Photomagnetic response type deep eutectic solvent for absorbing acrylonitrile and preparation method of photomagnetic response type deep eutectic solvent

Abstract

The invention discloses a photomagnetic response type deep eutectic solvent for absorbing acrylonitrile and a preparation method thereof, the photomagnetic response type deep eutectic solvent comprises a hydrogen bond donor and a hydrogen bond acceptor, the hydrogen bond donor is one of triethylene glycol monobutyl ether (TGBE), N-methyl pyrrolidone (NMP), triethylene glycol (TEG) and triethanolamine (TEOA); the hydrogen bond acceptor is one of tetraethylene glycol dimethyl ether (TGDE) and sulfolane (SUL). The ether bond is used as a hydrogen bond acceptor region, the hydroxyl is used as a hydrogen bond donor region, a negative electricity region of the ether bond and a positive electricity region of acrylonitrile form a hydrogen bond, a wide van der Waals force is formed between a non-polar region of TGBE and acrylonitrile, and the whole absorption efficiency is synergistically improved with the hydrogen bond effect of TGDE. In addition, the fluidity of the solvent is remarkably improved due to the low viscosity of the ethers, and mass transfer limitation caused by high viscosity is avoided, so that the ethers have excellent performance in a continuous absorption tower.

Description

Technical Field

[0001] The present invention relates to the technical field of volatile organic waste gas treatment, and in particular to a photomagnetic response deep eutectic solvent capable of absorbing acrylonitrile and a preparation method thereof. Background Art

[0002] Acrylonitrile, as an important chemical raw material, is widely used in the production process of synthetic resins, rubber and synthetic fibers. However, acrylonitrile is a highly toxic and carcinogenic organic compound, and waste gas containing acrylonitrile is the focus and difficulty of volatile organic compounds (VOCs) management. At present, commonly used acrylonitrile waste gas treatment technologies mainly include catalytic combustion, biodegradation, adsorption and absorption methods. Among them, the absorption method has been widely used in practical applications due to its advantages of simple process, stable operation and strong treatment capacity. At present, water or dilute sodium hydroxide solution is commonly used in industry to absorb acrylonitrile waste gas. Chinese patent CN106861398A discloses a hydrolysis and incineration treatment process for organic waste gas containing acrylonitrile, which adopts two-stage alkaline solution absorption, but the removal rate is only 80%, and the rich liquid generated after absorption is difficult to treat. For this reason, it is of great significance to develop a new type of efficient and recyclable absorbent.

[0003] In recent years, deep eutectic solvents (DESs), a new type of green solvent, have become a research hotspot due to their low toxicity, low volatility, and high designability. Among them, photomagnetically responsive DESs offer lower viscosity, superior gas-liquid mass transfer performance, and high recyclability. Therefore, developing photomagnetically responsive DESs and exploring their microscopic absorption mechanisms are of great significance for achieving green and efficient acrylonitrile waste gas treatment. Summary of the Invention

[0004] The present invention overcomes the deficiencies of the prior art and provides a photomagnetic response deep eutectic solvent absorbing acrylonitrile and a preparation method thereof.

[0005] To achieve the above object, the technical solution adopted by the present invention is: a method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile, comprising the following steps:

[0006] S1: Mixing ferrosoferric oxide and an azobenzene derivative, adding a mixed solution of a carbodiimide condensing agent and a hydroxyl activator to activate the carboxyl group, allowing the mixture to stand, and adding an aldehyde crosslinking agent to react to obtain optical and magnetic dual-responsive core-shell particles;

[0007] S2: stirring and mixing the hydrogen bond donor and the hydrogen bond acceptor, heating, and drying to obtain an absorbent;

[0008] S3: Ultrasonic dispersion of the particles obtained in S1 and the absorbent obtained in S2 is carried out in a weakly alkaline environment to obtain a uniform photomagnetic responsive deep eutectic solvent absorbent.

[0009] In a preferred embodiment of the present invention, in S1, the azobenzene derivative is selected from carboxylated azobenzene, aminoazobenzene or azidoazobenzene, and the ratio of the azobenzene derivative to ferrosoferric oxide is 1:4-6.

[0010] In a preferred embodiment of the present invention, in S1, the carbodiimide condensing agent is selected from one of EDC, DCC or CMC, the hydroxyl activator is selected from one of NHS, Sulfo-NHS or HOBt, and the molar ratio of the carbodiimide condensing agent to the hydroxyl activator is 1:1-2.

[0011] In a preferred embodiment of the present invention, in S1, the standing time is 3-5 hours, the temperature is 40-60°C; the aldehyde crosslinking agent is selected from one of glutaraldehyde, o-phthalaldehyde or succinaldehyde, the ratio of azobenzene derivative to aldehyde crosslinking agent is 1:1-3, the reaction pH is 8.0, and the reaction time is 0.5-1.5 hours.

[0012] In a preferred embodiment of the present invention, in S2, the hydrogen bond donor is one of triethylene glycol monobutyl ether, N-methylpyrrolidone, triethylene glycol and triethanolamine; the hydrogen bond acceptor is one of tetraethylene glycol dimethyl ether and cyclopentane sulfone, the heating temperature is 50°C-70°C, the stirring speed is 200-400r / min, and the time is 2-4h; the drying temperature is 70-90°C, and the drying time is 12-24h.

[0013] In a preferred embodiment of the present invention, in S3, the neutral environment is specifically adjusted by adding carbonate buffer to pH=7.5, and the mixture is allowed to stand for 1-2 hours; the ultrasonic dispersion is specifically at 35-45 kHz for 25-35 minutes.

[0014] In a preferred embodiment of the present invention, the preparation of ferrosoferric oxide is specifically as follows: under a nitrogen environment, ferrous chloride tetrahydrate and ferric chloride hexahydrate are mixed, ammonia water is added to adjust the pH to react and obtain ferrosoferric oxide particles; and citric acid is added to react and obtain neutral ferrosoferric oxide.

