CN109232781A - A kind of preparation method of nitrogenous porous organic polymer - Google Patents
A kind of preparation method of nitrogenous porous organic polymer Download PDFInfo
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Abstract
The present invention relates to a kind of preparation of environmental catalysts and its applications, and in particular to the preparation method of a kind of nitrogenous porous organic polymer and its in CO2The application of absorption and conversion aspect.The present invention selects nitrogen containing monomer and Isosorbide-5-Nitrae-to be crosslinked to synthesize nitrogenous porous organic polymer benzyl dichloride or vinyl chloride by alkylation induction under the conditions of Louis acid catalysis.Its obtained polymer with nitrogen has stable nitrogenous active site, the mesoporous macropore of larger proportion, unique carbon dioxide enriched characteristic, higher CO2/N2Selectivity, so that N-POPs adsorbent carries out CO in industrial waste gas2High-selectivity adsorption has a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation of environmental catalysts and its applications, and in particular to a kind of nitrogenous porous organic polymer
Preparation method and its in CO2The application of absorption and conversion aspect.
Background technique
After entering the industrial age from the world, atmospheric carbon dioxide levels be continuously increased and its caused global warming
It is paid close attention to the various weathers such as Ocean acidification and environmental problem by people.The discharge of the sour gas such as carbon dioxide is mainly derived from
Industrial activity, this relies primarily on the use of fossil fuel, as a large amount of in just having in water gas shift reaction tail gas in coal gas chemical industry
Carbon dioxide exclude, therefore eliminate carbon dioxide from industrial tail gas and to alleviate various environmental problems just seem particularly significant.
Currently, amine aqueous solution is due to CO2Reversible chemical reaction and low cost have been widely used for CO2Selectivity capture.But exist
The a large amount of volatilization losses of solvent so as to cause equipment heavy corrosion the problems such as.Therefore, a kind of effective and free of contamination suction is developed
Attached medium replaces amine aqueous solution to carry out CO2Selectivity capture it is particularly significant.
In recent years, scientists have carried out extensive research work to this, CO is selectively captured from industrial smoke2,
, using porous material as absorbent, these materials have many advantages, such as non-volatility, corrosion-free and easy regeneration for it.As a kind of most advanced
Material-porous organic polymer (POPs), the wide of researchers is caused with the diversification in synthetic route constructing with it
General concern, to provide a thinking for structure and function design.And usually have with the POPs of Covalent bonding together higher
Physics and chemical stability.Therefore, POPs is in CO2There is very big application potential in capture.However, POPs is to CO2Capture
Performance depends not only on its structural property, also depends on its active site having.Particular functional group especially nitrogen site is drawn
Enter to POPs frame, POPs can be greatly improved to CO2Capture rate, because of CO2The unique Lewis Acids and Bases phase between nitrogen site
Interaction, to realize higher CO2/N2Selectivity.
More CO is studied at present2The main active charcoal of adsorbent, aluminium oxide, molecular sieve, silica etc..The patent No.
CN107661748A discloses a kind of organic amino-functionalization large aperture capacity silicon oxide CO2Adsorbent, the adsorbent are with organic amine
Active component, organic amino-functionalization large aperture capacity silicon oxide CO of composition2The CO of adsorbent2Adsorption capacity is significantly enhanced,
Dynamic adsorption capacity reaches 208mg/g, and its regeneration cycle has good stability.But the organic amine during functionalization is to human body and ring
Border will cause influence, further apply and development to affect the adsorbent.Patent No. CN108079956A discloses one
The kind micro/meso porous solid amine absorption agent of new multistage, is mixed to get composite molecular screen by different quality ratio for HZSM-5 and MCM-41
Carrier, with tetraethylenepentamine (TEPA) for modifying agent, when the mass ratio of HZSM-5 and MCM-41 is that 1: 1, TEPA load capacity is
30%, when adsorption temp is 55 DEG C, charge flow rate is 30mL/min, equilibrium adsorption capacity is up to 3.57mmol/g, and inhales and take off through 10 times
After attached circulation, adsorbance decline 8.1%.Although above-mentioned adsorbent also has preferable adsorption effect, need living using organic amine
Change to obtain its active site, the stability of its absorption property is caused to be lacking.Therefore the present invention is in Louis acid catalysis item
Under part, nitrogen containing monomer and Isosorbide-5-Nitrae-is selected to be crosslinked to synthesize nitrogenous porous organic polymer benzyl dichloride by alkylation induction.
