CN110465277B - Ammonia gas molecular imprinting adsorbent for separating sludge aerobic composting mixed gas and recovering ammonia gas and preparation thereof - Google Patents
Ammonia gas molecular imprinting adsorbent for separating sludge aerobic composting mixed gas and recovering ammonia gas and preparation thereof Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C05—FERTILISERS; MANUFACTURE THEREOF
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- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention provides an ammonia molecular imprinting adsorbent for separating sludge aerobic composting mixed gas and recovering ammonia and a preparation method thereof. The preparation comprises the following steps: adding ammonia water and acrylic functional monomer into a solvent, and uniformly mixing; adding azodiisobutyronitrile initiator and ethylene glycol dimethacrylate cross-linking agent into the system, and mixing uniformly; performing free radical polymerization reaction, and collecting a precipitate; ultrasonically cleaning the precipitate to remove the template and the reaction solvent; transferring the eluted precipitated substances into a sulfuric acid solution with the pH value of 0.5, sealing, and reacting under stirring to hydrolyze ester functional groups in part of the crosslinking agent to form carboxyl functional groups; washing with deionized water, and vacuum drying. The adsorbent obtained by the invention has good adsorption selectivity for ammonia gas in mixed gas generated by sludge composting, has low adsorption capacity of dimethyl sulfide and dimethyl disulfide, and can realize efficient separation of ammonia gas, dimethyl sulfide and dimethyl disulfide.
Description
Technical Field
The invention belongs to a gas separation technology, and particularly relates to an ammonia gas molecular imprinting adsorbent for separating sludge aerobic compost mixed gas and recovering ammonia gas and a preparation method thereof.
Background
Aerobic composting is an important treatment mode for realizing sludge reduction, harmlessness and recycling. However, a large amount of malodorous gases, whose main components include ammonia gas, dimethyl sulfide and dimethyl disulfide, are generated in the sludge aerobic composting process. On-site monitoring shows that the discharge amount of ammonia in the sludge in the aerobic composting process is up to 4.35-10.95 g/kg of dry sludge, and the discharge amounts of dimethyl sulfide and dimethyl disulfide are 0.071-0.22 and 0.11-0.25 g/kg of dry sludge respectively. If no effective treatment measures are taken, the direct discharge pollutes the environmental air and harms the human health, and the development of the aerobic composting industry is seriously restricted.
The main methods for treating malodorous gas include biological method, absorption method and adsorption method. The biological method has the advantages of low cost and the disadvantage that the target substance cannot be separated and recovered. Many patents related to the treatment of malodorous gases by biological methods, for example, patent 201410460781.2 reports an apparatus and method for simultaneously removing malodorous gases and microbial aerosols, wherein the malodorous gases with good water solubility are removed in a wet scrubbing zone, and the remaining gases are decomposed into harmless substances in a biological filtration zone. Patent 201310177593.4 reports a device and method for treating malodorous gas by a combined biofiltration-activated carbon method, wherein most malodorous gas (including ammonia gas) is degraded by microorganisms in a biofiltration unit, and undegraded part is removed by adsorption in an activated carbon unit. The absorption method has the advantages of high removal rate of malodorous gas with good water solubility and poor absorption effect of water-insoluble components in the malodorous gas. For example, patent 201110105217.5 reports an ammonia gas absorption apparatus including a gas-liquid separation buffer, a first combined cooling absorption tower, etc., and ammonia gas is removed after being subjected to a multi-stage absorption process.
The adsorption method can realize the adsorption separation and then the recovery of the substances with recovery value. The ammonia gas can be easily converted into liquid ammonia at-33 ℃ or 700-800 kpa, and the liquid ammonia can be used as chemical raw materials and refrigerants and is a high-quality hydrogen storage fuel. Therefore, the high-emission ammonia gas in the sludge aerobic composting process has high recovery value. The mixed gas in the sludge composting process can be collected in a closed manner, and then the ammonia gas is absorbed and separated and then recovered after passing through the adsorbent with high selectivity to the ammonia gas, the dimethyl sulfide and the dimethyl disulfide.
Patent 201610277915.6 reports the use of microsphere grafted starch in ammonia adsorption, in which carboxylic acid polymers are grafted onto starch by polymerization to absorb ammonia gas generated during cigarette combustion. However, only single gas ammonia adsorption is tested, separation of ammonia in mixed components, such as dimethyl sulfide and dimethyl disulfide, is not studied, and the separation effect is unknown; in the dynamic adsorption experiment of the ammonia gas, whether the penetration time of the experimental group is prolonged or not compared with that of the blank group is only tested, and the adsorption quantity of the ammonia gas cannot be calculated according to given data; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, and the adsorption stability is unknown.