[0015] In a preferred embodiment of the present invention, the molar ratio of ferrous chloride tetrahydrate and ferric chloride hexahydrate is 1:1.5-2.5, the pH reaction is adjusted to 11, the reaction temperature is 55-65°C, and the time is 0.5-1.5h; the molar ratio of ferrosoferric oxide to citric acid is 1:2-4, the citric acid reaction temperature is 75-85°C, and the time is 1-3h.

[0016] A photomagnetic responsive deep eutectic solvent absorbing acrylonitrile, comprising: an absorbent and core-shell particles;

[0017] The core-shell particles are uniformly cross-linked and distributed in the absorbent body. The core-shell particles are used to form low-viscosity channels and destroy the hydrogen bond network structure.

[0018] In a preferred embodiment of the present invention, the absorbent includes a hydrogen bond donor and a hydrogen bond acceptor, and the non-polar region of the hydrogen bond donor is used to enhance attraction.

[0019] The present invention solves the defects existing in the background technology and has the following beneficial effects:

[0020] (1) The present invention provides a photomagnetic responsive deep eutectic solvent that absorbs acrylonitrile and a preparation method thereof. When tetraethylene glycol dimethyl ether is selected as a hydrogen bond acceptor to prepare a deep eutectic solvent, it can be seen from its structure that tetraethylene glycol dimethyl ether only has ether bonds, and has no alcoholic hydroxyl groups compared to other alcohol ethers HBA. Therefore, it only has acceptor ability, which eliminates the possibility of forming hydrogen bonds between its molecules, which makes the deep eutectic solvent HBA prepared by it more tightly bonded with HBD, and the formed DESs have lower volatility and melting point. At the same time, the synthesis process of tetraethylene glycol dimethyl ether is mature and low in price, which can greatly reduce the cost of raw materials. In addition, the ether bond of tetraethylene glycol dimethyl ether can also form a stable hydrogen bond with acrylonitrile, thereby improving the solvent absorption effect.

[0021] (2) The present invention provides a photomagnetic responsive deep eutectic solvent that absorbs acrylonitrile and a preparation method thereof. Triethylene glycol monobutyl ether is selected as a hydrogen bond donor to prepare a deep eutectic solvent. Triethylene glycol monobutyl ether has low toxicity and biodegradability and excellent recyclability, which is in line with the concept of sustainable and green development. In addition, due to the presence of butyl groups, the non-polarity of the longer carbon chain molecules in triethylene glycol monobutyl ether is increased, which greatly increases the van der Waals interaction between triethylene glycol monobutyl ether and acrylonitrile.

[0022] (3) The present invention provides a photomagnetic responsive deep eutectic solvent that absorbs acrylonitrile and a preparation method thereof. By using tetraethylene glycol dimethyl ether as a hydrogen bond acceptor and triethylene glycol monobutyl ether as a hydrogen bond donor, the absorbent does not require a complex ionization step during the synthesis process, and only physical mixing is required to form a homogeneous liquid, which is simple to operate and has low energy consumption. In addition, the non-ionic deep eutectic solvent has better biodegradability, reducing the environmental burden. By adjusting the molar ratio of the hydrogen bond acceptor (HBA) to the hydrogen bond donor (HBD), the solvent density and viscosity can be further optimized, and the adaptability to high-concentration AN waste gas can be enhanced. This design flexibility provides broad space for the development of customized solvents.

[0023] (4) The present invention provides a photomagnetic responsive deep eutectic solvent for absorbing acrylonitrile and a preparation method thereof, which utilizes the interaction mechanism between the hydrogen bond acceptor TGDE and the hydrogen bond donor TGBE. The oxygen atoms of TGDE act as strong hydrogen bond acceptors to bind to the hydrogen atoms of AN, while the non-polar regions in HBD enhance the attractive force through van der Waals forces. The high correlation between electrostatic interaction and hydrogen bond strength provides a theoretical basis for optimizing solvent design. This precise control capability at the molecular level ensures the high efficiency and scalability of the absorbent. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments described in the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive efforts.

[0025] picture Figure 1 , 2 is the density map of the photomagnetic responsive deep eutectic solvent prepared by SUL and TGDE and TGBE, NMP, TEG, and TEOA at a molar ratio of 1:1 to 1:3.

[0026] Figure 3 , 4 is the viscosity spectrum of the photomagnetic responsive deep eutectic solvent prepared by SUL and TGDE and TGBE, NMP, TEG, and TEOA at a molar ratio of 1:1 to 1:3.

[0027] Figure 5 It is an IGM spectrum analysis of quantum chemical calculations of the interaction between AN and SUL, TGDE, TGBE, NMP, TEG, and TEOA.

[0028] Figure 6 This is the absorption efficiency spectrum of acrylonitrile absorbed by the photomagnetic responsive deep eutectic solvent of the present invention.

[0029] Figure 7 This is a graph showing the absorption efficiency of acrylonitrile after multiple rounds of absorption / desorption cycles of the photomagnetic responsive deep eutectic solvent of the present invention. DETAILED DESCRIPTION

[0030] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0031] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.

[0032] As shown in the figure, a method for preparing a photomagnetic responsive deep eutectic solvent that absorbs acrylonitrile comprises the following steps:

[0033] S1: Mixing ferrosoferric oxide and an azobenzene derivative, adding a mixed solution of a carbodiimide condensing agent and a hydroxyl activator to activate the carboxyl group, allowing the mixture to stand, and adding an aldehyde crosslinking agent to react to obtain optical and magnetic dual-responsive core-shell particles;

[0034] S2: stirring and mixing the hydrogen bond donor and the hydrogen bond acceptor, heating, and drying to obtain an absorbent;

[0035] S3: Ultrasonic dispersion of the particles obtained in S1 and the absorbent obtained in S2 is carried out in a weakly alkaline environment to obtain a uniform photomagnetic responsive deep eutectic solvent absorbent.

