CN113144816A - Metal complex ion functionalized polyion liquid and preparation method and application thereof - Google Patents
Metal complex ion functionalized polyion liquid and preparation method and application thereof Download PDFInfo
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 78
- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 167
- 238000001179 sorption measurement Methods 0.000 claims abstract description 81
- -1 metal complex ion Chemical class 0.000 claims abstract description 74
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 59
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 9
- 238000005349 anion exchange Methods 0.000 claims abstract description 7
- 238000003795 desorption Methods 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000002440 industrial waste Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 description 14
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HMJBSMLRRXAVIP-UHFFFAOYSA-N BrCC1=CC(=CC(=C1)CBr)CBr.C1=CC=CC=C1 Chemical compound BrCC1=CC(=CC(=C1)CBr)CBr.C1=CC=CC=C1 HMJBSMLRRXAVIP-UHFFFAOYSA-N 0.000 description 1
- 101100326389 Papio anubis BTDD gene Proteins 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a metal complex ion functionalized polyion liquid, which comprises cations and anions, wherein the cations are polymeric imidazolium ions, and the anions are metal complex ions Co (SCN)4 2‑. The preparation method takes imidazole polyion liquid as a framework, carries out metal complex ion functionalization through anion exchange, and takes metal complex ion Co (SCN) as anion4 2‑. The invention has the beneficial effects that: aiming at the problems of low recovery efficiency, high energy consumption and the like of industrial waste ammonia discharge, the prepared metal complex ion functionalized polyion liquid improves the adsorption capacity of the metal complex ion functionalized polyion liquid on ammonia gas according to the coordination effect and the hydrogen bond effect of the metal complex ion functionalized polyion liquid and the ammonia gas. The invention has ammonia adsorption capacity of 0.3403g NH in the ammonia atmosphere of 100kPa at 25 DEG C3The desorption can be completed at 80 ℃ for 1 hour.
Description
Technical Field
The invention relates to the field of gas adsorption, in particular to a preparation method of metal complex ion functionalized polyion liquid and a method for selectively adsorbing ammonia gas by using the same.
Background
The ammonia gas is one of industrial raw materials produced and used in large scale in chemical industry, and the emission of industrial waste ammonia can cause serious waste of ammonia resources and environmental pollution to human skinSkin, mucous membranes, etc. can also cause damage. Therefore, the research on the storage, separation and recovery of the ammonia gas is of great significance. At present, the industrial waste ammonia is mainly treated by dissolving the waste ammonia in water or acid solution to achieve the purposes of absorbing, separating and recovering ammonia gas. For example, in patent CN201420348874.1, the ammonia gas absorbing device adopts water as ammonia gas absorbent; patent CN202020343535.X uses carbonic acid solution to react with ammonia gas to achieve the purpose of ammonia gas recovery. However, the methods have the problems of strong corrosivity, high energy consumption, high consumption of fresh water resources on the premise of meeting the ammonia emission standard and the like. Therefore, it is extremely important to develop a recyclable adsorbent that absorbs ammonia gas with high efficiency and low energy consumption. The solid adsorbent is popular for its simple operation, Yaghi O.M [ Nature chemistry 2010,2,235]The amount of ammonia adsorbed at 25 ℃ and 1bar by COF-10 was 15 mmol/g. Dinca M [ Journal of the American Chemical Society 2016,138,9401.]Prepared M2Cl2The adsorption amount of ammonia gas in BTDD (M ═ Mn, Co, Ni) at 25 ℃ and 1bar is 0.2496-0.3364 g of NH3(ii) in terms of/g. But the desorption conditions are all vacuum 200 ℃, and the desorption energy consumption is larger.
Accordingly, the present inventors have made extensive studies to solve the above problems and have made the present invention.
Disclosure of Invention
The invention aims to provide a polyion liquid which can adsorb ammonia gas with high capacity and high selectivity and can be recycled.
