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Applicable Strategy for Removing of Liquid Fuel Nitrogenated Contaminants using MIL-53-NH2@Natural Fabric Composites Reda M. Abdelhameed, heba el-deib, Farida M. S. E. El-Dars, Hanan B. Ahmed, and Hossam E. Emam Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b03936 • Publication Date (Web): 16 Oct 2018 Downloaded from http://pubs.acs.org on October 17, 2018

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Industrial & Engineering Chemistry Research

Applicable Strategy for Removing of Liquid Fuel Nitrogenated Contaminants using MIL-53-NH2@Natural Fabric Composites Reda M. Abdelhameed a,*, Heba R. El-Deib b, Farida M. S. E. El-Dars b, Hanan B. Ahmed b, Hossam E. Emam c, * [a]

Applied Organic Chemistry Department, National Research Centre, Scopus affiliation ID 60014618, 33 EL Buhouth St., Dokki, Giza, 12622, Egypt [b] Chemistry

Department, Faculty of Science, Helwan University, Ain-Helwan, Cairo 11795, Egypt

[c] Department

of Pretreatment and Finishing of Cellulosic based Textiles, Textile Industries Research Division, National Research Centre, Scopus affiliation ID 60014618, 33 EL Buhouth St., Dokki, Giza 12622, Egypt.

* Corresponding

authors. E-mail address: [email protected] (Hossam E. Emam) Tel.:+201008002487, Email address: [email protected] (R. M. Abdelhameed).

ABSTRACT Purification of liquid fuel from nitrogenated compounds is of interest in order to protect the automotive engines and the environment from its harmful effects represented in corrosion, formation of gums in engines and evolution of NOx gases. In the current report, composite from metal organic framework (MOF) and natural fabric (cotton and wool) was designed and applied in removal of nitrogenated compounds from liquid fuel. MOF based on Al, namely MIL-53-NH2 was immediately formed inside fabric to produce MIL-53-NH2@fabric composite. The contents of MOF onto fabrics were 185.0 mg/g (≈ 22.4 of Al mg/g) for cotton and 234.5 mg/g (≈ 28.4 of Al mg/g) for wool. Infrared and X-ray spectra confirmed the formation of MIL-53-NH2 MOF within natural fabrics. The microscopic observations for composites, showed that the compositions of fabrics played a main role in the morphology of the incorporated MOF. The formed composites were applied in adsorption of indole and quinoline from liquid fuel and the adsorption was fitted well to Langmuir isotherm. Maximum adsorption capacities of nitrogenated compounds were significantly enlarged from 87.7 mg/g and 125 mg/g onto cotton to 149.3 mg/g and 178.6 mg/g onto composite, respectively. In case of wool, maximum capacities were increased from 121.5 mg/g to 163.9 mg/g and 156.4 mg/g to 204.1 mg/g after incorporation of MIL-53-NH2 MOF into fabric. The adsorption capacity of composite was diminished by percentage of 19.2 – 40.0 % by applying 4 regenerated cycles. It was found that, adsorption 1 ACS Paragon Plus Environment

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capacities were linearly function with MOF and Al contents onto fabrics. Such stable composite against recycling could be highly applicable as filter in fuel purification and could be used for many times with substantial adsorption efficiency. Keywords: Natural fabrics; MIL-53-NH2 MOF; Fuel purification; Indole; Quinoline; Adsorption; Reusability

1. Introduction: The different types of fuels such like liquid, solid and gaseous fuels are important for firing in boilers, furnaces and other combustion equipments. The liquid fuel is combustible liquid and mostly used in transportation. It could be ascribed as energy-producing compounds as it can be usually harnessed to create kinetic energy. Most of liquid fuels are derived from fossil 1-2 and hence it contains organic contaminants as oxygenated, nitrogenated and sulphur compounds

3-4.

Nitrogenated compounds which are presented in crude petroleum or in its fractions are ascribed as undesirable compounds because of the problems that may be occurred in the refining process, such as catalyst poisoning, corrosion and gum or color formation 5. Additionally, it was reported that several basic and even neutral nitrogen compounds are toxic and were found to exhibit carcinogenic activities 6. Nitrogen containing compounds in liquid fuels are basically classified to two types; basic nitrogenated compounds (such as pyridine and quinoline) and non-basic nitrogenated compounds (e.g. carbazole and indole) 3-4. In the recent years, removing of nitrogen containing compounds from liquid fuels was extensively studied by researchers interested in such field, taking in consideration the strict environmental regulations in recent years. In the petroleum industrialization, Hydro-denitrogenation (HDN) technique

7

is commonly used for removing of nitrogen containing

compounds from liquid fuel, but this referred process is highly expensive due to, it requires high temperature for operation, pressure, and hydrogen consumption. Therefore, several non-hydrode-nitrogenation techniques, including adsorption, solvent extraction, and oxidation were developed to be used instead of HDN process 7. Adsorption technique as one of non-hydro-de-nitrogenation processes is basically used for removing of nitrogen-containing compounds from liquid fuel by employing solid material to act as adsorbent, in order to retain nitrogenated compounds when the liquid fuel is allowed to flow over such adsorbent. The adsorbent material is mainly chosen so that it can attract and 2 ACS Paragon Plus Environment

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retain the nitrogenated compounds by the interactions with the surface of such adsorbent. According to literatures, different types of adsorbents have been reported for removing of nitrogen containing compounds from liquid fuels such as silica gel 14,

activated carbon

polymers

18-19

13, 15,

and zeolites

modified silica–alumina

metal–organic frameworks

16-17,

8-12,

activated alumina

9, 13-

ion-exchange resins and modified

20-22

in addition to a number of diverse materials like solid acids and

23-24.