[0036] A photomagnetic responsive deep eutectic solvent for absorbing acrylonitrile comprises: an absorbent and core-shell particles; the core-shell particles are uniformly cross-linked and distributed within the absorbent body, the core-shell particles are used to form low-viscosity channels and destroy hydrogen bond network structures; the absorbent comprises a hydrogen bond donor and a hydrogen bond acceptor, and the non-polar region of the hydrogen bond donor is used to enhance attraction.

[0037] It should be noted that the prepared absorbent was used in a packed tower to absorb acrylonitrile (AN) waste gas, and then the regeneration performance of the absorbent was further explored through absorption / desorption cycle experiments. The operating temperature of the packed tower for acrylonitrile absorption was 30°C. The preparation steps of the deep eutectic solvent were: weighing HBA and HBD reagents of a fixed molar ratio, placing them in a round-bottom flask, mixing them, and preparing the absorbent by heating the stirrer in a water bath. The preparation temperature of the reagent was 70°C. The acrylonitrile waste gas was treated by a packed tower absorption system, operating at 30°C, and the solvent was recycled ≥9 times.

[0038] S1: Mixing ferrosoferric oxide and an azobenzene derivative, adding a mixed solution of a carbodiimide condensing agent and a hydroxyl activator to activate the carboxyl group, allowing the mixture to stand, and adding an aldehyde crosslinking agent to react to obtain optical and magnetic dual-responsive core-shell particles;

[0039] In the present invention, in S1, the azobenzene derivative is selected from carboxylated azobenzene, aminoazobenzene or azidoazobenzene, and the ratio of the azobenzene derivative to ferrosoferric oxide is 1:4-6.

[0040] In the present invention, in S1, the carbodiimide condensing agent is selected from one of EDC, DCC or CMC, the hydroxyl activator is selected from one of NHS, Sulfo-NHS or HOBt, and the molar ratio of the carbodiimide condensing agent to the hydroxyl activator is 1:1-2.

[0041] In the present invention, in S1, the standing time is 3-5 hours, the temperature is 40-60°C; the aldehyde crosslinking agent is selected from one of glutaraldehyde, o-phthalaldehyde or succinaldehyde, the ratio of azobenzene derivative to aldehyde crosslinking agent is 1:1-3, the reaction pH is 8.0, and the reaction time is 0.5-1.5 hours.

[0042] In the present invention, the preparation of ferroferric oxide is specifically as follows: under a nitrogen environment, ferrous chloride tetrahydrate and ferric chloride hexahydrate are mixed, ammonia water is added to adjust the pH and react to obtain ferroferric oxide particles; citric acid is added to react to obtain neutral ferroferric oxide; the ferrous chloride tetrahydrate and ferric chloride hexahydrate are mixed in a molar ratio of 1:1.5-2.5, the pH is adjusted to 11, the reaction temperature is 55-65°C, and the reaction time is 0.5-1.5h; the molar ratio of ferroferric oxide to citric acid is 1:2-4, the citric acid reaction temperature is 75-85°C, and the reaction time is 1-3h.

[0043] It should be noted that the preparation of core-shell particles begins with the synthesis of a magnetic core of ferroferric oxide. Under nitrogen protection, ferrous chloride tetrahydrate and ferric chloride hexahydrate were mixed in a 1:2 molar ratio via coprecipitation. The pH was adjusted to 11 with ammonia solution, and the mixture was reacted at 65°C for 1 hour to produce superparamagnetic Fe₃O₄ particles. Subsequently, citric acid (1:3 molar ratio) was added for carboxylation modification, and the reaction was continued at 80°C for 2 hours to impart a negative surface charge to the particles and enhance dispersion stability. Azobenzene derivatives (such as carboxylated azobenzene) were condensed with amino groups on the Fe₃O₄ surface using an EDC / NHS activation system. EDC first activated the carboxyl groups to form O-acylisourea intermediates under acidic conditions. NHS then converted these into stable succinimide esters under weak alkaline conditions, which then formed amide bonds with amino groups on the particle surface. Finally, glutaraldehyde (azobenzene:glutaraldehyde = 1:2) was added to introduce aldehyde groups via a Schiff base reaction at pH 8.0, enabling dynamic covalent crosslinking.

[0044] This core-shell structure exhibits both magnetic and optical responses (azobenzene cis-trans isomerization). The absorption devices employed include falling-film absorbers, rising-film absorbers, rotor liquid film columns, packed columns, plate columns, and Venturi absorbers. Operating pressures range from atmospheric pressure to pressurized pressure (2-40 bar) and temperatures between -20°C and 40°C. Electromagnetic fields and ultraviolet light fields are applied to these absorbers. When the electromagnetic field acts on the core-shell particles, the magnetic moments align along the magnetic field, forming chain-like structures approximately 500 nm wide. These particle chains act as "micro-paddles" in shear flow, with interchain slip producing a shear-thinning effect that reduces local viscosity. Furthermore, the oriented particle chains form low-resistance channels, reducing the tortuosity of the gas diffusion path. Furthermore, when the UV-light field triggers the trans-→cis isomerization of azobenzene, the larger dipole moment of the cis configuration generates strong electrostatic interactions with HBA (e.g., Cl-), competitively disrupting the existing HBD-HBA hydrogen bonds and leading to localized dissociation of the hydrogen bond network. The dual-field synergy further reduces the viscosity of the photomagnetically responsive deep eutectic solvent absorber. Upon removal of the external stimulus, the azobenzene reverts to its trans configuration under visible light irradiation, and the hydrogen bond network reorganizes through molecular thermal motion. This reversibility ensures the solvent maintains stable performance during the absorption-regeneration cycle. Furthermore, magnetically induced microconvection increases the frequency of gas-liquid interface renewal.

