber. The extractant used is ethylene glycol, and the mass of the extractant is 55% of the acetonitrile waste liquid. The extraction temperature is 15°C. After extraction, the raffinate phase is discharged from the upper and lower inlets and the heated extraction phase is rectified. The main structure height of the rectification column is 2200 mm, and the diameter is 350 mm. The heating temperature is set at 115°C, the reflux ratio at the top of the column is 5.5, the discharge temperature at the top of the column is controlled at 81.5°C, and the discharge speed at the top of the column is controlled at 70 mL / min. The distillate at the top of the column then enters the adsorption column. The main structure diameter of the adsorption column is 350 mm, the height of the upper adsorption layer is 600 mm, and the height of the lower adsorption layer is 700 mm. The adsorbent used in the upper adsorption layer is zirconium hydroxide and graphene oxide (the ratio of the two is 1:3), and the adsorbent used in the lower adsorption layer is calcium hydride. The acetonitrile discharged from the unqualified product outlet is 16% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0073] Comparative Example 3

[0074] Adopt as Figure 1The process shown below is used, but without distillation rectification. Only distillation is used to purify the acetonitrile in the reaction chamber. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis. Its composition (by mass percentage) is as follows: acetonitrile 63%, water 34%, inorganic salts 1.9%, organic salts 0.3%, unsaturated organic impurities 0.12%, saturated organic impurities 0.08%, other inorganic impurities 0.4%, and other solids and particles <0.1%. The salt-containing acetonitrile waste liquid is first filled in the waste liquid tank 1 and then fed into the upper inlet of the permeation chamber. The main structure height of the permeation chamber is 1500 mm, the diameter is 330 mm, and the number of internal reverse osmosis membranes is 5 to form a 5-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore diameter is 0.4 nm, and the material is chitosan. The working pressure during reverse osmosis is 2.4 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure length of the reaction chamber is 850 mm, the width is 800 mm, and the height is 800 mm. The number of ultrasonic generators at the bottom is 12, and the working frequency is 34 KHz. The acetonitrile waste liquid first reacts with the oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous sulfate (the ratio of the two is 1:3), and the added mass of the oxidant is 1% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 65 °C, and the reaction time is 3.5 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is DMAC, and the mass of the extractant is 60% of the acetonitrile waste liquid. The extraction temperature is 26 °C. After extraction, the raffinate phase is discharged from the upper and lower inlets, and the heated extraction phase is distilled. The overhead distillate then enters the adsorption tower. The main structure diameter of the adsorption tower is 400 mm, the height of the upper adsorption layer is 700 mm, and the height of the lower adsorption layer is 550 mm. The adsorbent used in the upper adsorption layer is activated carbon fiber and polyethyleneimine (the ratio of the two is 1:1), and the adsorbent used in the lower adsorption layer is magnesium sulfate and calcium chloride (the ratio of the two is 1:1). The acetonitrile discharged from the unqualified product outlet is 22% of the amount of acetonitrile entering the product collection tank. Then, the finished acetonitrile is obtained from the product collection tank.

[0075] Comparative Example 4

[0076] Adopt as Figure 1The process shown, but without using the adsorption tower. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis. The composition of the salt-containing acetonitrile waste liquid (by mass percentage) is: acetonitrile 48%, water 49%, inorganic salts 2.2%, organic salts 0.3%, unsaturated organic impurities 0.1%, saturated organic impurities 0.04%, other inorganic impurities 0.3%, other solids and particles <0.1%. The salt-containing acetonitrile waste liquid is first filled in the waste liquid tank 1, and then fed into the upper inlet of the osmosis chamber. The main structure height of the osmosis chamber is 1200 mm, the diameter is 320 mm, and the number of internal reverse osmosis membranes is 3 to form a three-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore diameter is 1.2 nm, the material is polysulfone, and the working pressure during reverse osmosis is 2.5 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure length of the reaction chamber is 1000 mm, the width is 700 mm, the height is 600 mm, and the number of ultrasonic generators at the bottom is 9, with a working frequency of 40 KHz. The acetonitrile waste liquid first reacts with the oxidant under ultrasonic waves. The oxidant used is hydrogen peroxide and ferrous oxide (the ratio of the two is 1:2), and the added mass of the oxidant is 0.5% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 50 °C, and the reaction time is 4 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is ethylene glycol, and the mass of the extractant is 35% of the acetonitrile waste liquid. The extraction temperature is 28 °C. After extraction, the raffinate phase is discharged from the upper and lower inlets and the heated extract phase is rectified. The main structure height of the rectification tower is 1600 mm, and the diameter is 240 mm. The heating temperature is set at 130 °C, the reflux ratio at the top of the tower is 5, the outlet temperature at the top of the tower is controlled at 81.5 °C, and the outlet speed at the top of the tower is controlled at 80 mL / min. The collected overhead distillate is directly used as the finished acetonitrile.