Its obtained polymer with nitrogen has stable nitrogenous active site, the mesoporous macropore of larger proportion, unique carbon dioxide richness
Collect characteristic, higher CO2/N2Selectivity, so that N-POPs adsorbent carries out CO in industrial waste gas2High-selectivity adsorption has
Good application prospect.
Summary of the invention
The purpose of the present invention is overcoming the problems, such as that existing adsorbent adsorbance deficiency and stability are poor, provide a kind of high nitrogenous
Amount, the preparation method with mesoporous macropore organic polymer are crosslinked, pyroreaction under nitrogen by induction, washing, and isopropylamine is living
Change, vacuum drying synthesizes nitrogenous organic polymer.
In order to achieve the above object, technical solution used in the present invention is as follows:
A kind of preparation method of nitrogenous porous polymer material carries out in accordance with the following steps:
A. the Isosorbide-5-Nitrae-of certain mass is dissolved in 1,2- dichloroethanes benzyl dichloride or vinyl chloride, wherein with second
When alkenyl benzyl chloride is raw material, need to be added initiator azodiisobutyronitrile AIBN；Then it is vigorously stirred 30-120s at 0 DEG C,
And the lewis acid catalyst of certain volume is added into mixture；
B. then, the nitrogen containing monomer of certain mass is added in mixture；
C. in N2In atmosphere, heat treatment a period of time；
D. it filters out the solid to be formed and is thoroughly washed with hot dehydrated alcohol to remove remaining reactant and lewis acid catalyst；
E. crude product is immersed in isopropylamine, handles 6-12h at room temperature and activated, is then dried in vacuo again；
Preferably, Isosorbide-5-Nitrae-is 0.5-2g to the quality of benzyl dichloride in a step, and volume is 15-30ml in 1,2- dichloroethanes；
The volume of vinyl chloride is 0.5-1.5 ml, initiator quality 0.05g
Preferably, the volume of lewis acid catalyst is 2-5ml, type SnCl in a step4Or TiCl4。
Preferably, in the b step, nitrogen containing monomer quality is 0.5-1.5g, and type is p-phenylenediamine, 4,4'- bipyridyls,
One of hexa or 4-vinylpridine.
Preferably, the heat treatment temperature of the step c is 60-90 DEG C, heat treatment time 2-6h.
Preferably, in the Step d, ethanol washing number is 6 ~ 12 times.
Preferably, in the step e, vacuum drying temperature is 60-120 DEG C, time 6-24h.
One kind such as above method prepares nitrogenous porous organic polymer, and the porous polymer with nitrogen is used for efficient selective
Adsorb carbon dioxide.
Preferably, the porous polymer with nitrogen is used for CO2In N2In selective absorption.
Preferably, the CO2Adsorption temp be 0 DEG C and 25 DEG C.
Preferably, the adsorbent inventory is 0.1g；It is pre-processed under vacuum conditions before absorption, treatment temperature is
160 DEG C, the processing time is 12h, is subsequently placed in 0 DEG C and 25 DEG C of Dewar bottle and carries out CO2And N2Absorption.
The present invention has the advantage that and the utility model has the advantages that
1, nitrogenous porous polymer adjustability of the invention is strong, and material thermal stability is high, and the simple green of preparation process, easily realization
Industrialized production has broad application prospects.
2, nitrogenous porous organic polymer surface area of the invention is up to 700~1200m2/ g, in carbon dioxide adsorption side
Face has good activity and selectivity；
3, nitrogenous porous organic polymer material prepared by the present invention without load or adds other active components, what itself contained
The surface alkalinty of material can be improved in nitrogen, increases the quantity of carbon margin location and defective bit, strengthens the absorption of carbon dioxide.