[0045] S2: stirring and mixing the hydrogen bond donor and the hydrogen bond acceptor, heating, and drying to obtain an absorbent;

[0046] In a preferred embodiment of the present invention, in S2, the hydrogen bond donor is one of triethylene glycol monobutyl ether, N-methylpyrrolidone, triethylene glycol and triethanolamine; the hydrogen bond acceptor is one of tetraethylene glycol dimethyl ether and cyclopentane sulfone, the heating temperature is 50°C-70°C, the stirring speed is 200-400r / min, and the time is 2-4h; the drying temperature is 70-90°C, and the drying time is 12-24h.

[0047] It should be noted that the choice of hydrogen bond donor (HBD) and acceptor (HBA) directly affects solvent viscosity. A nonionic HBD (e.g., polyethylene glycol PEG-200) and HBA (e.g., acetylcholine chloride) are mixed in a 2:1 molar ratio. The long-chain ether bonds (-O-) of PEG reduce intermolecular forces, and its flexible segments more easily integrate into the HBA lattice when heated and stirred at 70°C (300 rpm for 3 hours), disrupting the ionic bond network. A drying process (80°C for 24 hours) removes residual moisture and prevents hydrogen bond competition.

[0048] S3: Ultrasonic dispersion of the particles obtained in S1 and the absorbent obtained in S2 is carried out in a weakly alkaline environment to obtain a uniform photomagnetic responsive deep eutectic solvent absorbent.

[0049] In a preferred embodiment of the present invention, in S3, the weak alkaline environment is specifically adjusted by adding carbonate buffer to pH=7.5, and then allowed to stand for 1-2 hours; the ultrasonic dispersion is specifically 35-45kHz, and the time is 25-35 minutes.

[0050] It should be noted that when ether compounds act as hydrogen bond donors (HBDs), the ether bonds in their molecular chains exhibit unique flexibility. The lone electron pair of the oxygen atom forms a conformation with a low internal rotation barrier with the adjacent carbon-hydrogen bond, allowing the molecular chain to continuously change shape under thermal motion. This dynamic flexibility significantly reduces intermolecular forces compared to the rigid hydrogen bond network of traditional HBDs. The hydrogen bond binding energy between the ether oxygen atom and HBA is only 55% of the binding energy between urea-NH2 and HBA, resulting in a decrease in the viscosity of the DES system from 350 mPa·s to 180 mPa·s (at 30°C). At the same time, the non-polar ethoxy group (-CH2CH2O-) of PEG hinders the close packing of HBA-HBD through steric hindrance, forming more free volume (the free volume fraction increases by 0.15), further promoting molecular flow.

[0051] The absorption equipment used in the deep eutectic solvent absorbent of the present application is a falling film absorber, a rising film absorber, a rotor liquid film tower, a packed tower, a plate tower and a venturi absorber. The regeneration equipment used is a falling film evaporator, a distillation kettle, a gas stripping tower and a distillation tower. The specific operation process is as follows: when the acrylonitrile-containing waste gas absorption equipment is used, the acrylonitrile in the waste gas is absorbed by the photomagnetic responsive deep eutectic solvent, and the absorbed waste gas is discharged into the atmosphere or to other treatment devices. The photomagnetic responsive deep eutectic solvent that absorbs acrylonitrile enters the regeneration equipment to recover the acrylonitrile, and the regenerated photomagnetic responsive deep eutectic solvent enters the absorption tower for recycling.

[0052] Example 1

[0053] Raw material input:

[0054] Sulfolane (SUL) 0.61 mol

[0055] Triethylene glycol monobutyl ether (TGBE) 0.61 mol

[0056] Ferrous chloride tetrahydrate (FeCl2·4H2O) 2.5mmol

[0057] Ferric chloride hexahydrate (FeCl3·6H2O) 5.0mmol

[0058] Citric acid (C6H8O7) 7.5mmol

[0059] Carboxylated azobenzene (C 14 H 10 NO4)0.5mmol

[0060] EDC0.75mmol

[0061] NHS 1.125mmol

[0062] Glutaraldehyde 1.0 mmol

[0063] Preparation method:

[0064] S1: Dissolve FeCl2·4H2O and FeCl3·6H2O in 50mL of deoxygenated water, add ammonia water to pH 11 under nitrogen protection, and react at 60℃ for 1h; add citric acid and stir at 80℃ for 2h; at the same time, add DMF solution of carboxylated azobenzene, add EDC and NHS to the carboxyl-containing reactant at concentrations of EDC 2mM and NHSS 5mM, and react for 15 minutes; add the second reactant containing amino group to the reaction system (2). The second reactant containing amino group is dissolved in 0.1M sodium phosphate buffer system (pH=7.5). After mixing with the reaction system (2), the pH of the final mixture is about 7.0, which is conducive to the subsequent reaction of NHSS. The reaction is continued at room temperature for 2h to obtain the final product.

[0065] S2: SUL and TGBE were mixed and magnetically stirred at 60°C and 300 rpm for 3 h.

[0066] S3: The core-shell particles prepared in S1 were added to the product in S2, and ultrasonically dispersed in a pH 8.0 carbonate buffer (40 kHz, 30 min), and dried at 70°C for 18 h.

[0067] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 91.45%, wherein the packing height was 65 cm.

[0068] Example 2

[0069] The amount of raw materials put in in this embodiment is:

[0070] Sulfolane (SUL) 0.38 mol;

[0071] Triethylene glycol monobutyl ether (TGBE) 0.76 mol;

[0072] 200 g of a mixed solution of SUL-TGBE (1:2).

[0073] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0074] S1, 0.38 mol of SUL and 0.76 mol of TGBE reagent were mixed;

[0075] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0076] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TGBE (1:2).

[0077] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 90.12%, wherein the packing height was 65 cm.