[0077] Comparative Example 5

[0078] Adopt as Figure 1The process shown, but without using an ultrasonic generator. The acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated in pharmaceutical synthesis, and its composition (by mass percentage) is: acetonitrile 60%, water 37%, inorganic salts 1.5%, organic salts 1.2%, unsaturated organic impurities 0.2%, saturated organic impurities 0.05%, other inorganic impurities 0.04%, and other solids and particles <0.01%. The acetonitrile waste liquid is first filled in the waste liquid tank 1 and then fed into the upper inlet of the permeation chamber. The main structure height of the permeation chamber is 1300 mm, the diameter is 330 mm, and the number of internal reverse osmosis membranes is 4 to form a four-stage reverse osmosis. The distance between each reverse osmosis membrane is equal, its pore diameter is 1.5 nm, and the material is a composite material of cellulose acetate and polyamide. The working pressure during reverse osmosis is 1.5 Mpa. After reverse osmosis, the acetonitrile waste liquid enters the reaction chamber. The main structure length of this reaction chamber is 900 mm, the width is 700 mm, and the height is 600 mm. The acetonitrile waste liquid first reacts with an oxidant. The oxidant used is hydrogen peroxide and ferrous hydroxide (the ratio of the two is 1:2), and the mass of the oxidant is 0.6% of the acetonitrile waste liquid in the reaction chamber. The reaction temperature is 55°C and the reaction time is 4 h. After the reaction, an extractant is fed into the reaction chamber. The extractant used is DMAC, and the mass of the extractant is 55% of the acetonitrile waste liquid. The extraction temperature is 25°C. After extraction, the raffinate phase is discharged from the upper inlet and outlet, and the heated extraction phase is rectified. The main structure height of the rectification column is 1600 mm, and the diameter is 280 mm. The heating temperature is set at 125°C, the reflux ratio at the top of the column is 5, the outlet temperature at the top of the column is controlled at 82°C, and the outlet speed at the top of the column is controlled at 70 mL / min. The overhead distillate then enters the adsorption column. The main structure diameter of the adsorption column is 350 mm, the height of the upper adsorption layer is 700 mm, and the height of the lower adsorption layer is 600 mm. The adsorbent used in the upper adsorption layer is activated carbon fiber and silica (the ratio of the two is 2:1), and the adsorbent used in the lower adsorption layer is calcium hydride and calcium chloride (the ratio of the two is 1:2). The acetonitrile discharged from the unqualified product outlet is 10% of the amount of acetonitrile entering the product collection tank, and then the finished acetonitrile is obtained from the product collection tank.

[0079] Performance Detection and Comparison

[0080] Table 1: HPLC-grade Acetonitrile Detection Result Report of the Example

[0081] Table 1

[0082]

[0083] Table 2: Acetonitrile Detection Result Report of the Comparative Example

[0084] Table 2

[0085]

[0086] The preferred embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including the combination of each specific technical feature in any suitable manner. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods. However, these simple modifications and combinations should also be regarded as the content disclosed by the present invention and all fall within the protection scope of the present invention.

Claims

1. A method for recovering acetonitrile waste liquid, characterized in that, the recovery method includes: sequentially performing osmosis, oxidation, extraction, rectification, and adsorption on the acetonitrile waste liquid to obtain recovered acetonitrile.

2. The recovery method according to claim 1, wherein, the osmosis conditions include: the working pressure is 1 - 2.5 Mpa; and / or the osmosis includes performing multi-stage osmosis using a reverse osmosis membrane; preferably, the number of stages of the multi-stage osmosis is 2 - 5; and / or the pore size of the reverse osmosis membrane is 0.2 - 2 nm; and / or the material of the reverse osmosis membrane includes one or more of cellulose acetate, polysulfone, polyamide, and chitosan.

3. The recovery method according to claim 1 or 2, wherein, the oxidation includes contacting the osmosed acetonitrile waste liquid with an oxidant under the irradiation of ultraviolet light or in the presence of ultrasonic waves; preferably, the frequency of the ultrasonic waves is 25 - 40 KHz; and / or the added mass of the oxidant is 0.1% - 1% of the mass of the acetonitrile waste liquid obtained after osmosis; and / or the oxidation conditions include: the temperature is 40 - 70 °C, and the reaction time is 2 - 4 h; and / or the oxidant includes one or more of hydrogen peroxide, ferrous oxide, ferrous hydroxide, and ferrous sulfate.

