Controlled synthesis and aminating of poly (melamine

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Environmental and Carbon Dioxide Issues

Controlled synthesis and aminating of poly (melamine)paraformaldehyde mesoporous resin for CO2 adsorption Fengqin Yin, Haozhen Ou, Shuoyu Wang, Linzhou Zhuang, Zhejia Wu, and Shui-Xia Chen Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b03191 • Publication Date (Web): 29 Nov 2018 Downloaded from http://pubs.acs.org on November 30, 2018

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Controlled synthesis and aminating of poly (melamine)paraformaldehyde mesoporous resin for CO2 adsorption Fengqin Yin1, Haozhen Ou1, Shuoyu Wang1, Linzhou Zhuang1,3,

Zhejia Wu1,

Shuixia Chen1,2* 1. PCFM Lab, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, PR China 2. Materials Science Institute, Sun Yat-Sen University, Guangzhou 510275, PR China 3. School of Chemical Engineering, University of Queensland, St Lucia QLD 4072, Australia

Abstract A series of mesoporous amino resins (MA) with pore diameters of 2.82 to 9.87nm have been successfully synthesized at low temperature using polyethylene oxide polypropylene oxide - polyethylene oxide (P123) as surfactant template via HCl catalyzed sol-gel reactions of melamine and paraformaldehyde, followed by ethanol extraction. The mesoporous amino resin MA-P123-3.5g, prepared at optimal condition by adding 3.5g P123 as surfactant template, had higher specific surface area of 706.7 m2/g and larger pore size of 9.87 nm. After impregnating with polyethyleneimine (PEI), the obtained MA-P123-3.5g-PEI showed the highest CO2 uptakes of 4.68 mmol/g and amine utilization efficiency of 51.48% at 40oC, which is higher than the theoretical amine utilization efficiency (35%). The kinetics studies implied that the Avrami model could better describes the CO2 adsorption process on the MA-PEI adsorbent, indicating

*

Corresponding author. E-mail address: [email protected];


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the synergistic effect of chemical and physical adsorption mechanisms. The further analysis of CO2 diffusion model implied that the porous structure of MA is beneficial to the diffusion of CO2 in the particles. Due to the positive influence to the amine groups of the larger pore diameter in the accessibility and diffusion process, the MA samples impregnated with PEI also showed good regeneration stability after 10 cycles of CO2 adsorption-desorption. These results are helpful for developing high-performance CO2 adsorbents.

Keywords:

Melamine-paraformaldehyde

resin;

Mesoporous

materials;

Controllable pore size; Polyethyleneimine; CO2 adsorption ； Adsorption mechanism.

1. Introduction Mesoporous materials have received great attention due to their unique properties, such as highly ordered pore structure1, uniform pore size2, controllable pore size3, high specific surface areas4, 5 and plentiful pores6, 7. Since M41S series of materials (MCM41、MCM-48) with pore sizes between 2 nm and 50 nm were firstly synthesized by the Mobil Company in 19928, 9, mighty advances in mesoporous materials have been made. Recently, mesoporous materials are mainly synthesized through hydrothermal method10,

11,

evaporation-induced self-assembly method12,

13

and hard template

method14, 15. The pH range and the temperature of the synthesis are relatively broad, when temperature can vary from room temperature to about 200 oC. The choice of surfactant are also rich in variety, including anionic16, 17, cationic16, 18, non-ionic19, 20


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and special surfactants21, 22. Therefore, mesoporous materials have been widely applied in the chemical field23,

24,

biotechnology25,

26,

information, communication

engineering27, 28, environmental energy29, 30 and other fields31, 32. In the past decade, mesoporous materials have received a wide range of attention; they have been developed into an independent field. Melamine has been used to synthesize porous materials for CO2 adsorption because of its weak basicity (pKa = 5.5), diverse reactivity, inexpensive and extensive sources33,

34.