[0078] Example 3

[0079] The amount of raw materials put in in this embodiment is:

[0080] Sulfolane (SUL) 0.27 mol

[0081] Triethylene glycol monobutyl ether (TGBE) 0.71 mol

[0082] Ferrous chloride tetrahydrate (FeCl2·4H2O) 2.2mmol

[0083] Ferric chloride hexahydrate (FeCl3·6H2O) 4.4mmol

[0084] Citric acid (C6H8O7) 6.6mmol

[0085] Carboxylated azobenzene (C 14 H 10 NO4)0.44mmol

[0086] EDC0.66mmol

[0087] NHS 0.99mmol

[0088] Glutaraldehyde 0.88 mmol

[0089] Preparation method:

[0090] S1: FeCl2·4H2O and FeCl3·6H2O were dissolved in 50 mL of deoxygenated water at a ratio of 1:2, and the pH was adjusted to 11 with ammonia water under nitrogen protection, and the reaction was carried out at 60°C for 1 h; citric acid was added and the reaction was carried out at 80°C for 2 h; a DMF solution (10 mL) of carboxylated azobenzene was added, and EDC / NHS was added for activation for 30 min, and then ferrosoferric oxide and a sustained-release phosphoric acid solution were added to adjust the pH to 7.5 and the reaction was carried out for 3 h. Glutaraldehyde was then added to cross-link the mixture at pH 8.0 for 1 h; the mixture was washed with ethanol three times and dried in vacuo at 60°C to obtain a black powder (0.38 g).

[0091] S2: SUL and TGBE were magnetically stirred at 60°C and 300 rpm for 3 h.

[0092] S3: The core-shell particles prepared in S1 were added to the product of S2, and the mixture was ultrasonically treated in a pH 8.0 carbonate buffer (40 kHz, 30 min), and dried at 70°C for 18 h.

[0093] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 89.37%, wherein the packing height was 65 cm.

[0094] Example 4

[0095] The amount of raw materials put in in this embodiment is:

[0096] Sulfolane (SUL) 0.91 mol

[0097] N-methylpyrrolidone (NMP) 0.91 mol;

[0098] 200 g of a mixed solution of SUL-NMP (1:1).

[0099] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0100] S1, 0.91 mol of SUL and 0.91 mol of NMP reagent were mixed;

[0101] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0102] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a SUL-NMP (1:1) deep eutectic solvent.

[0103] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 88.67%, wherein the packing height was 65 cm.

[0104] Example 5

[0105] The amount of raw materials put in in this embodiment is:

[0106] Sulfolane (SUL) 0.63 mol

[0107] N-methylpyrrolidone (NMP) 1.26 mol

[0108] 0.6g of ferroferric oxide particles (Fe3O4, 20nm)

[0109] Polydopamine coating agent (PDA) 0.12g

[0110] Silane coupling agent KH-5500.06mL

[0111] Preparation method:

[0112] S1: Fe3O4 particles were dispersed in Tris-HCl buffer (pH 8.5), dopamine hydrochloride (2 mg / mL) was added and stirred at room temperature for 12 h; the PDA-coated particles were collected by centrifugation and modified with KH-550 ethanol solution (1 vol%) for 2 h; and black powder (0.65 g) was obtained by vacuum drying at 60°C.

[0113] S2: SUL and NMP were magnetically stirred at 60°C and 300 rpm for 3 h.

[0114] S3: The modified particles (0.6 g) prepared in S1 were added to the product of S2, and the mixture was ultrasonically dispersed (40 kHz, 30 min) and dried at 70°C for 18 h.

[0115] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 91.79%, wherein the packing height was 65 cm.

[0116] Example 6

[0117] The amount of raw materials put in in this embodiment is:

[0118] Sulfolane (SUL) 0.48 mol

[0119] N-methylpyrrolidone (NMP) 1.44 mol;

[0120] 200 g of a mixed solution of SUL-NMP (1:3).

[0121] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0122] S1, 0.48 mol of SUL and 1.44 mol of NMP reagent were mixed;

[0123] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0124] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-NMP (1:3).

[0125] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 93.12%, wherein the packing height was 65 cm.

[0126] Example 7

[0127] The amount of raw materials put in in this embodiment is:

[0128] Sulfolane (SUL) 0.74 mol

[0129] Triethylene glycol (TEG) 0.74 mol;

[0130] 200 g of SUL-TEG (1:1) mixed solution;

[0131] Ferrous chloride tetrahydrate (FeCl2·4H2O) 2.2mmol

[0132] Ferric chloride hexahydrate (FeCl3·6H2O) 4.4mmol

[0133] Citric acid (C6H8O7) 6.6mmol

[0134] Carboxylated azobenzene (C 14 H 10 NO4)0.44mmol

[0135] EDC0.66mmol

[0136] NHS 0.99mmol

[0137] Glutaraldehyde 0.88 mmol

[0138] Based on the above raw materials, this embodiment provides a method for preparing a photomagnetic responsive deep eutectic solvent absorbent, the specific steps of which are:

[0139] S1. Dissolve FeCl2·4H2O and FeCl3·6H2O in 50 mL of deoxygenated water at a ratio of 1:2, adjust the pH to 11 with ammonia water under nitrogen protection, and react at 60°C for 1 h; add citric acid and react at 80°C for 2 h; add carboxylated azobenzene in DMF (10 mL), add EDC / NHS for activation for 30 min, add ferrosoferric oxide and phosphoric acid slow-release solution to adjust the pH to 7.5, react for 3 h, and then add glutaraldehyde to crosslink at pH 8.0 for 1 h; wash three times with ethanol, and dry in vacuo at 60°C to obtain a black powder (0.38 g).

[0140] S2. Mix 0.74 mol of SUL and 0.74 mol of TEG reagent; heat and stir at 60°C and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0141] S3. Dry the prepared deep eutectic solvent in a drying oven at 70° C. for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TEG (1:1);

[0142] S4. The core-shell particles prepared in S1 were added to the product of S3, and ultrasonic treatment (40kHz, 30min) was carried out in a pH 8.0 carbonate buffer solution, and dried at 70°C for 18h to obtain a photomagnetic responsive deep eutectic solvent.