4. The recovery method according to any one of claims 1 - 3, wherein, the extraction conditions include: the temperature is 15 - 30 °C; and / or the added mass of the extractant is 30% - 60% of the mass of the acetonitrile waste liquid obtained after oxidation; and / or the extractant includes at least one of ethylene glycol, dimethyl sulfoxide, glycerol, or DMAC.

5. The recovery method according to any one of claims 1 - 4, wherein, the rectification conditions include: the temperature is 105 - 130 °C, the reflux ratio at the top of the column is 2 - 6, the temperature of the overhead product is controlled at 81 - 82 °C, and the discharge rate of the overhead product is controlled at 50 mL / min - 100 mL / min; and / or the adsorption includes sequentially adsorbing the rectified acetonitrile waste liquid using a first adsorbent and a second adsorbent, wherein, the first adsorbent includes one or more of activated carbon fiber, zirconium hydroxide, silica, polyethyleneimine, and graphene oxide; the second adsorbent includes one or more of phosphorus pentoxide, calcium hydride, magnesium sulfate, and calcium chloride.

6. The recovery method according to any one of claims 1 - 5, wherein, the acetonitrile waste liquid includes, by mass percentage: 30 - 70% acetonitrile, 25 - 65% water, 1 - 4% inorganic salts, 0.1 - 0.5% organic salts, 0.05 - 0.2% unsaturated organic impurities, 0.05 - 0.1% saturated organic impurities, 0.1 - 0.5% other inorganic impurities, and < 0.1% other solids and particles; and / or the acetonitrile waste liquid comes from the salt-containing acetonitrile waste liquid generated by pharmaceutical synthesis.

7. A recovery device for acetonitrile waste liquid, characterized in that, the recovery device includes: an osmosis unit (2), an oxidation unit (3), an extraction unit, a rectification unit (6), and an adsorption unit (7) connected in series in sequence to realize sequentially performing osmosis, oxidation, extraction, rectification, and adsorption on the acetonitrile waste liquid to obtain recovered acetonitrile.

8. The recovery device according to claim 7, characterized in that, The permeation unit (2) has a permeation chamber (21), in which a plurality of permeation layers (28) are installed at intervals in the height direction to perform multi-stage permeation on the acetonitrile waste liquid; preferably, 2-5 layers of the permeation layers (28) are installed at intervals in the permeation chamber (21); and / or The oxidation unit (3) is equipped with an ultrasonic component or an ultraviolet light emitter for bringing the permeated acetonitrile waste liquid into contact with an oxidant under the irradiation of ultraviolet light or in the presence of ultrasonic waves; Preferably, the oxidation unit (3) includes a reaction chamber (31) formed by surrounding with a housing, the ultrasonic component includes a plurality of ultrasonic generators (11) distributed on the housing, and more preferably, the number of the ultrasonic generators (11) is 8-16; and / or The rectification unit (6) includes a rectification column (61); and / or The adsorption unit (7) includes an adsorption column (71), the upper layer (714) of the adsorption column (71) is filled with a first adsorbent, and the lower layer (715) is filled with a second adsorbent to sequentially remove organic impurities and water in the rectified acetonitrile waste liquid.

9. The recovery device according to claim 8, characterized in that The permeation unit (2) and the rectification unit (6) are installed side by side on the top of the oxidation unit (3), and the discharge port of the permeation chamber (21) and the feed port of the rectification column (61) can be respectively communicated with the top of the reaction chamber (31), and the top of the adsorption column (71) is communicated with the top of the rectification column (61); and / or A lower material port (313) is opened at the lower part of the reaction chamber (31), and an upper material port (312) is opened at the upper part of the reaction chamber.

10. The recovery device according to claim 8 or 9, characterized in that The permeation chamber (21) is cylindrical, the height of the permeation chamber (21) is 1000 mm - 1500 mm, and the diameter is 250 - 400 mm; and / or The length of the reaction chamber (31) is 800 - 1200 mm, the width is 600 - 900 mm, and the height is 600 mm - 1000 mm; and / or The height of the rectification column (61) is 1200 - 2400 mm, and the diameter is 200 - 400 mm; and / or The diameter of the adsorption column (71) is 300 - 500 mm, wherein the filling heights of the first adsorbent and the second adsorbent are both 500 mm - 1000 mm.

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