Patent 201410422466.0 reports a modification method for effectively improving the adsorption performance of activated carbon on trace ammonia gas, which can be used for removing ammonia gas in indoor air, such as ammonia gas emitted from interior decoration materials, by sequentially modifying activated carbon with nitric acid, citric acid and butanetetracarboxylic acid. Patent 200810016263.6 reports an ammonia gas purifying adsorbent and a preparation method thereof, which is suitable for removing ammonia gas in indoor air by carrying out acid modification on carriers such as activated carbon or alumina. However, the above patents only test the concentration change of single gas ammonia before and after passing through the adsorbent, and the given data can not calculate the adsorption amount of ammonia; the separation of ammonia in the mixed components is not studied, and the separation effect is unknown; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, and the adsorption stability is unknown.
Patent 201810339275.6 reports the preparation of a metal foam/metal organic framework composite material that can be used to adsorb ammonia in ambient air by loading benzenetricarboxylic acid onto a copper foam framework to form a MOF composite material. However, the patent only studies the dynamic adsorption of single ammonia gas, does not study the separation of ammonia gas in mixed components, and the separation effect is unknown; in addition, the mass of the adsorbent is not given in the dynamic adsorption experiment of the ammonia gas, and the dynamic adsorption quantity of the ammonia gas cannot be calculated; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, and the adsorption stability is unknown.
Patent 201210238838.5 discloses a solid sample block containing a mixture of ceramic fiber and silica sol and a preparation method thereof, wherein anhydrous magnesium chloride, ceramic fiber and industrial silicon are mixed according to a certain proportion, and the mixture is filled into a closed container, stirred and dried to form a porous solid sample block. Patent 201210238802.7 reports an ammonia storage mixture and preparation of magnesium salt by filling a tank with powders of magnesium chloride salt, molecular sieves, clay, etc. to make a porous solid mass. The above patent is applicable to an SCR aftertreatment system for automobile exhaust gas and a fuel cell system. However, the above patents only study the static adsorption of single ammonia gas under high pressure, and cannot obtain the dynamic adsorption amount under normal pressure; the separation of ammonia in the mixed components is not studied, and the separation effect is unknown; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, and the adsorption stability is unknown.
Patent 201310013470.7 reports a preparation method of an ammonia removal material, and the ammonia removal agent is composed of a NaY molecular sieve, copper sulfate pentahydrate, a tartaric acid binder and the like, and is suitable for removing ammonia gas in industrial tail gas, sewage treatment plants and the like. But the ammonia remover only carries out single gas ammonia adsorption, and the dynamic adsorption quantity is low (1.0-2.35 mmol/cc); the separation of ammonia gas in the mixed components is not studied, and the separation effect is unknown; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, the adsorption stability is unknown, and the method is not suitable for separating and recycling the sludge aerobic composting ammonia gas.
Patent 201680071061.4 reports a method for preparing an ammonia removing agent, which is composed of silicon phosphate, sesbania powder, silicon dioxide, etc., for different temperatures, flow rates and various gas components (SO)2、N2O、NH3Humidity) is carried out, the dynamic adsorption capacity of ammonia is 0.99-1.64 mmol/g, and the method is suitable for ammonia treatment before a flue gas desulfurization and denitration and flue gas continuous monitoring system of a thermal power plant. But the dynamic adsorption capacity of the ammonia removal agent is low; the separation of ammonia in the mixed components is not studied, and the separation effect is unknown; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, the adsorption stability is unknown, and the method is not suitable for separating and recycling the sludge aerobic composting ammonia gas.
Patent 201680071061.4 reports a preparation method of an ammonia removal material, which is composed of a plurality of zeolites with different crystal structures and is suitable for removing ammonia gas remaining after a hydrogen energy source used by a fuel cell is converted from liquid ammonia, and the dynamic adsorption amount of the ammonia gas is 2.24-3.76 mmol/g. But the dynamic adsorption capacity of the ammonia removal agent is low; the separation of ammonia in the mixed components is not studied, and the separation effect is unknown; the research of ammonia gas simulated adsorption aiming at the conditions in the sludge aerobic composting process is not carried out, the adsorption stability is unknown, and the method is not suitable for separating and recycling the sludge aerobic composting ammonia gas.