[0143] The absorbent prepared by S4 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 75.31%, wherein the packing height was 65 cm.

[0144] Example 8

[0145] The amount of raw materials put in in this embodiment is:

[0146] Sulfolane (SUL) 0.47 mol

[0147] Triethylene glycol (TEG) 0.94 mol;

[0148] 200g of SUL-TEG (1:2) mixed solution.

[0149] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0150] S1, 0.47 mol of SUL and 0.94 mol of TEG reagent were mixed;

[0151] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0152] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TEG (1:2).

[0153] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 70.87%, wherein the packing height was 65 cm.

[0154] Example 9

[0155] The amount of raw materials put in in this embodiment is:

[0156] Sulfolane (SUL) 0.35 mol

[0157] Triethylene glycol (TEG) 1.05 mol;

[0158] 200 g of SUL-TEG (1:3) mixed solution;

[0159] 0.6g of ferroferric oxide particles (Fe3O4, 20nm)

[0160] Polydopamine coating agent (PDA) 0.12g

[0161] Silane coupling agent KH-5500.06mL

[0162] Based on the above raw materials, this embodiment provides a method for preparing a photomagnetic responsive deep eutectic solvent absorbent, the specific steps of which are:

[0163] S1. Disperse Fe3O4 particles in Tris-HCl buffer (pH 8.5), add dopamine hydrochloride (2 mg / mL) and stir at room temperature for 12 h; collect the PDA-coated particles by centrifugation and modify them with KH-550 ethanol solution (1 vol%) for 2 h; and dry them in a vacuum at 60°C to obtain a black powder (0.65 g).

[0164] S2. Mix 0.35 mol of SUL with 1.05 mol of TEG reagent; heat and stir at 60°C and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0165] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TEG (1:3).

[0166] S4, the modified particles (0.6 g) prepared in S1 were added to the product of S3, and ultrasonic dispersion (40 kHz, 30 min) was followed by drying at 70 ° C for 18 h to obtain a photomagnetic responsive deep eutectic solvent.

[0167] The absorbent prepared by S4 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 62.48%, wherein the packing height was 65 cm.

[0168] Example 10

[0169] The amount of raw materials put in in this embodiment is:

[0170] Sulfolane (SUL) 0.75 mol

[0171] Triethylene glycol (TEOA) 0.75 mol;

[0172] 200 g of a mixed solution of SUL-TEOA (1:1).

[0173] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0174] S1, 0.75 mol of SUL and 0.75 mol of TEOA reagent were mixed;

[0175] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0176] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TEOA (1:1).

[0177] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 51.32%, wherein the packing height was 65 cm.

[0178] Example 11

[0179] The amount of raw materials put in in this embodiment is:

[0180] Sulfolane (SUL) 0.48 mol

[0181] Triethylene glycol (TEOA) 0.96 mol;

[0182] 200 g of a mixed solution of SUL-TEOA (1:2).

[0183] Based on the above raw materials, this embodiment provides a method for preparing a photomagnetic responsive deep eutectic solvent absorbent, the specific steps of which are:

[0184] S1, 0.48 mol of SUL and 0.96 mol of TEOA reagent were mixed;

[0185] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0186] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TEOA (1:2).

[0187] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 42.31%, wherein the packing height was 65 cm.

[0188] Example 12

[0189] The amount of raw materials put in in this embodiment is:

[0190] Sulfolane (SUL) 0.35 mol

[0191] Triethylene glycol (TEOA) 1.05 mol;

[0192] 200 g of a mixed solution of SUL-TEOA (1:3).

[0193] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0194] S1, 0.35 mol of SUL and 1.05 mol of TEOA reagent were mixed;

[0195] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0196] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of SUL-TEOA (1:3).

[0197] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 30.18%, wherein the packing height was 65 cm.

[0198] Example 13

[0199] The amount of raw materials put in in this embodiment is:

[0200] Ferrous chloride tetrahydrate (FeCl2·4H2O) 2.5mmol

[0201] Ferric chloride hexahydrate (FeCl3·6H2O) 5.0mmol

[0202] Citric acid (C6H8O7) 7.5mmol

[0203] Carboxylated azobenzene (C 14 H 10 NO4)0.5mmol

[0204] EDC0.75mmol

[0205] NHS 1.125mmol

[0206] Glutaraldehyde 1.0 mmol

[0207] Tetraethylene glycol dimethyl ether (TGDE) 0.46 mol

[0208] Triethylene glycol monobutyl ether (TGBE) 0.46 mol;

[0209] 200 g of TGDE-TGBE (1:1) mixed solution.

[0210] Based on the above raw materials, this embodiment provides a method for preparing a photomagnetic responsive deep eutectic solvent absorbent, the specific steps of which are:

[0211] S1. Dissolve FeCl2·4H2O and FeCl3·6H2O in 50mL of deoxygenated water, add ammonia water to pH 11 under nitrogen protection, and react at 60℃ for 1h; add citric acid and stir at 80℃ for 2h; at the same time, add DMF solution of carboxylated azobenzene, add EDC and NHS to the carboxyl-containing reactant at concentrations of EDC 2mM and NHSS 5mM, and react for 15 minutes; add the second reactant containing amino group to the reaction system (2). The second reactant containing amino group is dissolved in 0.1M sodium phosphate buffer system (pH=7.5). After mixing with the reaction system (2), the pH of the final mixed solution is about 7.0, which is conducive to the subsequent reaction of NHSS. The reaction is continued at room temperature for 2h to obtain the final product.

[0212] S2. 0.46 mol of TGDE and 0.46 mol of TGBE reagent were mixed, and heated and stirred at 60°C and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0213] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TGBE (1:1).

[0214] S4. Add the core-shell particles prepared in S1 to the product of S3, ultrasonically disperse them in a pH 8.0 carbonate buffer (40kHz, 30min), and dry them at 70°C for 18h to obtain a photomagnetic responsive deep eutectic solvent.