Metal organic frame work are well known to be more

advantageous due to their high adsorption capacities 25-29. Metal–organic frameworks (MOFs) are mainly composed of two inorganic and organic components. The first component is a central metal ion or a cluster of metal ions, and the second component is an organic linker. MOFs contain specific chemical functionalities which could be exploited for selective adsorption of some species, and these functionalities are one of the most considerable properties of MOFs

30-33.

MOF materials could be successfully applied in different

purposes such like, gas adsorption/storage, separation, catalysis, adsorption of organic molecules, drug delivery, light emitting, electrode materials, carriers for nanomaterials, magnetism, polymerization, imaging, membranes, anti-mosquitoes and so on

33-44.

MOF

materials were showed very special physical and chemical characters to be usable in various applications; moreover, their properties can be further enhanced via different process such as, grafting active groups

45,

changing organic linkers

post synthetic ligands and ion exchange

48

46,

impregnating suitable active materials

and making composites with suitable materials

47,

49-53.

Few studies were reported for the application of MOFs in the removal of nitrogen containing compounds from liquid fuel. MIL-101(Cr) MOF was studied for its application in removing of nitrogenated compounds from straight-run gas oil and its mixtures with light cycle oil, and the percentage for removing of nitrogenated compounds was around 90%

16-17.

It was also reported

that a functionalized MOF could be able for removal of both indole and quinoline from model oils

18-19.

Moreover, employment of MOF in liquid fuel purification is still limited owing to the

difficulties in applicability. Thus, loading of MOF materials onto carrier such as fabric is a promising to be highly applicable. Removal of nitrogenated compounds from liquid fuel was performed in the current work through using composite from MIL-53-NH2 as Al containing metal organic framework (MOF) and natural fabric based on cotton and wool. The composite was firstly prepared by direct formation of MIL-53-NH2 MOF within fabric matrix. The as-prepared composites were 3 ACS Paragon Plus Environment


characterized by scanning electron microscope, energy dispersive X-ray, X-ray diffraction and FTIR. Materials (MOF and Al) contents onto fabrics and colorimetric data of fabrics were all measured. The formed MIL-53-NH2@fabric composites were applied in adsorption of different nitrogenated compounds (indole and quinoline) from liquid fuel. Kinetics and isotherm of adsorption process were both studied. Recycling process of the MIL-53-NH2@fabric composites were tested and the adsorption mechanism was also suggested. EXPERIMENTAL SECTION Chemicals and materials Aluminum chloride hexahydrate (AlCl3.6H2O, ≥ 98%), 2-aminoterephthalic acid (99%), sodium hydroxide (NaOH, 99%), N,N-dimethyl formamide (DMF, 99.9%), dimethyl sulfoxide (DMSO, ≥ 99.5%), hydrochloric acid (HCl, 37 %), methanol (absolute, 99.9%), ethanol (absolute, 99.9%) and ammonium hydroxide (NH3, ≈ 25%) were all supplied from SigmaAldrich with analytical grade and used without further purification. Desized, scoured and bleached plain-woven 100% cotton fabrics (160 gm/m2) and pure Australian merino scoured woven 100% wool fabrics (210 g/m2), were kindly supplied from Misr Company for Spinning and Weaving, El-Mehalla El-Kobra – Egypt. To remove the impurities, fabrics were washed for 30 min. at 50 °C with solution containing 2 g/L of nonionic detergent (Hospatal CV from Clariant) using material to liquor ratio of 1:50. Fabrics were taken out, rinsed twice with tap water and then dried at RT. Preparation of MIL-53-NH2@natural fabric composites Composites of MIL-53-NH2@cotton fabric and MIL-53-NH2@wool fabric were prepared in two steps including activation and metal organic framework (MOF) incorporation. In the first step, fabric specimens (20 × 40 cm2) were activated through immersion in 0.4 M of sodium hydroxide solution for 30 minutes, followed by rinsing with tab water for 15 minutes. In the second step, MIL-53-NH2 MOF was directly formed within fabric matrix by using layer by layer technique consisting of four layers from MOFs. In each layer, the activated fabrics were dipped in aqueous solution of Al+3 (0.4 M) for 15 minutes, followed by rinsing with tab water. Afterwards, Al-fabrics were immersed in ligand mixture solution containing 0.12 g of 2aminoterephthalic acid and 0.5 mL sodium hydroxide (0.4 M) dissolved in 100 mL water for 15 4 ACS Paragon Plus Environment

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minutes. The fabrics were then rinsed with tab water and were dried at 120 °C for 30-40 minutes. This process was repeated 4 times to get 4 layers of MOF. Characterization The contents of MIL-53-NH2 MOF onto fabrics before and after recycling were measured via the difference in weight of fabrics after removing of MOF from the MIL-53-NH2@fabric composites. The MOFs were completely removed by two sequential steps namely dissolution and washing steps. In dissolution step, a 0.1 g of composite was immersed in 10 mL of DMSO/HCl solution (90:10) under continuous shaking for 1 h, then composites were taken out and washed with DMSO followed by washing with ethanol. Furthermore, second step of washing was performed for complete dissolution of MOF. In the washing step, the composite was submerged in 10 mL of ammonia solution (5%) for 30 min. followed by rinsing with tab water. Finally, composites were air dried at room temperature and their weight were recorded. The differences between both weights were referred to the MIL-53-NH2 MOF contents. Considering the measured contents of MOF, amounts of Aluminum onto fabrics were estimated. The colorimetric data represented in lightness (L*, from black to white), a* (red/green ratio) and b* (yellow/blue ratio), were measured for the untreated fabrics and the prepared MIL53-NH2@natural fabric composites. The color coordinates were recorded by using a spectrophotometer (UltraScan Pro, Hunter Lab, USA) attached with light source lamp of pulsed xenon and using D65 illuminant with 10° observer at 8 mm measurement area. The measurements were performed at three independent areas including both sides of fabrics and the mean values were considered. The topographical properties of the untreated fabrics and the prepared MIL-53NH2@natural fabric composites were investigated by using a scanning electron microscope (SEM, Hitachi SU-70) running at 25 kV an accelerating voltage in room temperature. The elemental analysis of samples was recorded by field emission gun energy dispersive X-ray spectrometer (EDX) analyzer equipped with the same microscope. The X-ray diffraction analysis was measured for MOF powder, untreated fabrics and the MIL-53-NH2@natural fabric composites at room temperature. Samples were subjected to XRD, Philips X’Pert MPD diffractometer (Cu Kα X-radiation at 40 kV, 50 mA and λ = 1.5406 Å).