Patent 201611031050.1 discloses a method for absorbing and separating ammonia gas from ammonia-containing waste gas, which comprises contacting a hybrid eutectic solvent (weakly acidic compound, salt compound and additive) as an absorbent with the ammonia-containing waste gas to absorb the solvent to obtain an absorption liquid of the ammonia-containing waste gas, and separating the absorption liquid to obtain ammonia gas. The components of the adsorbed gas are tested to be hydrogen, nitrogen, ammonia, argon and methane, and the concentration of the ammonia is 2.5-72.3%. However, the patent can not obtain the dynamic adsorption amount of ammonia gas by static adsorption under high pressure; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, and the adsorption stability is unknown.
Patent 201510158450.8 reports a novel high-efficiency reversible ionic ammonia absorbent, which is a lewis acid ionic liquid composed of pyridine or imidazole and its derivative cations and divalent metal cobalt ion-containing anions, and is suitable for absorbing ammonia in tail gas discharged from urea prilling towers, coke oven gas and the like. The adsorption test condition of the patent is that the gas flow is 140ml/min, single gas ammonia gas is adsorbed under a plurality of temperatures and a plurality of pressures, and the ammonia gas adsorption quantity is 0.88-11.64 mmol/g. However, the patent does not study the separation of ammonia gas in the mixed components, and the separation effect is unknown; the research of ammonia gas adsorption simulation is not carried out aiming at the conditions in the sludge aerobic composting process, and the adsorption stability is unknown.
In summary, according to the reported ammonia adsorbent, the purposes of mixed gas separation and ammonia recovery in the sludge aerobic composting process are not designed, and the following problems exist: the dynamic adsorption amount of ammonia is unknown or lower, the adsorption and separation effect of ammonia in the mixed components is unknown, and the adsorption stability under different conditions in the sludge aerobic composting process is unknown. Therefore, the invention is needed to invent a material suitable for mixed gas separation and ammonia recovery in the sludge aerobic composting process.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides an ammonia molecular imprinting adsorbent and a preparation method thereof, wherein the ammonia molecular imprinting adsorbent is applied to ammonia adsorption and separation in a sludge aerobic composting process, and the adsorbent not only can realize effective separation of ammonia in mixed gas, but also has higher adsorption capacity for dynamic adsorption of ammonia, and has good stability in a simulated composting environment.
The ammonia gas molecular imprinting adsorbent provided by the invention is prepared by a method comprising the following steps:
1) adding ammonia water (template) and acrylic functional monomer into solvent, and mixing uniformly;
2) adding an azobisisobutyronitrile initiator and an ethylene glycol dimethacrylate cross-linking agent (EGDMA) into the system obtained in the step 1), and uniformly mixing;
3) carrying out free radical polymerization reaction on the system obtained in the step 2), and collecting a precipitate;
4) ultrasonically cleaning the precipitate obtained in the step 3) to remove the template and the reaction solvent to obtain an eluted precipitate;
5) transferring the eluted precipitated substances into a sulfuric acid solution with the pH value of 0.5, sealing, and reacting under stirring to hydrolyze ester functional groups in part of the crosslinking agent to form carboxyl functional groups;
6) and (3) drying the product obtained in the step 5) in vacuum to obtain the product.
In step 1) of the above method, the acrylic functional monomer may be methacrylic acid;
the solvent may specifically be toluene.
The mol ratio of ammonia in the ammonia water to the acrylic acid functional monomer can be 1: 2-1: 4;
the molar ratio of the functional monomer to the ethylene glycol dimethacrylate crosslinker (EGDMA) can be 1: 2-1: 5;
the ratio of the mass of polymerized monomer to the volume of solvent may be: 2.5-10 mg: 100ml, wherein the mass of the initiator accounts for 1 to 9 percent of the mass of the polymerized monomer;
wherein the mass of the polymerized monomer is the total mass of the functional monomer and the cross-linking agent;
in step 3), the radical polymerization is performed under the protection of an inert gas, which may be nitrogen;
the free radical polymerization reaction is carried out in a water bath kettle at the temperature of 50-70 ℃, and the time of the free radical polymerization reaction can be 10-18 hours, particularly 12 hours;
in the step 4) of the method, firstly deionized water is used for washing the precipitate for multiple times, and then ultrasonic cleaning is carried out in water for 0.25-1 hour, specifically half an hour, until no ammonium ions are detected in the filtrate.