Detailed description of the invention
Fig. 1 is the CO at 0 DEG C of the embodiment of the present invention 1~42And N2Adsorption curve；
Fig. 2 is the CO at 25 DEG C of the embodiment of the present invention 1~42And N2Adsorption curve；
Fig. 3 is the CO of the embodiment of the present invention 22Circulation absorption experiment；(adsorption conditions: pure CO2, 25 ℃, 50 mL/min,
180 min；Desorption conditions: pure N2, 75 DEG C, 150 mL/min, 120 min)；
Fig. 4 is N under the nitrogenous porous organic polymer liquid nitrogen temperature of the embodiment of the present invention 1~42Physics adsorption desorption curve；
Fig. 5 is the nitrogenous porous organic polymer graph of pore diameter distribution of the embodiment of the present invention 1~4；
Fig. 6 is the SEM figure of the nitrogenous porous organic polymer of the embodiment of the present invention 1~4；A figure is N-POP- p-phenylenediamine, b figure
For N-POP-4,4'- bipyridyl, c and d figure is N-POP- urotropine, e and f figure is N-POP- pyridine.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to example and attached drawing, to this hair
Bright to be described in detail, the example illustrated is the limitation to further explanation of the invention, rather than to the content of present invention.
Embodiment 1
N-POP- p-phenylenediamine: the Isosorbide-5-Nitrae-of 0.5g is dissolved in 1, the 2- dichloroethanes of 20ml benzyl dichloride, then at 0 DEG C
Under be vigorously stirred 60s, and into mixture be added 2ml SnCl4.Then 1g p-phenylenediamine monomer is added in mixture,
N2In 70 DEG C of reaction 3h under atmosphere.Then by the solid formed after suction filtration with hot dehydrated alcohol wash 8 times it is remaining anti-to remove
Answer object and lewis acid catalyst.Crude product is finally immersed in isopropylamine, 12h is handled at room temperature and is activated, at 80 DEG C
Nitrogenous porous organic polymer is obtained after lower vacuum drying 18h, remembers N-POP- p-phenylenediamine, and the specific surface area of the sample is
1116m2/ g, the content of nitrogen are 3.5%.
Embodiment 2
N-POP-4,4'- bipyridyl: the Isosorbide-5-Nitrae-of 2.0g is dissolved in 1, the 2- dichloroethanes of 25ml benzyl dichloride, then 0
It is vigorously stirred 30s at DEG C, and 4ml TiCl is added into mixture4.Then 1.5 g N-POP-4,4'- bipyridyl monomers are added
Enter into mixture, in N2In 90 DEG C of reaction 5h under atmosphere.Then the solid formed after suction filtration is washed 9 times with hot dehydrated alcohol
To remove remaining reactant and lewis acid catalyst.Crude product is finally immersed in isopropylamine, at room temperature handle 9h into
Row activation, obtains nitrogenous porous organic polymer after being dried in vacuo 12h at 100 DEG C, is denoted as N-POP-4,4'- bipyridyl.It should
The specific surface area of sample is 1047m2/ g, the content of nitrogen are 5.1%.
Embodiment 3
N-POP- hexa: the Isosorbide-5-Nitrae-of 1.0 g is dissolved in 1, the 2- dichloroethanes of 30ml benzyl dichloride, then exists
It is vigorously stirred 90s at 0 DEG C, and 3ml SnCl is added into mixture4.Then by 0.85 g N-POP- hexa list
Body is added in mixture, in N2In 75 DEG C of reaction 3h under atmosphere.Then the solid formed after suction filtration is washed with hot dehydrated alcohol
6 times are washed to remove remaining reactant and lewis acid catalyst.Crude product is finally immersed in isopropylamine, is handled at room temperature
6h is activated, and is dried in vacuo at 70 DEG C and is obtained nitrogenous porous organic polymer afterwards for 24 hours, and N-POP- hexa-methylene four is denoted as
Amine.The specific surface area of the sample is 1177m2/ g, the content of nitrogen are 3.3%.