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Data of diffraction were collected in the ranging of 2θ = 3.5 to 50° with scanning rate of 1 s and 0.03° step size. The infrared absorbance spectra of MOF powder, untreated fabrics, MIL-53NH2@natural fabric composites and MIL-53-NH2@natural fabric composites after adsorption of nitrogenated compounds, were measured by using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR, Mattson 5000 FTIR spectrometer). FTIR instrument was operating with a detector of deuterated triglycine sulfate and accessory attenuated total reflectance (ATR unit with Golden Gate diamond crystal). The absorption spectral data were collected in the wavenumber range of 350–4000 cm–1. Adsorption study of nitrogenated compounds The prepared composites (MIL-53-NH2@cotton fabric & MIL-53-NH2@wool fabric) were employed in elimination of indole and quinoline as different nitrogenated compounds from liquid fuel. In such adsorption study, a simulated liquid fuel was used through dissolving of indole and quinoline separately in n-heptane. To study the adsorption kinetics, 1000 mg/L nitrogenated compounds were used as adsorbate and the process was performed for 24 h at 30 °C. Nitrogenated compounds with concentrations ranged in 150-4000 mg/L were used in case of studying the adsorption isotherm. In each experiment, 50-60 mg fabrics or composites as adsorbent were added to 10 mL simulated liquid fuel under continuous shaking using a temperature-controlled shaker. At the end of experiments, fabrics were removed and the residual nitrogenated compounds were analyzed by using a JASCO UV 630 spectrophotometer in the wavelength range of 200-400 nm. The adsorption experiments were repeated 3 times and the mean values were recorded. For the regeneration of composites, the nitrogentaed compounds were removed by dissolution in ethanol for 2 h. Thereafter, the composite was washed by diethyl ether, dry and then reuse again in the second adsorption cycle. Statistical analysis The values of MOF contents, color coordinates and adsorption represented in the current study, were an average of 3 independent measurements. Adsorption kinetics parameters, correlation coefficient (R2) and standard deviations, were all calculated by using 2016 Microsoft


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Excel. All of the as-shown Figures were designed by using origin 8 program and the error bars were included in all Figures.

RESULTS AND DISCUSSION MIL-53-NH2@Fabric Before the addition of MOF mixture, the natural fabrics were firstly activated by treatment with sodium hydroxide. The formation of composites (MIL-53-NH2@cotton and MIL53-NH2@wool fabrics) was performed by addition of the MOF mixture solution consisting of Al+3 and 2-aminoterphthalic acid, to the pre-activated fabrics. As suggested in Figure 1, natural fabrics with its several hydroxyl groups, can act as another ligand able to form linkage with Al+3. Hence, during manufacturing of MIL-53-NH2 within fabric matrix, Al+3 may be formed linkage with 2-aminoterphethalic acid from one side and with natural fabrics as mixed linker from the other side 28-29, 54-55. …………..Figure 1………….. The estimated contents of MOF and Al within the natural fabrics after the direct formation of MIL-53-NH2, were summarized in Table 1. The content of MOF was 185.0 and 234.5 mg/g onto cotton and wool fabrics, respectively. As known, the molecular formula of MIL-53-NH2 MOF is Al(OH)(C8H5O4N) and consequently, each gram of MOF consists of 121 mg Al+3. Hence, the content of Al+3 onto fabrics was estimated to be 22.4 and 28.4 mg/g in case of cotton and wool, respectively. Compared to cotton, the higher MOF and Al+3 contents onto wool fabrics is attributed to the larger number of functional groups as binding sites for chelation with the ligand (2-aminoterephthalic acid) and Al+3, and therefore the affinity of wool was higher towards MOF 28. Owing to the incorporation of MIL-53-NH2 MOF within natural fabrics, the color of fabrics was changed as reported in Table 1. The color of cotton was turned from original white color (a*= -0.14; b*= 0.25) to yellow color (a*= -0.98; b*= 7.84) after formation of MOF within fabrics. In case of wool, the color was changed from greenish-yellow (a*= -6.69; b*= 24.37) for untreated to deeply greenish-yellow (a*= -9.02; b*= 36.45) for MIL-53-NH2@wool fabrics composite. The changing in color of fabrics due to treatment, was significantly bigger in case of wool, corresponding to the higher MOF content. 7 ACS Paragon Plus Environment


…………..Table 1…………..