In the step 5), the reaction time may be 10 to 14 hours, specifically 12 hours.
In the step 6), before the product is dried in vacuum, the operation of washing the product obtained in the step 5) with deionized water can be further included until the pH value of the eluent is about 5-7, the filtering is carried out, the obtained solid is placed in a vacuum drying oven, the vacuum drying is carried out for 12 hours at the temperature of 80 ℃, and the ammonia molecular imprinting adsorbent is obtained and is placed in a dryer for later use.
The ammonia gas molecular imprinting adsorbent prepared by the method also belongs to the protection scope of the invention.
The application of the ammonia molecular imprinting adsorbent in the separation and recovery of ammonia in sludge aerobic composting mixed gas also belongs to the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the adsorbent obtained by the invention has good adsorption selectivity for ammonia gas in mixed gas generated by sludge composting, has low adsorption capacity of dimethyl sulfide and dimethyl disulfide, and can realize efficient separation of ammonia gas, dimethyl sulfide and dimethyl disulfide;
(2) the adsorbent obtained by the invention can be adsorbed at normal temperature and normal pressure, the adsorption condition is mild, the adsorbent still keeps higher adsorption capacity to ammonia gas under the conditions of different flow, concentration, temperature and humidity, and the adsorption performance is stable;
(3) the method has the advantages of easily obtained raw materials, simple preparation conditions, no need of high temperature and high pressure, and easy realization of industrialization.
Drawings
FIG. 1 is a scanning electron microscope image of the ammonia gas molecularly imprinted adsorbent prepared in example 1 of the present invention. Wherein, the left image is magnified 2000 times, and the right image is magnified 8000 times.
FIG. 2 is a schematic view of a dynamic adsorption apparatus used in example 2 of the present invention; wherein, the flow and temperature control interface is 1, the ammonia gas/dimethyl sulfide/dimethyl disulfide/nitrogen gas is 2, the one-way valve is 3, the proton flow meter is 4, the mixer is 5, the adsorption column is 6, the heating furnace is 7, and the gas detector is 8.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of Ammonia gas molecularly imprinted adsorbent
48.66 mu l of ammonia water and 219.84 mu l of methacrylic acid functional monomer are added into a three-neck flask filled with 60ml of toluene, premixed for 10min with the aid of a magnetic stirrer, then added with 1.22ml of ethylene glycol dimethacrylate cross-linking agent and 10mg of azobisisobutyronitrile initiator, and stirred and mixed evenly. After the reagents are mixed evenly, a nitrogen bottle is opened, nitrogen is introduced into the three-neck flask, and the gas is exhausted for 10 min. The three-neck flask with the air exhausted is sealed and then continuously heated for 12 hours in water bath at the temperature of 60 ℃ to carry out free radical polymerization reaction. After the reaction is finished, removing the suspension, washing the precipitate with deionized water for multiple times, and performing ultrasonic treatment for half an hour until no ammonium ions are detected in the filtrate (by adopting the adsorption performance test method in example 2, measuring the ammonia adsorption capacity of the obtained precipitate, wherein the ammonia adsorption capacity is 0.42mmol/g (the gas flow is 200ml/min, the temperature is 20 ℃, the ammonia concentration is 100ppm, and the relative humidity is 0%). adding the precipitate into a sulfuric acid solution (200ml) with the pH of 0.5, stirring and mixing uniformly for 12 hours, then washing with deionized water until the pH of the filtrate is 5-7, performing suction filtration, finally drying the precipitate in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain an ammonia molecularly imprinted adsorbent, and placing the adsorbent in a dryer for later use.
FIG. 1 is a scanning electron microscope image of the prepared ammonia gas molecular imprinting adsorbent.
Example 2 adsorption Performance test of Ammonia gas molecular imprinting adsorbent
(1) 0.2g of the ammonia gas molecularly imprinted adsorbent prepared in example 1 was placed in an adsorption column of a dynamic adsorption apparatus, and an ammonia gas dynamic adsorption experiment was performed (the schematic diagram of the dynamic adsorption apparatus is shown in fig. 2), and the adsorption conditions and the ammonia gas adsorption amount are shown in table 1.
(2) The maximum discharge amount ratio of ammonia gas, dimethyl sulfide and dimethyl disulfide, which is monitored on a sludge aerobic composting site, is about 10:1:1, the ratio is the ratio of the inlet gas concentration of mixed gas, the selective adsorption test of ammonia gas is carried out, and the selection factors of the ammonia gas on the dimethyl sulfide and the dimethyl disulfide (ammonia gas adsorption amount/dimethyl sulfide or dimethyl disulfide adsorption amount) are shown in table 1.