In order to achieve the purpose, the invention adopts the following technical scheme:
the metal complex ion functionalized polyion liquid comprises a cation and an anion, wherein the cation is polymeric imidazole ion, and the anion is metal complex ion Co (SCN)4 2-。
The preparation method of the polyion liquid with metal complex ion functionalization is characterized in that imidazole polyion liquid is used as a framework, metal complex ion functionalization is carried out through anion exchange, and anions are metal complex ions Co (SCN)4 2-。
As a preferred mode of the present invention, the preparation of the polyion liquid comprises the following steps: adding 3.0-5.0g of halide and imidazole substituent with equal reaction equivalent into a reaction kettle, adding 50mL of N, N-dimethylformamide, stirring until the mixture is uniformly mixed, sealing, stirring at constant temperature of 110 ℃ for 120 hours, washing the obtained product with water, and centrifuging to obtain a solid which is polyion liquid.
In a preferred embodiment of the present invention, the halide is at least one of 1,3, 5-tris (bromomethyl) benzene, 1, 4-dichlorobenzyl and 4, 4' -biphenyldichlorobenzyl.
In a preferred embodiment of the present invention, the imidazole substituent is at least one selected from the group consisting of 1,3, 5-tris (1-imidazole) benzene, 1, 4-bis (1-imidazole benzyl), 4' -biphenylbis (1-imidazole) benzyl, and 1, 4-bis (1-imidazole) benzene.
As a preferred mode of the present invention, the metal complex ion functionalization by anion exchange is carried out by impregnating 10.0g of the polyionic liquid in 50mL of a solution containing 2.0mol/L KSCN and 0.5mol/L C ℃ L2The aqueous solution of (1) is stirred for 12 hours, centrifuged to remove supernatant, and the solid obtained after centrifugation is freeze-dried and then vacuum-dried at 80 ℃ to obtain the metal complex ion functionalized polyion liquid.
Application of metal complex ion functionalized polyion liquid in adsorption of ammonia gas, wherein the metal complex ion functionalized polyion liquid comprises cations and anions, the cations are polymeric imidazolium ions, and the anions are metal complex ions Co (SCN)4 2-。
In a preferred embodiment of the present invention, the ammonia adsorption pressure is in the range of 0 to 102 kPa.
As a preferred mode of the invention, 0.5000 g of metal ion functionalized polyion liquid is weighed into an adsorption tube and is subjected to vacuum drying treatment in a vacuum drying oven at 80 ℃ for 2 hours, ammonia isothermal adsorption is carried out at 25 ℃, a sample absorbs ammonia at a certain ammonia flow rate, the total mass of the adsorption tube after absorbing ammonia is weighed and recorded, and the sample can be considered to absorb ammonia to reach balance after the total mass is kept unchanged after the total mass is continuously weighed for three times.
As a preferable mode of the invention, after the isothermal adsorption of ammonia gas is finished, the metal ion functionalized polyion liquid after ammonia gas adsorption equilibrium is placed in a vacuum drying oven at 80 ℃ for vacuum heating desorption, and the recovered metal ion functionalized polyion liquid is subjected to next isothermal adsorption of ammonia gas.
After the scheme is adopted, the invention has the beneficial effects that: aiming at the problems of low recovery efficiency, high energy consumption and the like of industrial waste ammonia discharge, the prepared metal complex ion functionalized polyion liquid improves the adsorption capacity of the metal complex ion functionalized polyion liquid on ammonia gas according to the coordination effect and the hydrogen bond effect of the metal complex ion functionalized polyion liquid and the ammonia gas. The metal complex ion functionalized polyion liquid has ammonia adsorption capacity of 0.3403g NH in the ammonia atmosphere of 100kPa at 25 DEG C3The desorption can be completed at 80 ℃ for 1 hour.
Detailed Description
In order to further explain the technical solution of the present invention, the following detailed description is made with reference to the embodiments.
The metal complex ion functionalized polyion liquid comprises a cation and an anion, wherein the cation is polymeric imidazole ion, and the anion is metal complex ion Co (SCN)4 2-(i.e., cobalt (II) tetrasulfate anion).