In the past ten years, the synthesis of mesoporous amino resins with

melamine as the matrix, silica35,

36

or F127

37

as templates have been reported

successively. Kailasam 38 et al. prepared the orderly mesoporous amino resin in ethanol solution with hexahydroxy melamine (HMMM) as monomer and F127 as the soft template. When the mass ratio of HMMM to F127 is 1: 1, the specific surface area reaches 258 m2 / g and the pore volume and pore size are 0.53 cm3 / g and 7.8 nm, respectively. Wilke39 et al. prepared mesoporous amino resins in aqueous solution by employing methylated melamine formaldehyde oligomers as prepolymers and 12 nm diameter silica particles as templates. The specific surface area of the material was related to the curing temperature. When the curing temperature is 250 oC, the specific surface area is 234 m2 / g and the pore volume and pore size are 1.05 cm3 / g and 17.4 nm, respectively. Lee40 et al synthesize ordered mesoporous amino resin with melamine and phenol as the co-monomer and F127 as a soft template. The materials had surface areas of 256 m2 / g, pore volume of 0.13 cm3/ g and pore size of 2.9 nm. It must be noted, however, that the specific surface area of the reported amino resin


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was not high, especially those utilized as a support material for either amine grafting or impregnating for CO2 adsorption. The study imply that the mesoporous with suitable pores can enhance the sorption capacity since they are capable of loading sufficient amine to capture CO2 and also can maintain some space for the diffusion of CO241. However, the melamine does not have any hydrogen bonding sites with surfactants, it does not occur directly self-assembly with surfactants. Besides the condensation temperature is high, leading to the decomposition of surfactants. So it can be seen that the synthesis of mesoporous amino resin with high specific surface area and controllable pore size is an urgent problem to be solved. In this work, P123 was used as template to synthesize mesoporous amino resin with high specific surface area and controllable pore size by sol-gel method at low temperature. After impregnating PEI, the CO2 adsorption performance of the mesoporous amino resin with different pore size was tested to check the influence of pore size on the CO2 adsorption. Three kinetic models were also applied to investigate the CO2 adsorption behavior.

2. Experimental 2.1 Reagents Melamine (AR) and poly (ethylenimine) (PEI, Mw=600) were purchased from Aladdin Chemistry Co. Ltd, China. Paraformaldehyde was purchased from TianjinFuchen Chemical Reagent Factory, China. Dimethyl sulfoxide (DMSO, AR) and ethyl alcohol (AR) were purchased from Tianjin-Fuyu Chemical Co. Ltd, China. Polyethylene oxide - polypropylene oxide - polyethylene oxide (P123) were purchased


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from Sigma-Aldrich Co., Ltd. China. Hydrochloric acid (HCl, 37%) was purchased from Guangzhou Chemical Reagent Factory, China. All reagents were used without further purification.

2.2 Preparation of mesoporous amino resin In a typical preparation process, melamine (4.38g, 34.7 mmol) and paraformaldehyde (3.12 g, 104 mmol) were dissolved in 20 mL DMSO containing 1ml of 0.05M sodium hydroxide (NaOH) solution. The mixture was stirred until it became transparent, then it was added into10ml aqueous solution containing P123 and 1ml HCl (37 wt%). Then, the above mixture was carefully transferred into a Teflon container and stirred at 40 oC for 12h until solidification; after that it was heated to 140 oC to complete

the

polycondensation

of

melamine

and

paraformaldehyde.

The

polycondensation product, a white solid was ground, sieved, and then successively washed with ethanol. The obtained granules were extracted in ethanol to remove the template and then dried under vacuum at 80 oC, which was noted as MA-P123-X, where X presents the amount of P123 added. The formation mechanism was shown in scheme 1.

Scheme 1 the formation mechanism of MA

2.3 Preparation of PEI impregnation sorbents (MA-P123-X-PEI) PEI was loaded onto MA-P123-X by using a wet impregnation method. In a


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typical process, 0.3-0.7 g PEI was dissolved in 20 mL ethanol, and then 0.7g-0.3 g MAP123-X was added into the solution. The mixture was continuously stirred at 70 oC for 5h. After being centrifuged with 10000 r/min for 20 min, the adsorbent loading PEI was dried under vacuum at 80 oC. The resulting adsorbents were denoted as MA-P123-XPEI-Y%. Where Y% is used to identify the weight percentage of PEI and is normally within the range of 30%~70%.

