1. Introduction
With the world’s light oil reserves decreasing, the conversion of unconventional oil products, such as coal tar and heavy oil, into clean fuel oil has received increasing attention from researchers. The hydrofining of coal tar to produce light fuel oil is of great practical and strategic significance to replace certain petroleum resources. However, coal tar is rich in polycyclic aromatic hydrocarbons, colloids, asphalts, and a large number of impurity elements, such as metals, sulfur, and nitrogen, which can cause a negative effect on the further utilization of coal tar [
1,
2,
3]. In particular, the presence of nitrogen compounds in car tar not only produces NOx pollutants during the combustion process, but also deactivates the catalysts of the hydrocracking or hydrorefining process. Hench, nitrogen compounds in car tar must be removed by hydrodenitrogenation (HDN) reaction, and developing efficient hydrogenation catalysts is one of the key technologies for the HDN of coal tar [
4,
5,
6,
7,
8,
9].
Currently, scientists have made many attempts to prepare high performance catalysts, including the application of different active phases and various supports. The traditional hydrogenation catalysts supported molybdenum sulfide or tungsten sulfide with a Ni (Co) atom as the promoter are extensively applied in industry. NiW, as the active phase of catalysts, has excellent catalytic activity on the HDN performances, especially under harsh reaction conditions with higher hydrogen pressure and temperature [
10,
11,
12,
13,
14,
15]. Generally, γ-Al
2O
3 has been widely used as a conventional support of HDN catalysts due to its excellent mechanical performances, low price, and high thermal and hydrothermal stability [
3,
16]. However, the small surface area and single Lewis acid site distribution restrict the hydrogenation activity [
17,
18,
19]. Thus, modifications of γ-Al
2O
3 with fluorine or phosphorus have been conducted by researchers [
3,
10,
20]. For example, Shi et al. modified γ-Al
2O
3 with phosphorus and demonstrated that the addition of phosphorus could alter the acid site distributions and improve the HDN catalytic performance to an extent. However, the highest HDN conversion was only 74.36%, which cannot meet the need of commercial application [
20]. Guo et al. modified γ-Al
2O
3 with fluorine and found that the addition of fluoride decreased the specific surface area of the catalyst, which cannot significantly improve the HDN activity [
3].
To further improve the catalytic performance, the development of advanced supports for the HDN catalysts became a focus of scientific research. Certain mesoporous materials, such as MCM-48, SBA-15, and FDU-12, with orderly mesoporous structures, large specific surface areas, and uniform pore sizes, became a research hotspot of the catalyst supports [
21,
22,
23,
24,
25,
26,
27]. In particular, they showed potential for HDN catalytic reactions. However, weak acids limit the HDN activity to an extent.
Studies have shown that heteroatom introduction, including Zr
4+, Ti
4+, and Al
3+, can improve the acidity properties of a catalyst, which will promote the dispersion of active metals [
4,
28,
29,
30,
31,
32,
33,
34]. For example, Shao et al. prepared Al-modified MCM-48 supports for the NiW catalyst in the hydrodenitrogenation (HDN) reaction of quinoline and the activity results showed that Al-modified NiW/MCM-48 catalysts displayed higher HDN activity than aluminum free NiW/MCM-48, since the introduction of suitable aluminum atoms enhanced the acidity of the support and, hence, improved the sulfidation degree of the catalyst [
27].
As a novel mesoporous molecular sieve, KIT-5 can be a candidate for the support of HDN catalysts because it possesses an excellent face-centered-cubic
Fm3m symmetry structure with a large specific surface area and adjustable pore diameter [
22,
23,
24]. However, its weak acidity does not favor the HDN reaction. Thus, the aluminum atoms should be introduced to the KIT-5 material to improve its acidity and HDN activity [
35,
36,
37,
38].