Embodiment 4
N-POP- pyridine: 1mL vinyl chloride and 0.78mL 4-vinylpridine are dispersed in 30mL 1,2- dichloroethanes
In, 0.05g azodiisobutyronitrile AIBN initiator is then added.It is total to by being heated 24 hours at 80 DEG C to mixture
Polymerization, to generate the adhesive copolymer with linear character.Then super cross-linked network in order to obtain is vigorously stirred 90s at 0 DEG C
And by 4mL TiCl4It is introduced into mixture, and in N2In the case where atmosphere protection, it is 6 small which at 90 DEG C carries out reaction again
When.Obtained solid is filtered out, with hot dehydrated alcohol and salt acid elution to remove remaining reactant and lewis acid catalyst.Then
Crude product is immersed in isopropylamine, 12h is handled at room temperature and is activated, is then dried in vacuo 12 hours at 80 DEG C.It closes
At sample be expressed as N-POP- pyridine.The specific surface area of the sample is 969 m2/ g, the content of nitrogen are 3.0%.
Comparative example 1
POP undoped with nitrogen: the Isosorbide-5-Nitrae-of 2.0g is dissolved in 1, the 2- dichloroethanes of 15mL benzyl dichloride, then at 0 DEG C
It is vigorously stirred and is added into mixture the TiCl of 5mL4.Then, in N2Reaction 24 hours is carried out in atmosphere at 75 DEG C.It filters
The solid of formation is washed with hot dehydrated alcohol to remove remaining reactant and lewis acid catalyst, and vacuum is dry at 80 DEG C
Dry 24 hours.Sample is denoted as POP.The specific surface area of the sample is 592 m2/g。
Comparative example 2
PDVB-VP porous organic polymer: it weighs 0.065 g azodiisobutyronitrile and is dissolved in 25 mL ethyl acetate, then land
It is continuous that 2 mL divinylbenzenes (DVB) and 1 mL 4-vinylpridine (VP) is added, all mixtures are filled after 3 h are stirred at room temperature
120 DEG C of kettle 24 h of processing.After the reaction was completed, 24 h of solvent is evaporated at room temperature, and by obtained solid, vacuum is done at 80 DEG C
Dry 24 h, obtains pale pink powder.The porous organic polymer of synthesis is expressed as PDVB-VP-0.5, wherein 0.5 is VP/DVB
Volume ratio.The specific surface area of the polymer is 479m2/ g, nitrogen content 4.18%.
CO2Absorption property and selectivity test
Before test, sample handles 12h in the case of being placed in 160 DEG C (0.1 Pa).It is transferred to 3020 physical adsorption appearance of Mike later
In, and CO is tested in the case of 0 and 25 DEG C2And N2Adsorption isotherm.And CO2Circulation absorption test in plum Teller
Is carried out in TGA/SDTA 851e firstly, weighing about 5mg(accurate weighing) sample is placed in ceramic crucible, and is transferred to TGA days
It is flat.When sample is stable at 25 DEG C, is purged 30 minutes with nitrogen (150ml/min), gas is then switched to pure CO2Gas
(50 ml/min) simultaneously keeps 2h.Then, by CO2Gas is switched to N2And it is warming up to 75 °C. CO2The circulation experiment of absorption waits for temperature
It is tested 10 times after degree and steady air current.
1. N-POPs sample of table CO at different temperatures and pressures2Adsorbance and CO2/N2IAST selectivity
[a]According to gaseous mixture CO2/N2The IAST model of (0.15/0.85) in 1 bar is calculated.