SEM The morphological features of the fabric surface after the insertion of MOF, were examined by electron microscope (SEM) and the results were presented in Figure 2. Both of electronic images and EDX analysis confirmed the direct preparation of MIL-53-NH2 MOF within fabric matrix. Signal of Al element at 1.5 Kev was detected in EDX spectra for both treated fabrics. Fabrics were fully covered with densely masses of MIL-53-NH2 MOF and the morphological structures of MOF were relied on the type of fabric. Crystalline MOF with cracks like structure was observed onto cotton fabrics, while smaller sized particle like shape of MOF was showed in case of wool fabric. This observation indicates to the role of fabrics composition in the nature of incorporated MOF, which is related to the contribution of different functional groups in fabrics (-OH for cotton and, -NH and -OH for wool) in MOF formation. The data of MOF/Al contents further confirmed this hypothesis, where, wool showed much higher contents compared to cotton. …………..Figure 2…………..

XRD Further confirmation for the formation of MIL-53-NH2 MOF within fabric matrix was performed via measurement the X-ray diffraction (Figure 3). For MOF powder, several diffraction peaks were recorded at 2θ= 8.5°, 10.2°, 12.4°, 15.0°, 17.4° and 26.2°, which are characterized for MIL-53-NH2 56. Cotton fabrics exhibited diffraction peaks of 2θ= 14.2°, 16.4° and 22.6°, corresponding to the crystalline structure of cellulose I 57-59. Two diffraction peaks at 2θ= 21.2° and 23.7° were recorded for wool fabrics 28. For the MIL-53-NH2@fabric composite, all diffraction peaks of MOF were clearly observed beside the diffraction peaks of fabrics, which confirmed the presence of MOF in the composite. …………..Figure 3…………..

FTIR The chemical structures of the fabric before and after modification with MIL-53-NH2 MOF were investigated by FTIR spectroscopy and the spectral results were shown in Figure 4. 8 ACS Paragon Plus Environment

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The characteristic absorption peaks of cotton were obviously seen at wavenumber of 3322 – 3292 cm-1, 2887 cm-1, 1630 cm-1 and 1426 cm-1. These peaks are corresponding to the stretching vibration of OH, asymmetric stretching vibration of CH aliphatic, stretching vibration of C=O, and scissoring vibration of CH2, respectively

60-64.

For wool, significant absorption peaks of

stretching and deformation vibration for NH were appeared at 3320 and 1410 cm-1. Amide I, II and III were observed at absorption peaks of 1670, 1560 and 1250 cm-1, respectively

28, 54.

Additionally, asymmetric stretching vibration of CH and symmetric bending of C-C were noticed at 2900 – 3100 cm-1and 1100 cm-1, respectively. In case of MIL-53-NH2@fabric composite, the absorption peaks of MIL-53-NH2-MOF were appeared besides the absorption peaks of fabrics, affirming the formation of MOF within fabrics. The absorption peaks at 760, 1440, 1508 and 1580 cm-1 are attributing to the chelation between Al ions and carboxylate of ligand in the MOF

27-29, 54-55.The

absorption peak at 1690

cm−1 is referred to the carbonyl of 2-aminoterphthalic acid 28-29. The intensities of the new peaks were significantly showed in case of cotton fabrics. As a summary, the MIL-53-NH2 is interacted with fabrics through its function groups; hydroxyl groups of cotton and amide groups of wool. …………..Figure 4…………..

Removal of nitrogentaed compounds The prepared composites of MIL-53-NH2@cotton fabric and MIL-53-NH2@wool fabric were both applied in the elimination of N-containing compounds from the liquid fuel model. Indole and quinoline were selected in this study as two different N-containing compounds exist in the liquid fuel. Untreated fabrics (cotton and wool) as references were used to compare the elimination results of nitrogenated compounds by composites. The adsorption of N-containing compounds onto the prepared composites was confirmed by measurement the infrared spectra as presented in Figure 5. After indole adsorption onto MIL53-NH2@fabric composite, new absorption peaks are obviously appeared at 421, 770 and 805 cm-1 which are the characterized absorption peaks for indole molecules 65-66. For composite after quinoline adsorption, many new absorption bands were recorded at 737-806 and 1496 cm-1 which are referring to the bending vibration of =CH and stretching vibration for C ‫ـــ‬C of the ring, respectively 66-68.



…………..Figure 5………….. Adsorption kinetics Adsorption kinetics of nitrogentaed compounds (indole & quinoline) onto untreated fabrics (cotton & wool) and MIL-53-NH2@fabric composites (cotton & wool) were studied at low concentration and the data were presented in Figure 6. Whatever fabrics type and adsorbed compound, the adsorption percentage was gradually increased with contact time up to 24 h and adsorption rates were higher in the first 6 hrs, owing to the equilibrium behavior. The adsorption rates were start to decrease after this limit due to the lower availability of free binding sites ready for adsorption. Similar trends were observed for adsorption of nitrogenated compounds and indole showed much higher affinity towards fabrics compared to quinoline. Because of its several binding sites, composites exhibited greater adsorption rates and the adsorption capacities were follow the order of MIL-53-NH2@wool fabric composite > MIL-53-NH2@cotton fabric composites > wool > cotton. After incorporation of MIL-53-NH2 MOF, the adsorption percentage of nitrogenated compounds onto cotton was enlarged from 68.1 and 59.4 to 87.2 and 76.8 for indole and quinoline, respectively after 24 h. The adsorbed indole and quinoline within 24 h were respectively increased from 66.8-75.5 % for wool to 85.1-96.0 % for MIL-53NH2@wool composites. These results clarified that, the adsorption of nitrogenated compounds onto fabrics were enlarged by similar percentage of 17.4-20.5, due to MOF incorporation. …………..Figure 6………….. The linear relationship between adsorption amounts and adsorption time was performed and introduced in supplementary file (Figure S3). From the linear function, kinetic parameters (adsorption at equilibrium qe, the constant rate of adsorption K2 and relation coefficient R2) were all calculated and collected in Table 2. The adsorption of nitrogenated compounds onto fabrics and composites were found to be fitted well with second order kinetic model, as a result of achieving the best linearity (R2 = 0.98-0.99). The constant rate of indole adsorption was significantly increased from 85.6 g/mg min and 124.2 g/mg min to 229.8 g/mg min and 311.1 g/mg min for cotton and wool before and after MOF incorporation, respectively. However, values of K2 for adsorption of quinoline were raised from146.4 g/mg min for cotton fabrics to 227.2 g/mg min for MIL-53-NH2@cotton composite and from 234.2 g/mg for wool fabrics to 264.8 g/mg min for MIL-53-NH2@wool composite. These results indicated that the adsorption 10 ACS Paragon Plus Environment