The preparation method of the polyion liquid with metal complex ion functionalization is characterized in that imidazole polyion liquid is used as a framework, metal complex ion functionalization is carried out through anion exchange, and anions are metal complex ions Co (SCN)4 2-。
As a preferred mode of the present invention, the preparation of the polyion liquid comprises the following steps: adding 3.0-5.0g of halide and imidazole substituent with equal reaction equivalent into a reaction kettle, adding 50mL of N, N-dimethylformamide, stirring until the mixture is uniformly mixed, sealing, stirring at constant temperature of 110 ℃ for 120 hours, washing the obtained product with water, and centrifuging to obtain a solid which is polyion liquid.
As a preferred mode of the present invention, the metal complex ion functionalization by anion exchange is carried out by immersing 10.0g of the polyionic liquid in 50mL of a solution containing 2.0mol/L KSCN and 0.5mol/L CoCl2After stirring for 12 hours, the mixture is separatedRemoving supernatant by centrifugation, freeze-drying the solid obtained after centrifugation, and vacuum-drying at 80 ℃ to obtain the metal complex ion functionalized polyion liquid.
Example 1
Preparation of metal complex ion functionalized polyion liquid
1. Preparation of polyionic liquids
The method for producing the polyion liquid matrix used in the present invention will be described by taking an example of synthesis of 1, 4-bis (1-imidazole) benzene-1, 3, 5-tris (bromomethyl) benzene (Ph2 Im-TBB). Adding 3.57g of 1,3, 5-tri (bromomethyl) benzene, 3.15g of 1, 4-di (1-imidazole) benzene and 50mL of N, N-dimethylformamide into a 100mL hydrothermal kettle, adding a stirrer, stirring at normal temperature until the mixture is uniform, sealing, placing the hydrothermal kettle at the temperature of 100 ℃ and 110 ℃ and stirring at constant temperature for 120 hours, washing the obtained product with water, and centrifuging to obtain a solid which is a polyion liquid matrix Ph2 Im-TBB.
In addition, the halide used is not only the above-mentioned 1,3, 5-tris (bromomethyl) benzene; 1, 4-dichlorobenzyl can also be adopted; 4, 4' -Biphenyldichlorobenzyl.
The imidazole substitute is prepared by adopting the 1, 4-di (1-imidazole) benzene; 1,3, 5-tris (1-imidazole) benzene may also be used; 1, 4-diimidazole benzyl; 4, 4' -Biphenyldiimidazole benzyl.
2. Preparation of metal complex ion functionalized polyion liquid
The preparation method of the polyion liquid functionalized by metal complex ions comprises the following steps: 10.0g of polyionic liquid Ph2Im-TBB was immersed in 50mL of a solution containing 2.0mol/L KSCN and 0.5mol/L CoCl2After stirring for 12 hours, the supernatant was removed by centrifugation. The above steps were repeated three times. The solid obtained after centrifugation was washed with water until the supernatant was clear. Freezing the solid obtained after centrifugation at-20 deg.C for 4 hr, removing water in a freeze drier, and fully drying in a vacuum drying oven at 80 deg.C to obtain metal complex ion functionalized polymerAnd the ionic liquid Ph2 Im-TBB-TA.
The metal complex ion functionalized polyion liquid adopted by the invention is used as an adsorbent to adsorb ammonia, and the adsorption performance of the material to ammonia is enhanced by utilizing the synergistic hydrogen bond effect and coordination effect. Aiming at the technical problems of high energy consumption and the like in the ammonia gas recovery treatment in the chemical industry at present, the metal complex ion functionalized polyion liquid prepared by the invention enables ammonia gas to be easily desorbed by virtue of competitive coordination action of thiocyanate ions and ammonia gas molecules, and an adsorbent can be recovered.