The adsorption capacity of the ammonia gas molecularly imprinted polymer to ammonia gas/dimethyl sulfide/dimethyl disulfide is obtained by drawing a penetration curve in a calculation mode. Taking ammonia as an example, according to the ammonia concentration at the outlet of the fixed bed at different time points measured in the experiment by an ammonia concentration measuring instrument, an adsorption curve graph corresponding to the polymer material is drawn by Origin85 software, and the adsorption curve is integrated, wherein the integrated value is the amount of ammonia overflowing from the outlet of the fixed bed. In the experiment, the adsorption amount m (mmol) of the ammonia gas molecularly imprinted polymer to the ammonia gas can be calculated by the formula (1):
wherein t (min) -adsorption time;
C0(mg/m3) -the inlet concentration of the gas;
van outlet(mg/m3) The amount of ammonia gas escaping at the outlet of the fixed bed, i.e. the integral value of the adsorption curve;
v (ml/min) -the inlet gas flow rate.
M of ammonia molecularly imprinted polymer on ammonia/dimethyl sulfide/dimethyl disulfideAmount of adsorption(mmol/g material) can be calculated from equation (2):
wherein m (mmol) -the amount of adsorption of gas by the polymer in the experiment;
mmaterial(g) -mass of ammonia molecularly imprinted polymer added to the adsorption column.
(3) The conditions of the sludge aerobic composting site are simulated, namely the dynamic adsorption quantity of ammonia is determined under different ammonia concentrations, temperatures, humidity and flow rates in the composting site, and the results are shown in table 2.
TABLE 1 Ammonia adsorption capacity and selectivity to dimethylsulfide and dimethyldisulfide of the Ammonia molecularly imprinted adsorbent
| Flow (ml/min) | 200 |
| Ammonia gas concentration (ppm) | 100 |
| Temperature (. degree.C.) | 20 |
| Relative humidity (%) | 0 |
| Amount of Ammonia adsorbed (mmol/g) | 7.54 |
| Ammonia selective factor (dimethyl sulfide) | 256 |
| Ammonia selective factor (dimethyl disulfide) | 352 |
TABLE 2 dynamic adsorption of ammonia by molecular imprinting adsorbent under different conditions
Comparative example (c),
Preparing an adsorbent by taking an acrylamide functional monomer as a polymerization monomer (under other conditions unchanged) according to the method of example 1, wherein the ammonia adsorption capacity of the obtained adsorbent material (before soaking in an acid solution) is 0.28 mmol/g; wherein the conditions are as follows: the gas flow is 200ml/min, the temperature is 20 ℃, the ammonia gas inlet concentration is 100ppm, and the relative humidity is 0%.
Example 3
The ammonia adsorption of the product obtained by hydrolysis (step 5) under different pH conditions was examined and shown in Table 3:
TABLE 3
| Adsorbents prepared under different pH solutions | Adsorption Capacity (mmol/g) |
| Alkaline solution with pH value of 13.5 | 0.03 |
| Alkaline solution with pH 12 | 0.29 |
| Acid solution with pH 2 | 0.71 |
| Acid solution with pH of 0.5 | 7.54 |
| Not hydrolyzed | 0.42 |
Wherein, the detection conditions of the adsorption quantity are as follows: the gas flow is 200ml/min, the temperature is 20 ℃, the ammonia gas inlet concentration is 100ppm, and the relative humidity is 0%.
As can be seen from Table 3: the ammonia adsorption capacity of the prepared adsorbent is greatly different by hydrolysis under different pH conditions, and the ammonia adsorption capacity of the adsorbent prepared by hydrolysis in an acid solution with the pH of 0.5 is the highest and can reach 7.54mmol/g, so that the ammonia molecular imprinting adsorbent is prepared by hydrolysis under the condition of the pH value.