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rate of nitrogentaed compounds onto fabrics was dramatically speeded up insertion of MOF and wool fabrics showed faster adsorption rate. Insertion of 185.0 mg of MIL-53-NH2 MOF in 1 g cotton, resulted in acceleration of the adsorption rate by factor of 1.7 and 0.6 times for indole and quinoline, respectively. In accordance to the represented data, in case of wool, the accelerative effect for the rate of adsorption with incorporation of MIL-53-NH2 MOF was much lower. For all tested samples, the adsorption rate of quinoline was mainly slower than that for indole. Based on the principle of pseudo-second order reaction, the adsorption of nitrogentaed compounds onto the applied composites was carried out through a pseudo-chemical interaction. Consequently, the adsorption amounts were dependent on the number of binding sites, where increased by MOF incorporation and hence, further increment in the adsorption capacities could be achieved by increment the amount of incorporated MIL-53-NH2 MOF within fabrics. …………..Table 2………….. Adsorption isotherm Adsorption isotherm of nitrogenated compounds onto fabrics was studied through plotting the adsorbed amounts (Qe, mg/g) with the initial concentration of nitrogenated compounds and data were represented in Figure 7. Nitrogenated compounds were studied in the concentration range of 250 – 3500 mg/L and the applied dose of fabrics were 10 g/L. Regardless to the adsorbed nitrogenated compound and fabric type, a plateau shape was observed. Adsorption amounts of nitrogenated compounds were linearly increased with its concentration up to the optimal concentration (500 mg/L). Negligible increment in adsorption amounts was almost performed after this concentration. Adsorption capacities of wool fabrics against nitrogenated compounds were higher than that of cotton and the affinity towards indole was showed higher. By increment the fabric dose from 10 mg/L to 100 mg/L (supplementary file, Figure S4), the adsorbed amount was gradually increased as a result of enlargement of the binding sites. Within 24 hours, the removal percentage of nitrogenated compounds onto MIL-53NH2@cotton and MIL-53-NH2@wool fabric composites was dramatically grown from 27.1-46.2 % and 34.4-55.2 % by using 10 mg/L to 76.8-87.2 % and 85.1-96.0 % by using 100 mg/L, respectively. The linearity function of adsorption isotherm was performed with best fitting for Langmuir model. The as-shown Langmuir isotherm for adsorption of nitrogenated compounds is 11 ACS Paragon Plus Environment


characterized by the formation of one adsorption layer onto the homogenous surface of fabrics 27, 69-70.

As during the adsorption process, the nitrogenated compounds are supposed to be adsorbed

by the aid of fabrics’ binding sites and within intermolecular spaces. Therefore, the adsorption is mainly limited by the binding sites and every nitrogenated compound molecule is typically adsorbed on only one active site, building up one adsorbed layer 27-29, 70. The parameters of isotherm (maximum adsorption capacity Qmax, Langmuir constant KL and relation coefficient R2) were calculated and reported in Table 2. Due to insertion of MIL-53NH2 MOF, the maximum adsorption capacities of indole and quinoline onto cotton fabrics were significantly enlarged from 125.0 mg/g and 87.7 mg/g to 178.6 mg/g and 149.3 mg/g, respectively. In case of wool fabrics, the maximum adsorption capacities were maximized from 156.4 mg/g to 204.1 mg/g for indole and from 121.5 mg/g to 163.9 mg/g for quinoline, after MIL-53-NH2 MOF incorporation. Therefore, the maximum capacities of nitrogenated compounds adsorption were increased by percentage of 42.9– 70.2 for cotton and 30.5–34.9 for wool when fabric composites were used. These results declared the role of MIL-53-NH2 MOF in the great increment of nitrogenated compounds adsorption, attributing to increment of the active sites onto fabric. Subsequently insertion of higher MOF contents onto fabrics or using of much higher fabric dose are more required in case of fuel highly contaminated with nitrogenated compounds. …………..Figure 7………….. Comparing to the data in literature concerning with adsorption of indole and quinoline as nitrogenated compounds, Table 3 was designed to include the adsorption capacities for different adsorptive materials. By Qmax values of 149.3 – 204.1 mg/g, better adsorption data were recorded for MIL-53-NH2@natural fabric composite compared to that of aluminum silicate (14.1 mg/g) and activated alumina (49.1 mg/g)

13, 23.

However, similar adsorption capacities were observed

by using of activated carbon (162.8 – 194.6 mg/g) and MOF materials (194.0 – 239.0 mg/g) 71-74. Employment of pure MOF materials is logically resulted in much higher adsorption capacities of nitrogenated compounds

13, 71, 74.

