Page 97 - AJWEP-22-6

Adsorption desulfurization

to ammonium ion. The NH Y-zeolite was obtained based on adsorption data in the relative pressure range
4
from Wako, Japan (SiO /Al O = 7.0), whereas all from 0.0000165 to 0.1546. The pore width and volume
3
2
2
metal salts—RuCl ∙xH O (37.5% Ru), ZrOCl ∙8H O were also calculated using the HK method. Hydrogen
2
2
3
2
(99%), SbCl 99%), and Bi(NO ) ∙5H O (99%)—were temperature-programmed reduction (H -TPR) of the
2
3 3
2
3 (
purchased from Sinopharm Group Chemical Reagent adsorbents was measured by a Micromeritics AutoChem
(China). The hydrogen-form Y-zeolite (HY sample) was 2920 analyzer (Micromeritics Instrument Co., LTD,
prepared by calcining the NH Y-zeolite at 500°C for 2 h USA). The adsorbents were swiped at 300°C for 30 min
4
in air. under helium flow (10 mL/min) and then cooled to 40°C
before being reacted with H . The profile was recorded
2
2.2. Adsorption experiment by increasing the temperature from 100°C to 800°C at a
Adsorption experiments were performed using a batch ramp rate of 10°C/min.
method. A model gasoline solution was prepared Temperature-programmed desorption of ammonia
consisting of n-heptane (99 wt%), toluene (1 wt%), (NH -TPD) was used to calculate the intensity and
3
and TP (20 ppmw of sulfur). N-heptane (98.5%), number of acidic sites in the adsorbents. This was
TP (99%), and toluene (99%) were purchased from conducted using a TP-5080 automatic analyzer (Tianjin
Sinopharm Group Chemical Reagent (China). The Xianquan Instrument Co., LTD, China). About 0.1 g of
model gasoline (10 mL) and the adsorbent (0.1 g) were adsorbent was placed in a U-shaped quartz microreactor.
mixed in a Teflon tube, and the mixture was stirred at The adsorbent was activated at 550°C for 30 min
80°C. After adsorption, the sulfur concentration in the under helium flow (20 mL/min), cooled to 100°C, then
liquid phase was analyzed using a gas chromatograph exposed to ammonia. The adsorbents were flushed again
with a flame ionization detector (GC-FID; Agilent in helium for 3 h to remove any physisorbed ammonia.
7890, Agilent Technologies Co., LTD., USA) equipped A desorption profile was then recorded by increasing
with a capillary column (Thermo TG-WAXMS; USA; the adsorbent temperature from 100°C to 800°C at a
30 m × 0.53 mm × 1 µm). ramp rate of 10°C/min.
The adsorption capacity (q ) and sulfur removal The pyridine-Fourier transform infrared (Py-FTIR)
e
efficiency were calculated using Equations I and II. was used to analyze the amount and type of acidic sites,
with pyridine as the probe molecule. Measurements
0
qe VC ( Ci) (I) were conducted using an FTIR spectrometer (Tensor 27,
m BRUKER Technology Co., LTD, USA). Transmission

(C0 Ci ) electron microscopy (TEM) imaging was performed on
Sulfur removal % 100 (II) a FEI Tecnai F20 system (FEI Co., LTD, USA) operated
C0
at an accelerating voltage of 200 kV. The size and
where V (mL) is the volume of model gasoline; C and morphology of the adsorbents were observed by using
0
C (mg/L) are the concentrations of sulfur in the model field emission scanning electron microscopy (FE-SEM)
i
gasoline before and after adsorption, respectively; and (Hitachi s-4800, Hitachi, Japan).
m (g) is the mass of adsorbents.
3. Results and discussion
2.3. Adsorbent characterization
The powder X-ray diffraction (XRD) patterns were 3.1. Adsorbent characterization
performed on a PANalytical Empyrean diffractometer 3.1.1 XRD analysis of adsorbents
(PANalytical B.V., Holland) operated at 40 kV XRD patterns of the MY-1 adsorbents and NH Y-zeolite
4
and 40 mA, using copper K-alpha radiation. X-ray are shown in Figure 1. Both adsorbents maintained the
photoelectron spectroscopy (XPS) analysis was carried characteristic framework structure of NH Y-zeolite
4
out using a THS-103X spectrometer (Thermo Fisher framework, although a reduction in the intensity of some
Scientific, USA) equipped with an aluminum K-alpha diffraction peaks was observed for the MY-1 samples.
X-ray source (photon energy, hv = 1486.6 eV). The This decrease is attributed to partial lattice collapse
nitrogen (N ) adsorption-desorption isotherms were following calcination treatment. In addition to the
2
measured on a 3H-2000PM2 system (Tianjin Xianquan typical diffraction peaks of NH Y-zeolite, the BiY-1,
4
Instrument Co., LTD, China) at –196°C. The adsorbents ZrY-1, and RuY-1 samples exhibited the additional
were degassed at 300°C for 5 h. The Horvath–Kawazoe peaks corresponding to the oxide phases of the
(HK) method was used to calculate the surface area, incorporated metals. Specifically, diffraction peaks for

Volume 22 Issue 6 (2025) 91 doi: 10.36922/AJWEP025250204