In this study, a series of Al-modified KIT-5 supports with different silicon-aluminum ratios (10, 40, 80, and 200) as well as the pure KIT-5 supports were successfully fabricated by the one-step direct hydrothermal method. In addition, the corresponding NiW/Al-KT-X catalysts were synthesized with the incipient impregnation method. The catalysts were characterized by X-ray diffraction (XRD), N2 absorption−desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Pyridine-Fourier transform infrared spectroscopy (Py-IR), and X-ray photoelectron spectra (XPS). The HDN activity of the catalysts was evaluated in a fixed bed with quinoline as the reactant under different reaction conditions.
3. Discussion
The results of the hydrodenitrification of quinoline demonstrated that the introduction of aluminum atoms into KIT-5 had a positive influence on the HDN activity of catalysts. According to a series of characterization results mentioned above, the HDN activities of catalysts had a close relation with the structural characteristics of the supports, acidities of the catalysts, sulfidation degree of active species, and the structure of active phases [
37,
57,
58].
The pore structural properties greatly affected the dispersion of active metals and the molecular diffusion behavior in a channel [
21]. The modified Al-KT-X supports still maintained the relatively orderly mesoporous channels. The specific surface area, pore volume, and pore diameter increased when aluminum atoms were introduced into the KIT-5 framework, leading to more active sites of the catalysts and higher catalytic activity. All Al-modified catalysts exhibited a higher HDN activity than the pure NiW/KIT-5 catalyst. This was due to the large pore size, pore volume, and highly specific surface area of Al-modified catalysts, which promoted the transfer of reactants and products and reduced the diffusion resistance remarkably [
4].
Similarly, the acid amount of the catalysts is of great importance for catalytic activity and product selectivity [
32,
59,
60]. The acid amount of various catalysts first increased and then decreased with increasing aluminum. The NiW/Al-KT-40 catalyst possessed the highest acid amount and the highest hydrodenitrogenation activity, indicating that the acid sites were favorable for the improvement of the HDN activity of the catalyst.
In addition, the structure of the active phase catalysts had a significant impact on the catalytic activity, which is closely connected with the dispersion of WS
2 particles and the interaction between metal species and supports [
27,
59,
60]. With the increase of the aluminum content in the catalysts, the sulfidation degree increased first and then decreased, and this indicates that an appropriate aluminum content can promote the interaction between the active metal and support leading to a deeper sulfidation for the catalyst, which improves the HDN catalytic activity.
4. Materials and Methods
4.1. Materials
We used hydrochloric acid (HCl; Kemio, Tianjin, China; 36–38%), sodium aluminate (NaAlO2; Kemio, Tianjin, China; 98%), tetraethylorthosilicate (TEOS; Aldrich, Shanghai, China; 98%), poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (F127; MW = 12,600; EO106EO70EO106; Aldrich, Shanghai, China), nickel nitrate hexahydrate (Tianjin Shentai chemical factory 98%), ammonium paratungstate (Kemio; Tianjin, China; 98%), carbon disulfide (CS2; Merck, Beijing, China; 99%), quinoline (Kemio, Tianjin, China; 99%), cyclohexane (Merck, Beijing, China; 99%), and decalin (Kemio, Tianjin, China; 98%).
4.2. Catalyst Synthesis
The pure KIT-5 support was prepared following the procedure reported in the literature [
35]. Typically, 5.0 g of F127 was dissolved in 250 mL of 0.5 M hydrochloric acid with vigorous stirring for 24 h at 45 °C; next, 25.0 g of TEOS was added into the mixture drop by drop and stirred constantly at 45 °C for 24 h. Afterward, the reaction solution was transferred into a Teflon-lined stainless steel autoclave and heated at 100 °C for 24 h. After the hydrothermal reaction was completed, the solution was cooled down to room temperature. The obtained sample was collected by filtering, drying in air at 100 °C for 12 h and calcining at 550 °C (1 °C min
−1) for 6 h for removal of the template.