Secondly, the metal ion-matched functionalized polyion liquid is used for adsorbing ammonia gas
0.5000 g of metal ion functionalized polyion liquid is filled in an adsorption tube and is dried in a vacuum drying oven for 2 hours under the temperature of 80 ℃. And (3) placing the adsorption tube in a constant temperature device at 25 ℃ for 30 minutes, carrying out ammonia isothermal adsorption on ammonia with set partial pressure through an adsorbent, and indicating that the ammonia adsorption reaches balance after the total mass of the adsorption tube weighed for three times is unchanged, wherein the mass increased by the adsorbent is the ammonia adsorption amount of the adsorbent at the pressure of 25 ℃. The ammonia adsorption pressure is in the range of 0-102 kPa. The adsorption capacity of the metal complex ion functionalized polyionic liquid Ph2Im-TBB-TA under different ammonia pressures is listed in the following table 1.
TABLE 1 comparison table of isothermal ammonia adsorption capacities of Ph2Im-TBB-TA at 25 deg.C
As can be seen from the data in Table 1, the metal complex ion functionalized polyionic liquid can adsorb 0.1103g of NH at lower pressure, such as 2kPa3The/g adsorbent shows that the material has the capacity of adsorbing ammonia under the condition of low ammonia pressure. And the adsorption capacity increased with the increase of the ammonia gas pressure, and the adsorption capacity reached 0.3403g NH when the ammonia gas pressure was 100kPa3/g。
Example 2
The invention relates to a method for adsorbing ammonia gas by a metal complex ion functionalized polyion liquid under different temperature conditions, which comprises the following steps:
0.5000 g of metal ion functionalized polyion liquid is filled in an adsorption tube and is dried in a vacuum drying oven for 2 hours under the temperature of 80 ℃. And (3) placing the adsorption tube at a set adsorption temperature for 30 minutes at a constant temperature, introducing ammonia gas with the gas flow rate of 40sccm, weighing the total mass of the adsorption tube every 5 minutes, and after weighing the total mass for three times and keeping the total mass unchanged, indicating that the ammonia gas adsorption reaches balance, wherein the increased mass of the adsorbent is the ammonia gas adsorption amount of the adsorbent at the temperature. The adsorption temperatures were controlled at 25 deg.C, 35 deg.C, 45 deg.C, 55 deg.C, 65 deg.C, respectively. The adsorption amount of ammonia at different temperatures for Ph2Im-TBB-TA is shown in Table 2.
TABLE 2 Ammonia adsorption Capacity of Ph2Im-TBB-TA at different temperatures
| Adsorption temperature of Ammonia gas (. degree.C.) | Ammonia adsorption capacity (g NH)3/g) |
| 25 | 0.3403 |
| 35 | 0.2633 |
| 45 | 0.2264 |
| 55 | 0.2026 |
| 65 | 0.1860 |
From the data in table 2 it can be seen that in the range of 25-65 c, the adsorption capacity of ammonia gas decreases with increasing temperature, indicating that the adsorbed ammonia gas can be desorbed by heating. And Ph2Im-TBB-TA still has higher ammonia adsorption capacity under the condition of 65 ℃, so the material can be used for ammonia adsorption under some higher-temperature environments.
Example 3
The invention relates to a metal complex ion functionalized polyion liquid for selectively adsorbing ammonia, which comprises the following steps:
and (3) placing the metal complex ion functionalized polyion liquid in a vacuum drying oven at 80 ℃ for processing for 2 hours, and testing the adsorption capacity of the polyion liquid at 25 ℃ by using a microscopic JW-DEL 200 physical adsorption instrument, so as to calculate the ammonia adsorption selectivity. The ammonia adsorption selectivity results of the metal complex ion functionalized polyion liquid Ph2Im-TBB-TA are shown in Table 3.
From the results in Table 3, it can be seen that Ph2Im-TBB-TA can adsorb ammonia gas with high selectivity, and the material is expected to realize the adsorption and separation of ammonia gas in the mixed gas.
TABLE 3 ammonia adsorption selectivity at 25 ℃ Ph2 Im-TBB-TA.