2.4 Characterization Nitrogen adsorption-desorption isotherms were tested on an automatic gas adsorption instrument (ASAP2020, Micromeritics Corp., USA) at 77K with the range of relative pressure from10-6 to 1. Before each measurement, the samples were dried under vacuum at 100 oC overnight. Vtotal was calculated based on the nitrogen amount adsorbed at P/P0 = 0.95. Specific surface area and pore parameters were calculated by using the Brunauer-Emmett-Teller (BET) method and density functional theory (DFT) method, respectively. Scanning electron microscope (SEM, S4800, Hitachi, Japan) was employed to observe the morphology and microstructure of the samples, and transmission electron microscope (TEM, JEM-2010HR, JEOL, Japan) was used to observe the porous structure. Powder X-ray diffraction (XRD, D8 ADVANCE, BRUKER Textile Technologies GmbH & Co., KG, Germany) was applied to analyze the crystal structure of MA and the profile was collected in the 2θ angle between 0.6o and 5o with scan rate of 1o /min.

2.5 The CO2 adsorption measurement The CO2 adsorption capacity was measured in a fixed bed flow system. Before


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measurement, the sample was dried under vacuum at 80 oC for 12 h. Then 0.5 g dried adsorbent was loaded into a glass tube (Φ = 1.3 cm). The dry nitrogen with a flow rate of 30 mL/min was introduced into the column at 90 oC for 20 minutes to remove the air and residue water. Then the column was cooled down to room temperature. A mixed gas that include 10 % CO2 and 90 % N2 with a flow rate of 30 mL/min was introduced to the tube for the adsorption test. The CO2 concentrations at the inlet and outlet were determined by an Agilent 6820 gas chromatography that is equipped with a thermal conductivity detector. After completing the CO2 adsorption, the adsorbent was regenerated by purging with N2 with a flow rate of 30 ml/min at 90 oC. The adsorption capacity was calculated by follow equation: 𝑡

𝑄 = ∫0(𝐶𝑖𝑛 ― 𝐶𝑒𝑓𝑓) ∙ 𝑉 ∙ 𝑑𝑡/22.4𝑊

(1)

where Q is the adsorption capacity of the adsorbent (mmol CO2/g), t is the adsorption time (min), and Cin and Ceff are the influent and effluent concentrations of CO2 (vol%), respectively; V is the total flow rate, 30 mL/min; W and 22.4 are the weight of the adsorbent (g) and molar volume of gas (mL/mmol), respectively.

3. Results and discussion 3.1 Preparation and pore tailoring of amino resins MA Mesoporous amino resin with pore diameters of 2.82 to 9.87nm have been successfully prepared at low temperature using P123 as surfactant template via HCl catalyzed sol-gel reactions of melamine and paraformaldehyde, followed by ethanol extraction. To better understand the relationship between pore width distribution and


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the dosage of P123, the N2 adsorption-desorption isotherms were used to characterize the pore structure of the MA resins (Figure 1). As exemplified in Figure 1a, MA prepared with high P123 template dosage (>1.5g) exhibited type TV isotherms with type H2 hysteresis coops, whereas the sample prepared with low template addition amount ( 0.85) 𝑞𝑡

𝐹 = 𝑞𝑒

(6) (7) (8)

The interparticle diffusion model is express as: 6

𝑞𝑡 = 𝑞𝑒 ― 𝑞𝑒𝜋2𝑒

― 𝜋2𝑘𝑓𝑡 15


（9）

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The intraparticle diffusion model is express as: 𝑞𝑡 = 𝑘𝑖𝑑𝑡1/2 +𝐶

（10）

where qe(mmol·g-1) and qt (mmol·g-1) refer to the amount of CO2 adsorbed at equilibrium and at a given point of time, respectively. t (min) refers to the adsorption time. C refers to the boundary layer thickness. kf (mmol·g-1) and kid (mmol·g-1) refer to the interparticle diffusion and intraparticle diffusion rate constant, respectively. F is the fractional attainment of equilibrium at a given point of time. Bt is a mathematical function of F. The Boyd’s film-diffusion plots for Bt against time are displayed in Figure 7b. Referring to the Boyd’s film-diffusion theory, the plots are not linear so that the adsorption of CO2 is not only controlled by film-diffusion but also the pore-diffusion and chemical reaction. Figure 7c shows the CO2 adsorption amount of MA-PEI at different temperature with fitting curves of interparticle diffusion models drawn on it. The plots of interparticle diffusion cannot overlap the points of experiment data and the predicted adsorptions are higher than their actual value.