Fig. 1-2 is that embodiment and comparative example measures CO at 0 DEG C, 25 DEG C2And N2Adsorption isotherm.Difference is summarized in table 1
CO under temperature and pressure2Adsorption capacity and its selectivity.By chart it is found that N-POP- urotropine is with higher
CO2Adsorption capacity when 1 bar (at 0 DEG C and 25 DEG C, respectively 5.67 and 3.93mmol/g), and POP corresponding CO2Absorption is held
Amount is respectively 1.05 and 0.96 mmol/g, the CO of PDVB-VP-0.52Adsorption capacity is 1.84 and 1.48 mmol/g, all bright
It is aobvious to be lower than N-POP- in embodimentxCO2Absorption property.The addition for illustrating nitrogen containing monomer provides more nitrogen active sites,
Therefore the CO of material is substantially increased2Absorption property.Except CO2Outside adsorption capacity, CO2/N2Selectivity is also one very important
Parameter, table 1 give embodiment and comparative example to CO2And N2The CO of the gaseous mixture of (0.15/0.85 v/v)2/N2Absorption selection
Property, it is calculated according to perfect solution adsorption theory (IAST).The selectivity of embodiment is apparently higher than comparative example, especially N-POP-
4,4'- bipyridyl is up to 73.9 and 75.6 in 0 DEG C and 25 DEG C of selectivity respectively.Illustrate nitrogenous porous prepared by the embodiment
Polymer has good CO2Selective absorption performance.The circulation experiment of N-POP- urotropine also demonstrates in Fig. 2
The material is with good stability.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nitrogenous porous organic polymer, which is characterized in that by nitrogen containing monomer and Isosorbide-5-Nitrae-to benzyl dichloride or
Vinyl chloride is crosslinked the nitrogenous porous organic polymer of synthesis by being alkylated induction under the conditions of Louis acid catalysis.
2. a kind of preparation method of nitrogenous porous organic polymer according to claim 1, which is characterized in that described nitrogenous
Monomer is p-phenylenediamine, 4,4'- bipyridyls, one of hexa or 4-vinylpridine.
3. a kind of preparation method of nitrogenous porous organic polymer according to claim 1, which is characterized in that by nitrogenous list
Body and Isosorbide-5-Nitrae-are crosslinked the nitrogenous porous organic polymer of synthesis by being alkylated induction under the conditions of Louis acid catalysis to benzyl dichloride,
Specific steps are as follows: firstly, the Isosorbide-5-Nitrae-of certain mass is dissolved in 1,2- dichloroethanes benzyl dichloride, then at 0 DEG C acutely
30-120s is stirred, and lewis acid catalyst is added into mixture；Then nitrogen containing monomer is added in mixture, in N2
A period of time is heat-treated under atmosphere and high temperature；After suction filtration formed solid and with hot dehydrated alcohol wash 3 ~ 5 times it is remaining to remove
Reactant and lewis acid catalyst；Finally crude product is immersed in isopropylamine, 6 ~ 12h is handled at room temperature and is activated,
Nitrogenous porous organic polymer is obtained after vacuum drying, is denoted as N-POP-x, and wherein x is nitrogen containing monomer.
4. a kind of preparation method of nitrogenous porous organic polymer according to claim 3, which is characterized in that the Isosorbide-5-Nitrae-
Quality to benzyl dichloride is 0.5 ~ 2g, and nitrogen containing monomer quality is 0.5-1.5g, and volume is 15-30ml in 1,2- dichloroethanes.
5. a kind of preparation method of nitrogenous porous organic polymer according to claim 1, which is characterized in that nitrogen containing monomer
The nitrogenous porous organic polymer of synthesis, tool are crosslinked by being alkylated induction under the conditions of Louis acid catalysis with vinyl chloride
Body step are as follows: firstly, the Isosorbide-5-Nitrae-of certain mass is dissolved in 1,2- dichloroethanes benzyl dichloride, azodiisobutyronitrile is added
Then AIBN initiator is vigorously stirred 30-120s at 0 DEG C, and lewis acid catalyst is added into mixture；Then will
Nitrogen containing monomer is added in mixture, in N2A period of time is heat-treated under atmosphere and high temperature；Solid is formed after suction filtration and with hot nothing
Water-ethanol washs 3 ~ 5 times to remove remaining reactant and lewis acid catalyst；Finally crude product is immersed in isopropylamine,
6 ~ 12h of processing is activated at room temperature, and nitrogenous porous organic polymer is obtained after vacuum drying, is denoted as N-POP-x, wherein x
It is nitrogen containing monomer.