Example 4
Investigating the influence of a solvent of the free radical polymerization reaction on the adsorption performance of the adsorbent, wherein the ammonia adsorption amount of a product (before soaking in an acid solution) prepared after the free radical polymerization reaction is replaced by ethanol is 0.088 mmol/g; the ammonia adsorption capacity of a product (before being soaked in an acid solution) prepared by using chloroform to replace toluene for free radical polymerization reaction is 0.082 mmol/g; therefore, toluene is selected as the solvent for the free radical polymerization.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (9)
1. A method for preparing an ammonia gas molecular imprinting adsorbent comprises the following steps:
1) adding ammonia water and acrylic functional monomer into a solvent, and uniformly mixing; the solvent is toluene;
2) adding an azobisisobutyronitrile initiator and an ethylene glycol dimethacrylate cross-linking agent into the system obtained in the step 1), and uniformly mixing;
3) carrying out free radical polymerization reaction on the system obtained in the step 2), and collecting a precipitate;
4) ultrasonically cleaning the precipitate obtained in the step 3) to remove the template and the reaction solvent to obtain an eluted precipitate;
5) transferring the eluted precipitate to sulfuric acid solution with pH of 0.5, sealing, and reacting under stirring to hydrolyze ester functional groups in part of the crosslinking agent to form carboxyl functional groups;
6) and (4) drying the product obtained in the step 5) in vacuum to obtain the product.
2. The method of claim 1, wherein: in the step 1), the acrylic functional monomer is methacrylic acid;
the mol ratio of ammonia in the ammonia water to the acrylic functional monomer is 1: 2-1: 4.
3. The method according to claim 1 or 2, characterized in that: the molar ratio of the functional monomer to the ethylene glycol dimethacrylate cross-linking agent is 1: 2-1: 5;
the ratio of the mass of the polymerized monomer to the volume of the solvent is: 2.5-10 mg: 100ml, wherein the mass of the initiator accounts for 1-9% of the mass of the polymerization monomer;
wherein the mass of the polymerized monomer is the total mass of the functional monomer and the cross-linking agent.
4. The method according to claim 1 or 2, characterized in that: in the step 3), the free radical polymerization reaction is carried out under the protection of inert gas;
the free radical polymerization reaction is carried out in a water bath kettle at the temperature of 50-70 ℃, and the time of the free radical polymerization reaction is 10-18 hours.
5. The method of claim 4, wherein: the inert gas is nitrogen.
6. The method according to claim 1 or 2, characterized in that: in the step 5), the reaction time is 10-14 hours.
7. The method according to claim 1 or 2, characterized in that: and 6) before the product is dried in vacuum, washing the product obtained in the step 5) with deionized water until the pH value of the eluent is 5-7, performing suction filtration, putting the obtained solid into a vacuum drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the ammonia molecular imprinting adsorbent, and putting the ammonia molecular imprinting adsorbent into a dryer for later use.
8. An ammonia gas molecular imprinting adsorbent prepared by the method of any one of claims 1-7.
9. The ammonia gas molecular imprinting adsorbent of claim 8 is applied to separation and recovery of ammonia gas in sludge aerobic composting mixed gas.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698721A (en) * | 2012-06-04 | 2012-10-03 | 江苏大学 | Preparation method for adsorbent for separating salicylic acid surface imprint from waste water |
| CN104072692A (en) * | 2014-07-03 | 2014-10-01 | 江苏大学 | Method for preparing magnetic/core-shell molecularly imprinted adsorbent employing miniemulsion polymerization |
| CN104725556A (en) * | 2015-04-08 | 2015-06-24 | 福州大学 | PH-sensitive glucose selective adsorbent and preparation method thereof |
| CN105944704A (en) * | 2016-07-15 | 2016-09-21 | 华北电力大学（保定） | Adsorbent for separating NO in smoke and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SE9903958D0 (en) * | 1999-11-02 | 1999-11-02 | Boerje Sellergren | Porous materials for selective binding or transport of molecular guests |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698721A (en) * | 2012-06-04 | 2012-10-03 | 江苏大学 | Preparation method for adsorbent for separating salicylic acid surface imprint from waste water |
| CN104072692A (en) * | 2014-07-03 | 2014-10-01 | 江苏大学 | Method for preparing magnetic/core-shell molecularly imprinted adsorbent employing miniemulsion polymerization |
| CN104725556A (en) * | 2015-04-08 | 2015-06-24 | 福州大学 | PH-sensitive glucose selective adsorbent and preparation method thereof |
| CN105944704A (en) * | 2016-07-15 | 2016-09-21 | 华北电力大学（保定） | Adsorbent for separating NO in smoke and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Preparation and characterization of molecularly imprinted solid amine adsorbent for CO2 adsorption;Liu Fenglei et al;《NEW JOURNAL OF CHEMISTRY》;20180514;第42卷(第12期);第10017页第2节 * |
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