[0215] The absorbent prepared by S4 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 96.34%, wherein the packing height was 65 cm.

[0216] Example 14

[0217] The amount of raw materials put in in this embodiment is:

[0218] Tetraethylene glycol dimethyl ether (TGDE) 0.32 mol

[0219] Triethylene glycol monobutyl ether (TGBE) 0.64 mol;

[0220] 200 g of TGDE-TGBE (1:2) mixed solution.

[0221] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0222] S1, 0.32 mol of TGDE and 0.64 mol of TGBE reagent were mixed;

[0223] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0224] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TGBE (1:2).

[0225] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 94.67%, wherein the packing height was 65 cm.

[0226] Example 15

[0227] The amount of raw materials put in in this embodiment is:

[0228] Tetraethylene glycol dimethyl ether (TGDE) 0.24 mol

[0229] Triethylene glycol monobutyl ether (TGBE) 0.72 mol;

[0230] 200 g of TGDE-TGBE (1:3) mixed solution.

[0231] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0232] S1, 0.24 mol of TGDE and 0.72 mol of TGBE reagent were mixed;

[0233] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0234] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TGBE (1:3).

[0235] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 93.88%, wherein the packing height was 65 cm.

[0236] Example 16

[0237] The amount of raw materials put in in this embodiment is:

[0238] Tetraethylene glycol dimethyl ether (TGDE) 0.62 mol

[0239] N-methylpyrrolidone (NMP) 0.62 mol;

[0240] 200 g of a mixed solution of TGDE-NMP (1:1).

[0241] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0242] S1, 0.62 mol of TGDE and 0.62 mol of NMP reagent were mixed;

[0243] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0244] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-NMP (1:1).

[0245] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 93.02%, wherein the packing height was 65 cm.

[0246] Example 17

[0247] The amount of raw materials put in in this embodiment is:

[0248] Tetraethylene glycol dimethyl ether (TGDE) 0.48 mol

[0249] N-methylpyrrolidone (NMP) 0.96 mol;

[0250] 200 g of a mixed solution of TGDE-NMP (1:2).

[0251] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0252] S1, 0.48 mol of TGDE and 0.96 mol of NMP reagent were mixed;

[0253] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0254] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-NMP (1:2).

[0255] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 94.13%, wherein the packing height was 65 cm.

[0256] Example 18

[0257] The amount of raw materials put in in this embodiment is:

[0258] Tetraethylene glycol dimethyl ether (TGDE) 0.38 mol

[0259] N-methylpyrrolidone (NMP) 1.14 mol;

[0260] 200 g of a mixed solution of TGDE-NMP (1:3).

[0261] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0262] S1, 0.38 mol of TGDE and 1.14 mol of NMP reagent were mixed;

[0263] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0264] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-NMP (1:3).

[0265] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 96.67%, wherein the packing height was 65 cm.

[0266] Example 19

[0267] The amount of raw materials put in in this embodiment is:

[0268] Tetraethylene glycol dimethyl ether (TGDE) 0.54 mol

[0269] Triethylene glycol (TEG) 0.54 mol;

[0270] 200 g of TGDE-TEG (1:1) mixed solution.

[0271] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0272] S1, 0.54 mol of TGDE and 0.54 mol of TEG reagent were mixed;

[0273] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0274] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TEG (1:1).

[0275] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 86.32%, wherein the packing height was 65 cm.

[0276] Example 20

[0277] The amount of raw materials put in in this embodiment is:

[0278] Tetraethylene glycol dimethyl ether (TGDE) 0.38 mol

[0279] Triethylene glycol (TEG) 0.76 mol;

[0280] 200 g of TGDE-TEG (1:2) mixed solution.

[0281] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0282] S1, 0.38 mol of TGDE and 0.76 mol of TEG reagent were mixed;

[0283] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0284] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TEG (1:2).

[0285] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 82.79%, wherein the packing height was 65 cm.

[0286] Example 21

[0287] The amount of raw materials put in in this embodiment is:

[0288] Tetraethylene glycol dimethyl ether (TGDE) 0.30 mol

[0289] Triethylene glycol (TEG) 0.90 mol;

[0290] 200 g of TGDE-TEG (1:3) mixed solution.

[0291] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0292] S1, 0.30 mol of TGDE and 0.90 mol of TEG reagent were mixed;

[0293] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0294] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TEG (1:3).

[0295] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 75.35%, wherein the packing height was 65 cm.

[0296] Example 22

[0297] The amount of raw materials put in in this embodiment is:

[0298] Tetraethylene glycol dimethyl ether (TGDE) 0.54 mol

[0299] Triethanolamine (TEOA) 0.54 mol;

[0300] 200 g of TGDE-TEOA (1:1) mixed solution.

[0301] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0302] S1, 0.54 mol of TGDE and 0.54 mol of TEOA reagent were mixed;

[0303] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0304] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TEOA (1:1).

[0305] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 60.31%, wherein the packing height was 65 cm.

[0306] Example 23

[0307] The amount of raw materials put in in this embodiment is:

[0308] Tetraethylene glycol dimethyl ether (TGDE) 0.38 mol

[0309] Triethanolamine (TEOA) 0.76 mol;

[0310] 200 g of TGDE-TEOA (1:2) mixed solution.

[0311] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0312] S1, 0.38 mol of TGDE and 0.76 mol of TEOA reagent were mixed;

[0313] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0314] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TEOA (1:2).

[0315] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was 53.44%, wherein the packing height was 65 cm.

[0316] Example 24

[0317] The amount of raw materials put in in this embodiment is:

[0318] Tetraethylene glycol dimethyl ether (TGDE) 0.30 mol

[0319] Triethanolamine (TEOA) 0.90 mol;

[0320] 200 g of a mixed solution of TGDE-TEOA (1:3).