But using of pure MOF increased the final cost of fuel

purification and hence the application of the current prepared composite (MIL-53-NH2@natural fabric) is quite preferred due to the achievement of sufficient purification with lower cost in addition to the applicability. 12 ACS Paragon Plus Environment

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…………..Table 3………….. Regeneration of MIL-53-NH2 @fabric composites The capability of adsorbate materials to regenerate and reuse with sufficient adsorption capacity is an important issue to be widely applicable. Hence, the regeneration (desorption) of MIL-53-NH2@fabric composites after adsorption of nitrogenated compounds was carried out by using ethanol as organic solvent. Afterwards, the reusing of regenerated composites in readsorption of nitrogenated compounds was then performed. The regeneration/reusing process was repeated for four consecutive cycles and adsorption data were presented in Figure 8. Regardless to the types of fabric and nitrogenated compounds, and depending on the number of cycles, the efficiency of MIL-53-NH2@fabric composites in adsorption of nitrogenated compounds were gradually decreased as a function of regeneration. The adsorption capacities of indole and quinoline were decreased from172.0 mg/g and 142.0 mg/g to 122.5 mg/g and 83.9 mg/g for MIL-53-NH2@cotton fabric composite, and from 201.0 mg/g and 159.0 mg/g to 162.5 mg/g and 108.1 mg/g for MIL-53-NH2@wool fabric composite, respectively after four regenerated cycles. The decrement in adsorption capacities by regeneration cycles was related to the decrement of MIL-53-NH2 MOF content onto fabrics due to its releasing out to the surrounding environment. The MOF contents were reduced from 185.0 mg/g and 234.5 mg/g to 95.6 – 103.4 mg/g and 141.7 – 145.0 mg/g after 4 regeneration cycles for MIL-53-NH2@cotton and MIL-53-NH2@wool fabric composites, respectively. The adsorption capacities were reduced by 28.8 – 40.9 % for MIL-53-NH2@cotton fabric composite and 19.2 – 32.0 % for MIL-53NH2@wool fabric composite, due to the reduction in MOF contents by percentage of 44.1 – 48.3 and 38.2 – 39.6, respectively. This proves the substantial durability of MIL-53-NH2@fabric composite against the regeneration process and consequently maximizing its efficient in the adsorption of nitrogenated compounds. From Figure 9, it was found that, the adsorption of nitrogenated compounds onto composites was linearly proportional with the contents of MOF. This confirms that, much higher adsorption capacities against nitrogenated compounds and/or higher regeneration cycles than 4 processes, could be both realized by incorporation higher contents of MIL-53-NH2 MOF within natural fabrics. The prepared MIL-53-NH2@fabric composites based on cotton and wool, are considered as highly adsorptive composites for



removal of nitrogenated compounds (indole and quinoline) from liquid fuel and capable of regeneration several times for achievement of high economic impact. …………..Figure 8………….. …………..Figure 9………….. Tentative mechanism of adsorption The adsorption of nitrogenated compounds on to the MIL-53-NH2@natural fabric composite was confirmed by FTIR spectra and results of adsorption capacities. The adsorption mechanism could be supposed in accordance with the adsorption data and chemical structures of reactants (indole, quinoline, MIL-53-NH2, cotton and wool), as presented in Figure 10. The composites contain many active sites represented in functional groups of MIL-53-NH2 MOF (Al, OH and NH2), cotton (OH) and wool (NH and OH), in addition to the porosity of MOF. Therefore, the nitrogenated compounds could be adsorbed onto the composite through the chemical interaction between the whole functional groups of composite and N- of indole or quinoline

70.

Hydrogen and/or coordination bonding as weak interactions may mostly take a

place 70. Moreover, physical deposition of nitrogenated compounds into the pores of MOF and/or fabric, may be carried out with minor relevant 27-28, 70. …………..Figure 10…………..

CONCLUSIONS: The MIL-53-NH2@fabric (cotton and wool) composites were designed through in-situ formation of MOF within fabric matrix. The designated composites were investigated by SEM, EDX, XRD and FTIR. The contents of MOF and Al onto fabrics were 185.0 mg/g and 22.4 mg/g for cotton, and 234.5 mg/g and 28.4 mg/g for wool, respectively. The fabric compositions played an important role in the nature of the incorporated MOF. The adsorption of indole and quinoline as nitrogenated compounds from the liquid fuel onto the designated composites was studied. The adsorption of nitrogenated compounds onto composites is fitted well to Langmuir isotherm and second order kinetic model. The maximum adsorption capacities of indole and quinoline were 125.0 mg/g and 87.7 mg/g onto cotton, 156.4 mg/g and 121.5 mg/g onto wool, 178.6 mg/g and 149.3 mg/g onto MIL-53-NH2@cotton fabric composite and 204.1 mg/g and 163.9 mg/g onto MIL-53-NH2@wool fabric composite, respectively. After 4 regeneration cycles, the adsorption 14 ACS Paragon Plus Environment

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capacities of composites were reduced by 28.8 – 40.9 % and 19.2 – 32.0 % for MIL-53NH2@cotton and MIL-53-NH2@wool fabric composites, respectively. The relation between the adsorption capacities and MOF/Al contents on fabrics was revealed to be as a linear relationship. According to these results, the designated Al based MOF@natural fabric composite could be successfully applicable in fuel purification from nitrogenated compounds. This composite is recyclable and subsequently, could be highly applicable as filter in purification of liquid fuel, and could be used several times with sufficient adsorption efficiency.