6. a kind of preparation method of nitrogenous porous organic polymer according to claim 5, which is characterized in that the ethylene
The volume of base benzyl chloride is 0.5-1.5 ml, and initiator quality 0.05g, nitrogen containing monomer quality is 0.5-1.5g, 1,2- dichloro
Volume is 15-30ml in ethane.
7. a kind of preparation method of nitrogenous porous organic polymer according to claim 3 or 5, which is characterized in that described
Lewis acid catalyst is SnCl4Or TiCl4；Its additional amount is 2-5ml.
8. a kind of preparation method of nitrogenous porous organic polymer according to claim 3 or 5, which is characterized in that described
Heat treatment temperature is 60-90 DEG C, heat treatment time 2-6h.
9. a kind of preparation method of nitrogenous porous organic polymer according to claim 3 or 5, which is characterized in that vacuum
Dry temperature and time is respectively 60-120 DEG C and 6-24h.
10. a kind of a kind of nitrogenous porous organic polymer of method preparation as described in claim 1 is being used for CO2Selectivity inhale
Appended application, which is characterized in that the CO2Selective absorption temperature is 0 DEG C and 25 DEG C.Adsorbent inventory is 0.1g；It inhales
It is pre-processed under vacuum conditions before attached, treatment temperature is 160 DEG C, and the processing time is 12h, is subsequently placed in 0 DEG C and 25 DEG C
CO is carried out in Dewar bottle respectively2And N2Absorption.
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| CN110026228A (en) * | 2019-05-22 | 2019-07-19 | 福州大学 | A kind of preparation of nitrogenous porous carbon materials and its H2S selective catalytic oxidation application |
| CN110354702A (en) * | 2019-06-20 | 2019-10-22 | 郑州大学 | One kind being used for CO2/N2The mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof of gas separation |
| CN111848931A (en) * | 2020-08-01 | 2020-10-30 | 青岛科技大学 | Preparation method and application of pyridine group-containing porous organic polymer |
| CN112279236A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Nitrogen-doped hollow carbon sphere and preparation method and application thereof |
| CN114307995A (en) * | 2022-01-26 | 2022-04-12 | 山西潞安矿业(集团)有限责任公司 | Preparation method and application of composite material for capturing carbon dioxide |
| CN115008851A (en) * | 2022-07-01 | 2022-09-06 | 江苏欧晟新材料科技有限公司 | High-density polyethylene composite film and processing technology thereof |
| US11685852B2 (en) | 2020-09-03 | 2023-06-27 | Aramco Services Company | Reservoir drilling fluids consist of cationic heterocyclic polymers, synthesis, formulation, and applications |
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| CN110026228B (en) * | 2019-05-22 | 2021-08-31 | 福州大学 | Preparation of nitrogen-containing porous carbon material and H thereof2S-selective catalytic oxidation applications |
| CN110354702A (en) * | 2019-06-20 | 2019-10-22 | 郑州大学 | One kind being used for CO2/N2The mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof of gas separation |
| CN110354702B (en) * | 2019-06-20 | 2021-10-08 | 郑州大学 | For CO2/N2Mixed matrix membrane for gas separation and preparation method thereof |
| CN111848931A (en) * | 2020-08-01 | 2020-10-30 | 青岛科技大学 | Preparation method and application of pyridine group-containing porous organic polymer |
| CN111848931B (en) * | 2020-08-01 | 2022-05-20 | 青岛科技大学 | Preparation method and application of pyridine group-containing porous organic polymer |
| US11685852B2 (en) | 2020-09-03 | 2023-06-27 | Aramco Services Company | Reservoir drilling fluids consist of cationic heterocyclic polymers, synthesis, formulation, and applications |
| CN112279236A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Nitrogen-doped hollow carbon sphere and preparation method and application thereof |
| CN114307995A (en) * | 2022-01-26 | 2022-04-12 | 山西潞安矿业(集团)有限责任公司 | Preparation method and application of composite material for capturing carbon dioxide |
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