Since the interparticle diffusion model cannot explain the diffusion behavior of CO2 adsorption of MA-PEI, the intraparticle diffusion model is applied for analyzing the diffusion behavior of CO2. Figure 8 shows that intraparticle diffusion plots can be divided into three stages of intraparticle diffusion: (1) film diffusion in boundary layer: at the initial stage, film diffusion controls the adsorption rate when the CO2 is outside the particles. (2) pore diffusion inside particle: the CO2 penetrates through the boundary layer, into the particles, when the pore diffusion controls the adsorption rate. (3)


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equilibrium stage: at the adsorption equilibrium stage, CO2 penetrates into each pore and the surface reaction controls the adsorption rate. As is shown in Figure8, except for the plots at 40 oC, the slopes of third stage are the lowest slopes of three stages, demonstrating that the surface reaction controls the adsorption rate. In addition, at all the temperature in the experiment, the slopes of second stage are the highest, indicating that the porous structure of MA is conductive to the diffusion of CO2 in the particles.

Figure 8 Intraparticle diffusion simulation curves of MA-PEI under different temperature

Conclusion In summary, we have successfully prepared a series of mesoporous amino resins （MA） with pore diameters of 2.82 to 9.87nm at low temperature using polyethylene oxide - polypropylene oxide - polyethylene oxide (P123) as surfactant template via HCl catalyzed sol-gel reactions of melamine and paraformaldehyde, followed by ethanol extraction. After impregnating polyethyleneimine (PEI 50%), the PEI supported MA resin exhibited higher CO2 uptakes of 4.68 mmol/g and amine utilization efficiency of 51.48%, which is higher than theoretical amine utilization efficiency (35%) at 40 oC.


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The kinetics observation showed that the Avrami model could better describe the CO2 adsorption process and the whole process exist both physisorption and chemisorption. Analysis using intraparticle diffusion model showed that there were three stages of intraparticle diffusion, including film diffusion, pore diffusion and equilibrium stage (surface reaction). Among the three stage, the slopes of second stage (pore diffusion) are the highest, indicating that the porous structure of MA is beneficial to the diffusion of CO2 in the particles. Due to the positive influence to the amine groups of the larger pore diameter in the accessibility and diffusion process, the MA samples impregnated with PEI also showed good stability after 10 adsorption-desorption cycles of CO2. These results provide a way to synthesis an excellent solid amino adsorbent for CO2 capture.

Acknowledgement The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (Grant No. 51473187), Natural Science Foundation of Guangdong Province (2016A010103013).

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Figures Figure 1

Figure 1 N2 adsorption-desorption isotherms at 77 K (a) and pore size distributions (b) of MAs


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Figure 2

Figure 2 (a) TEM and (b) SEM images of MA-P123-3.5g, (C) PXRD analysis of MAP123-0g and MA-P123-3.5g


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Figure 3

Figure 3 Effect of P123 dosage on the CO2 adsorption breakthrough curves (a), capacity and amine utilization efficiency (b) of MA (adsorbent mass: 1.0 g; adsorption temperature: 30 oC; N2: 27 mL/min; CO2: 3 mL/min)


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Figure 4

Figure 4 The effect of PEI-loading amount on CO2 adsorption breakthrough curves (a), capacity and amine utilization efficiency (b) of MA - P123 -3.5g-PEI


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Figure 5

Figure 5 CO2 adsorption breakthrough curves (a), capacity and amine utilization efficiency (b) of MA-P123-3.5g-PEI 50% at different temperature


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Figure 6

Figure 6 Adsorption capacities of CO2 on fresh and regenerated MA-P123-3.5g-PEI 50%


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Energy & Fuels

Figure 7

Figure 7 (a) Experimental CO2 capacities on MA-PEI under different temperature and corresponding fit to kinetic models, (b) Boyd’s film diffusion simulation curves of MAPEI under different temperature, (c) Interparticle diffusion simulation curves of MAPEI under different temperature.


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Figure 8

Figure 8 Intraparticle diffusion simulation curves of MA-PEI under different temperature


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Energy & Fuels

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Controlled synthesis and aminating of poly (melamine

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