Compliance with ethical standards The authors declare that they have no competing financial interest

Supporting Information The manuscript includes supporting information file as supplementary data related to the current article. The file contains of magnification of FTIR spectra for untreated fabrics and MIL53-NH2@fabrics composite before and after adsorption of indole and quinoline, linearization fitting of second order kinetics, and effect of fabric dose on the adsorption capacity. References: (1) EPA-Diesel, R. Regulatory impact analysis: heavy-duty engine and vehicle standards and highway diesel fuel sulfur control requirements. United States Environmental Protection Agency, Air and Radiation EPA420-R-00-026 2000. (2) Song, C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catalysis today 2003, 86 (1-4), 211-263. (3) Zhou, Z.; Li, W.; Liu, J. Removal of Basic Nitrogen Compounds from Fuel Oil with [Hnmp] H2PO4 Ionic Liquid. Chemical and biochemical engineering quarterly 2017, 31 (1), 63-68. (4) Zhang, J.; Xu, J.; Qian, J.; Liu, L. Denitrogenation of straight-run diesel with complexing extraction. Petroleum Science and Technology 2013, 31 (8), 777-782. (5) Choi, J.; Gray, M. Identification of nitrogen compounds and amides from spent hydroprocessing catalyst. Fuel Processing Technology 1991, 28 (1), 77-93. (6) Oliveira, E. C.; de Campos, M. C. l. V.; Lopes, A. S. A.; Vale, M. G. R.; Caramão, E. B. Ion-exchange resins in the isolation of nitrogen compounds from petroleum residues. Journal of Chromatography A 2004, 1027 (1-2), 171-177. (7) Yu, H.; Li, S.; Jin, G. Hydrodesulfurization and hydrodenitrogenation of diesel distillate from Fushun shale oil. Oil Shale 2010, 27 (2), 126.



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List of Tables Table 1: Contents of MOF/Al and color data for MIL-53-NH2@fabric composite

Fabric/Composite

MOF Content (mg/g)

Al Content (mg/g)

L*

a*

b*

K/S

Cotton

0.0

0.0

84.02 ± 1.92

-0.14 ± 0.21

0.25 ± 0.11

0.03 ± 0.02

Wool

0.0

0.0

81.59 ± 2.18

-6.69 ± 1.03

24.37 ± 2.24

0.03 ± 0.02

MIL-53-NH2@Cotton

185.0 ± 6.2

22.4 ± 1.2

80.37 ± 1.55

-0.98 ± 0.15

7.84 ± 1.04

0.11 ± 0.06

MIL-53-NH2@Wool

234.5 ± 8.7

28.4 ± 1.4

76.31 ± 1.92

-9.02 ± 1.40

36.45 ± 3.88

0.65 ± 0.11


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Table 2: Kinetics and isotherm parameters for adsorption of nitrogenated compounds onto untreated and MIL-53-NH2@fabric composite.

Kinetics parameters N-compounds

Fabric/Composite

Isotherm parameters

K2 x 10-4 (g/mg min)

R2

Qmax (mg/g)

KL x 10-4 (mg/L)

R2

Cotton

85.6

0.983

125.0

58.1

0.983

Wool

124.2

0.990

156.4

59.6

0.990

MIL-53 -NH2@Cotton

229.8

0.992

178.6

117.8

0.974

MIL-53-NH2@Wool

311.1

0.998

204.1

182.6

0.967

Cotton

146.4

0.989

87.7

56.5

0.994

Wool

234.2

0.982

121.5

53.8

0.994

MIL-53-NH2@Cotton

227.2

0.991

149.3

94.7

0.995

MIL-53-NH2@Wool

264.8

0.999

163.9

118.2

0.982

Indole

Quinoline



Page 22 of 36

Table 3: Maximum uptake (qmax) of nitrogenated compounds onto different adsorptive materials reported in literature. Adsorbent

Nitrogenated compound

Maximum adsorption capacity (mg/g)

Reference

MIL-53-NH2@natural fabric composite

Indole

178.6 – 204.1

Current study

Aluminum silicate

Indole

14.1

13

Activated alumina

Indole

44.5

23

Activated carbon

Indole

194.6

73

Cu-BTC

Indole

220

72

MIL-101(Cr)

Indole

194

71

UiO-66(Zr)-SO3H

indole

239

72

MIL-100 and MIL-101

Indole

360 - 420

13, 71, 74

MIL-53-NH2@natural fabric composite

Quinoline

149.3 – 163.9

Current study

Activated alumina

Quinoline

49.1

23

Activated carbon

Quinoline

162.8

71

MIL-101

Quinoline

336-498

13, 71, 74


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List of Figures Figure captions Figure 1: Scheme represents the formation mechanism of MIL-53-NH2@natural fabrics [a] Cotton and [b] Wool. Figure 2: Micrographs and EDX analysis for MIL-53-NH2@fabrics composite at different magnification; [a] Cotton and [b] Wool. Figure 3: XRD spectra for untreated fabrics, MIL-53-NH2 and MIL-53-NH2@fabrics composite; [a] Cotton and [b] Wool. Figure 4: FTIR spectra for untreated fabrics, MIL-53-NH2 and MIL-53-NH2@fabrics composite; [a] Cotton and [b] Wool. Figure 5: FTIR spectra for MIL-53-NH2@fabrics composite before and after adsorption of indole and quinoline; [a] Cotton and [b] Wool. Figure 6: Effect of contact time on adsorption capacity of nitrogenated compounds onto fabrics and MIL-53-NH2@fabrics composite [a] Indole and [b] Quinoline. Figure 7: Isotherm profiles for adsorption of nitrogenated compounds onto untreated fabrics and MIL-53-NH2@fabrics composite; [a, b] Cotton, [b] Wool [a, c] Indole and [b, d] Quinoline. Figure 8: Effect of regeneration process on the efficiency of reusable MIL-53-NH2@fabrics composite for the removal of nitrogenated compounds; [a] Indole and [b] Quinoline. Figure 9: The relationship between MOF contents onto MIL-53-NH2@fabrics composite and the adsorption capacities of nitrogenated compounds. Figure 10: Representative scheme describes the intermolecular interactions between nitrogenated compounds and MIL-53-NH2@fabrics composite during the adsorption process; [a] Cotton and [b] Wool.