Example 4
The invention prepares the functionalized polyion liquid with different metal ions for ammonia adsorption performance comparison, which comprises the following specific steps:
0.5000 g of metal ion functionalized polyion liquid is filled in an adsorption tube and is dried in a vacuum drying oven for 2 hours under the temperature of 80 ℃. And (3) placing the adsorption tube at the constant temperature of 25 ℃ for 30 minutes, introducing ammonia gas with the flow rate of 40sccm, weighing the total mass of the adsorption tube every 5 minutes, and after weighing the total mass for three times and keeping the total mass unchanged, indicating that the ammonia gas adsorption reaches balance, wherein the increased mass of the adsorbent is the ammonia gas adsorption amount at 25 ℃. The ammonia adsorption capacity of the polyionic liquid functionalized by different metal complex ions at 25 ℃ is shown in Table 4.
TABLE 4 comparison table of ammonia adsorption amount of metal complex ion functionalized polyion liquid at 25 deg.C
| Adsorbent and process for producing the same | Ammonia adsorption capacity (g NH)3/g) |
| Ph2Im-TBB-TA | 0.3403 |
| Ph3Im-TBB-TA | 0.3213 |
| Bz2Im-TBB-TA | 0.2922 |
| 2Bz2Im-TBB-TA | 0.2239 |
| Ph3Im-BCP-TA | 0.2514 |
| Ph3Im-DCB-TA | 0.2931 |
From the data in Table 4, it can be seen that the polyion liquid functionalized by metal complex ions in the class has high capacity of adsorbing ammonia, and particularly, the ammonia adsorption capacity of Ph2Im-TBB-TA, Ph3Im-TBB-TA and Bz2Im-TBB-TA is higher than that of most of the metal organic frameworks and the ionic liquid reported at present under the condition of 25 ℃.
Example 5
As a preferred embodiment, the invention relates to recycling of ammonia adsorbed by a metal complex ion functionalized polyionic liquid, which comprises the following steps:
step 1, 0.5000 g of metal ion functionalized polyion liquid is filled in an adsorption tube and is dried in a vacuum drying oven for 2 hours under the temperature of 80 ℃. And (3) placing the adsorption tube at a constant temperature of 25 ℃ for 30 minutes, introducing ammonia gas with the gas flow rate of 40sccm, weighing the total mass of the adsorption tube every 5 minutes, and after weighing the total mass for three times and keeping the total mass unchanged, indicating that the ammonia gas adsorption reaches balance, wherein the increased mass of the adsorbent is the ammonia gas adsorption amount. And (3) placing the adsorption tube after adsorbing the ammonia gas in a vacuum oven at 80 ℃ for heating for 1 hour, and taking out for next ammonia gas adsorption.
And 2, placing the adsorption tube subjected to ammonia desorption in the step 1 at the temperature of 25 ℃ for constant temperature for 30 minutes, introducing ammonia with the gas flow rate of 40sccm, weighing the total mass of the adsorption tube every 5 minutes, and after weighing the total mass for three times and keeping the total mass unchanged, indicating that the ammonia adsorption reaches balance, wherein the mass increased by the adsorbent is the ammonia adsorption amount. And (3) placing the adsorption tube after adsorbing the ammonia gas in a vacuum oven at 80 ℃ for heating for 1 hour, and taking out for next ammonia gas adsorption.
And 3, repeating the step 2 to obtain the trapping capacity of the 5-cycle ammonia adsorption times of Ph2Im-TBB-TA listed in the table 5.
TABLE 5 adsorption capacity of Ph2Im-TBB-TA against ammonia adsorption for 5 cycles.
| Number of cycles | Ammonia adsorptionCapacity (g NH)3/g) |
| 1 | 0.3403 |
| 2 | 0.3276 |
| 3 | 0.3291 |
| 4 | 0.3288 |
| 5 | 0.3417 |
The data in the table 5 can show that the metal complex ion functionalized polyion liquid Ph2Im-TBB-TA can be recycled, and the ammonia adsorption amount is not reduced in 5 cycles.