The Al-KT-X (X represents Si/Al molar ratios of 10, 40, 80, and 200, respectively) samples were synthesized with aluminum isopropoxide as aluminum source. First, 25.0 g TEOS and 5.0 g F127 were added to 250 mL of 0.5 M HCL and stirred continuously to form the white suspension. Next, different amounts of the aluminum source were added into the above solution under stirring for 12 h at the same temperature. Subsequently, the solution was transferred into the autoclave for 24 h at 100 °C. Finally, the as-synthesized materials were obtained by filtering, drying, and calcining.
The corresponding NiW/Al-KT-X catalysts and NiW/KIT-5 were prepared using the one-step incipient impregnation method. Nickel nitrate hexahydrate and ammonium paratungstate were used as Ni and W sources for the catalysts, respectively. The loading of 35.0 wt% WO3 and 4.2 wt% NiO were impregnated on the support overnight. After impregnation, each sample was dried at 100 °C for 12 h in an oven and calcined for 6 h at 550 °C (2 °C min−1) in the muffle furnace. The catalysts obtained were denoted as NiW/Al-KT-10, NiW/Al-KT-40, NiW/Al-KT-80, NiW/Al-KT-200, and NiW/KIT-5.
Prior to the catalytic reaction, the catalyst was activated by sulphidation in situ with the 3 wt% CS2 solution (cyclohexane as the solvent) at a flow rate of 2.4 mL h−1 under a pressure of 3.8 MPa and a temperature of 150 °C for 4 h. Then, the temperature was increased to 350 °C with a heating rate of 1 °C min−1 and held for 12 h at 350 °C. The sulfide catalysts were characterized to study their physical and chemical properties.
4.3. X-ray Diffraction
Powder X-ray diffraction (XRD) patterns of the samples were analyzed on a Rigaku MiniFlexII X-ray diffractometer Buker with Cu Kα (λ = 0.1541 nm) radiation with a step of 0.002° s−1 over a range of 0.5–3.0° (2θ) for the supports and 2° s−1 over a range of 5–90° (2θ) for the oxide precursors.
4.4. N2 Physisorption
With the Tristar-3020 Micrometrics volumetric apparatus, the nitrogen physisorption isotherms were tested. The total specific surface area was calculated by the standard Brunauer–Emmett–Teller (BET) method. The pore distribution derived from the absorption branch were obtained by the Barett–Joyner–Halenda (BJH) method, and the pore volume was acquired by pore size distribution curves.
4.5. Fourier Transform Infrared (FTIR) and Py-IR
Fourier transform infrared (FTIR) spectra of the supports were analyzed at a resolution of 2 cm
−1 in the range of 400–4000 cm
−1 using the Thermos Fisher Scientific Nicolet-380 instrument. Brønsted and Lewis acid distribution of the oxide precursors catalysts were performed by an FTIR spectrometer using pyridine as a probe molecule. The Py-IR investigation was conducted at different desorbed temperatures (100, 200, and 300 °C), The pyridine adsorption infrared (Py-IR) spectra were recorded at 100, 200, and 300 °C reflecting weak acid, medium acid, and strong acid, respectively [
28].
4.6. Scanning Electron Microscopy
The morphologies of all the samples were studied using scanning electron microscopy (SEM) on a JSM-7900 F apparatus. Additionally, the surface element contents of the materials were measured by the SEM equipped with energy dispersive spectroscopy (EDS).
4.7. High Resolution Transmission Electron Microscopy
The WS2 morphologies over the sulfide catalysts were observed through the high resolution transmission electron microscopy (HRTEM) on a JEOL (JEM-2100F, Tokyo, Japan). The corresponding samples were evenly dispersed in the ethanol solution and dropped on the ultra-thin carbon supporting film. Subsequently, the samples were naturally dried.
We used the following formulas to calculate the average slab number of stacks (
) and average length (
) of WS
2 stacking layers [
5,
8,
11]:
where n
i, N
i, and L
i represent the number of slabs, stacking layers of a WS
2 unit and the slab length of the WS
2 unit, respectively
4.8. X-ray Photoelectron Spectroscopy
Prior to the X-ray photoelectron spectroscopy (XPS) analysis, all the sulfide catalysts were ground into powder in an Ar-filled glovebox and stored in a sealed bag to avoid reoxidation. Then, the sample was transferred to the chamber of the XPS instrument without exposure to air. The XPS spectra were obtained with a Thermo Escalab 250Xi spectrometer equipped with an Al Kα source (1486.6 eV), operating at 15.0 kV and 8.6 mA. The operating pressure inside the analysis chamber was below 1.0 × 10
−7 Pa. Using the Al 2p band at 76.4 ev as a standard, the peak shift was corrected [
5,
61].