Page 24 of 36

Figure 1 [a]

[b]

R OH

HO HO

O

O HO

O OH O

O

Cotton

OH

n

OH H N

H N

O

O

O

HO

O

R Wool

O

HO

N H

O

O N H

R

AlCl3

O

O

Al

Al

O

O NH2

O

H N

COOH H N

O

H N

N H

O

H O

N H

O

O

H N

R

NH2 H N

AlCl3

O

O

H N

N H

O

S H

R

S

N H HO

HN O

O

H N

OH

O

O HO

O

O HO

O

O H O

O

R

OH n

H N

HN O

O

H N

R N H

O

O

O

O Al S H N O


O N H

O

R

N H

H N O

H 2N

O Al

O

O O

O

O O

H N O

R N H

H2N

S

N H

O

H N

O

H N O

R

N H

Page 25 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 2

[a]



[b]


Page 26 of 36

Page 27 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 3 [a]

MIL-53-NH2@Cotton

Cotton

MIL-53-NH2 5

10

15

20

25

30

35

40

45

50

2 Theta degree

[b]

MIL-53-NH2@Wool

Wool

MIL-53-NH2 5

10

15

20

25

30

35

2 Theta degree


40

45

50


Page 28 of 36

Figure 4: [a]

MIL-53-NH2@Cotton

Cotton

MIL-53-NH2 4000

3500

3000

2500

2000

1500

1000

500

1000

500

-1

Wavenumber (cm ) [b]

MIL-53-NH2@Wool

Wool

MIL-53-NH2 4000

3500

3000

2500

2000

1500 -1

Wavenumber (cm ) 28 ACS Paragon Plus Environment

Page 29 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 5: [a]

MIL-53-NH2@Cotton@Qinoline

MIL-53-NH2@Cotton@Indole

MIL-53-NH2@Cotton 4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm ) [b]

MIL-53-NH2@Wool@Quinoline

MIL-53-NH2@Wool@Indole

MIL-53-NH2@Wool

4000

3500

3000

2500

2000

1500 -1

Wavenumber (cm ) 29 ACS Paragon Plus Environment

1000

500


Figure 6:

[a] 100

Indole

% indole uptake

80

60

40

Cotton MIL-3-NH2@Cotton

20

Wool MIL-3-NH2@Wool

0 0

5

10

15

20

25

Time (hours)

[b]

100

Quinoline 80

% quinoline uptake

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 36

60

40


20

Wool MIL-3-NH2@Wool

0 0

5

10

15

Time (hours)


20

25

Page 31 of 36

Figure 7 180

[b]

160

Indole

160

140

140

120

Q e (mg/g)

Q e (mg/g)

120 100 80 60

20

100 80 60

20


0 0

500

1000

1500

2000

2500


0

3000

0

Ce (mg/L)

200

Quinoline

40

40

500

1000

1500

2000

2500

3000

Ce (mg/L)

[d]

Indole

180 160

Quinoline

140

150

120

Q e (mg/g)

Q e (mg/g)

1 2 3 4 5 [a] 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 [c] 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


100

100 80 60

50

40

Wool MIL-53-NH2@Wool

0 0

500

1000

1500

2000

2500

20

Wool MIL-53-NH2@Wool

0

3000

0

Ce (mg/L)

500

1000

1500

Ce (mg/L)


2000

2500

3000

3500


Figure 8 [a] 225

) orbed (mg/g Amount ads

200 175 150 125 100 75 50 25 0 1

MIL-53-NH2@Wool

2

N

es cl cy of

MIL-53-NH2@Cotton

4

r be

3

um

[b]

175

rbed (mg/g) Amount adso

150 125 100 75 50 25 0 1

Nu mb er of cyc les

MIL-53-NH2@Wool

2

MIL-53-NH2@Cotton 4

3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 36


Page 33 of 36

Figure 9

220

Indole Quinoline

200

Adsorption capacity (mg/g)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


180 160 140 120 100 80 80

100

120

140

160

180

200

MOFs content (mg/g)


220

240


Page 34 of 36

Figure 10 [a] H H N

O

O

O

O

O

O

Al

Al O

O HO

O

O HO

O

O

O

H O

OH n

N H N H

N H

H

O

O

O

O

O

O

O

O

O

O

O H O H N

O

O

O O

O

O H O

OH

HO

O

O HO

O

O

Al

O

HO

O

O

Al

Al

Al

O HO

H N

N

H N

n


O O H N

n

Page 35 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


[b] R N H

O

H N

N H

O H2N O

O Al N

R

O

R

N H

O

H2N

O Al O

O O

O

H N

O O

H N

H N

O

H N O

R

N H

NH2

NH2 R N H

O

H N

R N H

O N O

O Al

O

R

N H

NH

N H

O

O

O

H N R

H N

O

O

O

Al

R N H

R


O

O Al O

O

O

O

N H

O

O

O

H N

H N

N

H N

H H N O

O O

H N

N H

O

H N O

O Al O

O O

H N

O H

R

H N

R

N H

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

ACS Paragon Plus Environment

Page 36 of 36

Applicable Strategy for Removing Liquid Fuel ... - ACS Publications

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