[0321] Based on the above raw materials, this embodiment provides a method for preparing a deep eutectic solvent absorbent, and the specific steps are:

[0322] S1, 0.30 mol of TGDE and 0.90 mol of TEOA reagent were mixed;

[0323] S2. The mixed reagents were placed in a flask and heated and stirred in a magnetic stirring water bath at 60° C. and 300 rpm for 3 h to prepare a deep eutectic solvent;

[0324] S3. The prepared deep eutectic solvent was placed in a drying oven at 70° C. and dried for 18 h to remove moisture, thereby obtaining a deep eutectic solvent of TGDE-TEOA (1:9).

[0325] The absorbent prepared by S3 was subjected to a dynamic absorption test in a packed tower at 30°C and a standard atmospheric pressure, and the absorption effect was found to be 42.36%, wherein the packing height was 65 cm.

[0326] Example 25

[0327] By revealing the interactions between DESs and AN through quantum chemical calculations (QC), IGM analyzes the weak interactions within molecules, helping to observe and quantify the effects of these interactions on molecular behavior and properties.

[0328] Experimental Example 26

[0329] In this experiment, eight photomagnetically responsive deep eutectic solvent absorbents were tested for continuous absorption of acrylonitrile in a simulated industrial waste gas treatment system (at 30°C and standard atmospheric pressure) using a packed column with a 25 mm inner diameter, 4×4 mm θ-rings, and a height of 65 cm. The results revealed that TGDE-TGBE and TGDE-NMP deep eutectic solvents exhibited the best absorption efficiency for acrylonitrile. However, due to the high volatility of NMP, significant solvent evaporation losses, certain toxicity, and poor biodegradability, TGDE-TGBE was ultimately selected. Furthermore, the regeneration of the absorbent was verified through continuous absorption / desorption cycles. After 10 cycles, the absorbent's absorption capacity remained unchanged, confirming the regeneration capability of the absorbent. Its excellent acrylonitrile absorption performance and reproducibility demonstrate that the TGDE-TGBE (1:1) deep eutectic solvent is a promising absorbent for waste gas treatment.

[0330] The above description is based on the ideal embodiment of the present invention. Based on the above description, relevant personnel can make various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the content of the specification and must be determined according to the scope of the claims.

Claims

1. A method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile, characterized in that: The following steps are involved: S1: Mixing ferrosoferric oxide and an azobenzene derivative, adding a mixed solution of a carbodiimide condensing agent and a hydroxyl activator to activate the carboxyl group, allowing the mixture to stand, and adding an aldehyde crosslinking agent to react to obtain optical and magnetic dual-responsive core-shell particles; S2: stirring and mixing the hydrogen bond donor and the hydrogen bond acceptor, heating, and drying to obtain an absorbent; S3: Ultrasonic dispersion of the particles obtained in S1 and the absorbent obtained in S2 is carried out in a weakly alkaline environment to obtain a uniform photomagnetic responsive deep eutectic solvent absorbent.

2. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 1, characterized in that: In S1, the azobenzene derivative is selected from carboxylated azobenzene, aminoazobenzene or azidoazobenzene, and the ratio of the azobenzene derivative to ferrosoferric oxide is 1:4-6.

3. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 1, characterized in that: In S1, the carbodiimide condensing agent is selected from one of EDC, DCC or CMC, the hydroxyl activating agent is selected from one of NHS, Sulfo-NHS or HOBt, and the molar ratio of the carbodiimide condensing agent to the hydroxyl activating agent is 1:1-2.

4. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 1, characterized in that: In S1, the standing time is 3-5 hours, the temperature is 40-60° C.; the aldehyde crosslinking agent is selected from one of glutaraldehyde, o-phthalaldehyde or succinaldehyde, the ratio of azobenzene derivative to aldehyde crosslinking agent is 1:1-3, the reaction pH is 8.0, and the reaction time is 0.5-1.5 hours.

5. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 1, characterized in that: In S2, the hydrogen bond donor is one of triethylene glycol monobutyl ether, N-methylpyrrolidone, triethylene glycol and triethanolamine; the hydrogen bond acceptor is one of tetraethylene glycol dimethyl ether and cyclopentane sulfone; the heating temperature is 50°C-70°C, the stirring speed is 200-400 r / min, and the time is 2-4 hours; the drying temperature is 70-90°C, and the drying time is 12-24 hours.

6. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 1, characterized in that: In the S3, the neutral environment is specifically adjusted by adding carbonate buffer to make pH=7.5, and then standing for 1-2 hours; the ultrasonic dispersion is specifically 35-45 kHz, and the time is 25-35 minutes.

7. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 2, characterized in that: The preparation of ferroferric oxide is specifically as follows: under a nitrogen environment, ferrous chloride tetrahydrate and ferric chloride hexahydrate are mixed, ammonia water is added to adjust the pH reaction to obtain ferroferric oxide particles; citric acid is added to react to obtain neutral ferroferric oxide.

8. The method for preparing a photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 7, characterized in that: The molar ratio of ferrous chloride tetrahydrate and ferric chloride hexahydrate is 1:1.5-2.5, the pH is adjusted to 11, the reaction temperature is 55-65°C, and the reaction time is 0.5-1.5h; the molar ratio of ferrosoferric oxide to citric acid is 1:2-4, the reaction temperature of citric acid is 75-85°C, and the reaction time is 1-3h.

9. A photomagnetic responsive deep eutectic solvent absorbing acrylonitrile, based on the preparation method according to any one of claims 1 to 8, characterized in that: include: absorbents and core-shell particles; The core-shell particles are uniformly cross-linked and distributed in the absorbent body. The core-shell particles are used to form low-viscosity channels and destroy the hydrogen bond network structure.

10. The photomagnetic responsive deep eutectic solvent absorbing acrylonitrile according to claim 9, characterized in that: The absorbent includes a hydrogen bond donor and a hydrogen bond acceptor, and the non-polar region of the hydrogen bond donor is used to enhance attraction.

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