4.9. Catalytic Activity Evaluation
The HDN activities of the series NiW/Al-KT-X and NiW/KIT-5 catalysts were evaluated in a fixed-bed reactor with a feed of quinolone (Q) in decalin (0.5 wt% N). One gram of fresh catalyst of 20–40 mesh size was loaded into the stainless steel reaction tube. After sulphidation, the hydrodenitrogenation reaction was carried out under the pressure of 3.8 MPa with a H2/oil of 1250 mL/mL, and a constant weight hourly space velocity (WHSV) of 3 h−1. The reaction temperatures were 340–380 °C. All reaction products were collected by the condensing system at 12–24 h reaction time and analyzed. The nitrogen compounds in the products were qualitatively analyzed using a Agilent-7890A GC–MS equipped with a capillary column (HP-5MS). The nitrogen contents in the samples were quantitatively analyzed using a GC equipped with a flame ionization detector (FID) and a HP-5 column using an internal standard method. All the experiments were preformed two or three times with good repeatability.
The hydrogenation reaction network of quinoline has two pathways in
Figure 12: the pathway(I) is Q → 1,2,3,4-tetrahydroquinoline (THQ1) → ortho-propylaniline (OPA) → propylbenzene (PB), and the other pathway(II) is Q → decahydroquinoline (DHQ) → 2-propyl-cyclohexylamine (PCHA) → propyl-cyclohexene (PCHE) + propyl-cyclohexane (PCH). Generally, the hydrodenitrogenation conversion (HDN
C) of each catalyst was calculated using the following equation [
53,
54,
55]:
in which the Q, PB, PCH, and PCHE concentrations collected in the products are defined as n
Q, n
PB, n
PCH, and n
PCHE, respectively.
represents the sum of all product concentrations obtained from quinoline, including PB, THQ5, OPA, PCH, DHQ, THQ1, PCHE, and PCHA.
The reaction rates (r
HDN) and the rate constants (k) of the series of catalysts for quinoline denitrogenation were calculated by the following formulas based on the pseudo first-order kinetics [
61,
62,
63]:
where r
HDN represents the reaction rate (mol s
−1 g
−1), k represents the rate constant (s
−1), C
A and C
A0 are the concentration of quinoline (mol L
−1) in the product and feed, V
R represents the volume of catalysts (L), and F
A0 stands for the molar flow rate of quinoline (mol s
−1).
5. Conclusions
A series of Al-KT-X and KIT-5 materials were successfully synthesized using the direct hydrothermal method, and they supported the NiW active phases for the quinoline hydrodenitrification reaction. All supports and catalysts were characterized by XRD, N2 isotherm absorption–desorption, FTIR, Py-IR, and SEM, and the series of sulfide catalysts were characterized by HRTEM and XPS. The results showed that the addition of aluminum atoms did not destroy the orderly mesoporous structure of KIT-5 and exhibited a larger pore size, pore volume, and specific surface area. Among all the Al-modified supports, the Al-KT-40 support possessed a suitable surface area (1057.15 m2g−1), pore volume (0.64 cm3·g−1), and orderly 3D channel (5.43 nm). The addition of aluminum atoms into the framework of KIT-5 resulted in an increase of acid sites and a good distribution of active phases. Overall, the modified NiW/Al-KT-X catalysts were superior in activity compared with the pure NiW/KIT-5 catalyst, which was attributed to the large pores, more acidic sites, and more sulfided active metals. The NiW/Al-KT-40 catalysts exhibited the highest HDNc of 95.14% at 380 °C.