The product form of the present invention is not limited to the embodiments, and any suitable changes or modifications of the similar ideas by anyone should be considered as not departing from the patent scope of the present invention.
Claims (10)
1. The metal complex ion functionalized polyion liquid comprises cations and anions, and is characterized in that: the cation is polymeric imidazolium, and the anion is metal complex ion Co (SCN)4 2-。
2. The preparation method of the metal complex ion functionalized polyion liquid is characterized by comprising the following steps: the imidazole polyion liquid is used as a framework to carry out metal complex ion functionalization through anion exchange, and the anion is metal complex ion Co (SCN)4 2-。
3. The method of claim 2, wherein the polyionic liquid functionalized with metal complex ions is prepared by the following steps: the preparation method of the polyion liquid comprises the following steps: adding 3.0-5.0g of halide and imidazole substituent with equal reaction equivalent into a reaction kettle, adding 50mL of N, N-dimethylformamide, stirring until the mixture is uniformly mixed, sealing, stirring at constant temperature of 110 ℃ for 120 hours, washing the obtained product with water, and centrifuging to obtain a solid which is polyion liquid.
4. The method of claim 3, wherein the polyionic liquid functionalized with metal complex ions is prepared by the following steps: the halide is at least one of 1,3, 5-tri (bromomethyl) benzene, 1, 4-dichlorobenzyl and 4, 4' -biphenyl dichlorobenzyl.
5. The method of claim 4, wherein the polyionic liquid functionalized with metal complex ions is prepared by the following steps: the imidazole substituent is at least one of 1,3, 5-tri (1-imidazole) benzene, 1, 4-di (1-imidazole benzyl), 4' -biphenyl di (1-imidazole) benzyl and 1, 4-di (1-imidazole) benzene.
6. The method of claim 5, wherein the polyionic liquid functionalized with metal complex ions is prepared by the following steps: metal complex ion functionalization by anion exchange is carried out by immersing 10.0g of the polyionic liquid in 50mL of a solution containing 2.0mol/L KSCN and 0.5mol/L CoCl2The aqueous solution of (1) is stirred for 12 hours, centrifuged to remove supernatant, and the solid obtained after centrifugation is freeze-dried and then vacuum-dried at 80 ℃ to obtain the metal complex ion functionalized polyion liquid.
7. The application of the metal complex ion functionalized polyion liquid is characterized in that: the polyion liquid functionalized by metal complex ions is used for adsorbing ammonia gas, and comprises cations and anions, wherein the cations are polymeric imidazole ions, and the anions are metal complex ions Co (SCN)4 2-。
8. The use of a metal complex ion functionalized polyionic liquid according to claim 7, wherein: the ammonia adsorption pressure is in the range of 0-102 kPa.
9. The use of a metal complex ion functionalized polyionic liquid according to claim 8, wherein: weighing 0.5000 g of metal ion functionalized polyion liquid into an adsorption tube, carrying out vacuum drying treatment in a vacuum drying oven at 80 ℃ for 2 hours, carrying out ammonia isothermal adsorption at 25 ℃, absorbing ammonia by a sample at a certain ammonia flow rate, weighing and recording the total mass of the adsorption tube after absorbing ammonia, and considering that the ammonia adsorption of the sample reaches balance after the total mass is kept unchanged after continuously weighing for three times.
10. Use of a metal complex ion functionalized polyionic liquid according to claim 9, wherein: after the isothermal adsorption of ammonia gas is finished, putting the metal ion-doped functionalized polyion liquid with ammonia gas adsorption balance into a vacuum drying oven at 80 ℃ for vacuum heating desorption, and carrying out the next isothermal adsorption of ammonia gas on the recovered metal ion-doped functionalized polyion liquid.
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| CN114471074A (en) * | 2022-02-22 | 2022-05-13 | 华侨大学 | Application of macromolecule-metal complex in reversible ammonia gas trapping |
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