Electronic Supplementary Information (ESI)
Quantitative relationship model between support properties and dibenzothiophenehydrodesulfurization conversionover NiMo/Al2O3
Xiuna Liu1, Shaoyang Jiang2, Weikun Lai1,*, Xiaodong Yi1, Lefu Yang1,Weiping Fang1
1National Engineering Laboratory for Green Chemical Productions of Alcohols-ethers-esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
2SINOPEC Catalyst CO LTD, Beijing 100029, China
HRTEM imagesof NiMoS active phase
Fig. S1HRTEM images of the sulfidedNiMo-x/Al2O3 catalysts.
Table S1 Statistical analysis of MoS2 slabs over sulfidedNiMo-x/Al2O3 catalysts.
Catalyst / (nm) / / f MoNiMo-0 / 3.7 / 2.5 / 0.288
NiMo-1h / 3.8 / 2.5 / 0.283
NiMo-2h / 3.4 / 2.1 / 0.292
NiMo-4h / 3.1 / 2.3 / 0.315
NiMo-10h / 3.9 / 2.7 / 0.261
NiMo-15h / 4.1 / 2.9 / 0.246
NiMo-24h / 4.5 / 3.2 / 0.219
: Average slab length of the MoS2 crystals.
: Average number of layers of the MoS2 crystals.
fMo: Fraction of Mo atoms on the edge of MoS2 crystals.
Compared with conventional analytic method
Fig. S2Relationship between theDBT HDS conversion and the surface area of supports.
Model applied to the NiMo catalysts with different metal loading
In order to make sure that this approach not only be worked for this series of catalysts but also can be worked for other samples. We have prepared a series of NiMo catalysts with different metal loading by wet co-impregnation method with aqueous solutions of ammonium heptamolybdate and nickel nitrate.In addition,statistical results of the MoS2dispersion by TEM measurements and the activity of DBT HDS reaction over the NiMo-x catalysts have been provided in Table S2.In present study, NiO loading (N), MoO3 loading (M) and dispersion of the MoS2 slabs (f) properties of the catalysts will be considered.
According to Eq. (21) (Page 12), we have
(S-1)
Using the model to fit the experimental data(listed in Table S2) and the fitting results are listed in Table S3.The results show that the model satisfactorily predictsthe experimental data with theaverage relative deviation (ARD) of 2.42%，which reveal its applicability of the model.
The model validity was verified by various catalyst samples in DBT HDS reaction. It provides a new way to predict the activities of HDS catalysts and contributes to understand the influence rule of support’s properties, since it is unable to only change one property variable of the support and make other variables unchanged. It would be significant in researching and producing hydrotreating catalyst.
Table S2Thedispersion of MoS2 slabs by TEM measurements and the DBT HDS activity.
Catalysts / Cat-1 / Cat-2 / Cat-3 / Cat-4 / Cat-5 / Cat-6NiO (%) / 1 / 2 / 3 / 3 / 3 / 3
MoO3 (%) / 12 / 12 / 12 / 8 / 10 / 14
f(Mo) / 0.297 / 0.278 / 0.257 / 0.268 / 0.281 / 0.265
Xexp / 0.394 / 0.776 / 0.882 / 0.821 / 0.846 / 0.889
Table S3Calculation parameters of the model.
Parameters / Value / Parameters / Value / Parameters / ValueαN / 1.230 / αM / 0.506 / αf / -0.384
A0 / 2.218 / ARD(%) / 2.42
Model applied to the NiMo-0 catalyst with different operating conditions
The NiMo-0 catalyst has been tested at different operating conditions. The activity of DBT HDS has been provided in Table S4.
According to Eq. (4) (Page 8),we can get the relative forms of different operating conditions variables
(S-2)
in which is relative reaction temperature, is relative reaction pressure and denotes relative liquid hourly space velocity. Eq. (S-2) can be rearranged as
(S-3)
Eq. (S-3) was used to fit the experimental data tested at different operating conditions. As shown in Table S5, the average relative deviation is 2.56 %, which indicate the validity of the presented model applied to different reaction conditions.
According to Eq. (S-2), we get
(S-4)
Depending on Eq. (S-4), a plot of [] versus () is shown in Fig. S3,the experimental curves were approximately linear with correlation coefficients of 0.985. It can be seen that k0 can be obtained as a slope and does not change under different operating conditions for fixed catalyst.
Table S4TheDBT HDS activity at different operating conditions.
T (oC) / P (MPa) / LHSV (h-1) / Xexp (%)260 / 2 / 20 / 44.3
270 / 2 / 20 / 54.8
280 / 2 / 20 / 66.4
290 / 2 / 20 / 78.1
300 / 2 / 20 / 84.8
300 / 2 / 10 / 89.6
300 / 2 / 30 / 81.8
300 / 2 / 40 / 68.1
300 / 1.5 / 20 / 83.6
300 / 1 / 20 / 80.6
300 / 0.7 / 20 / 75.7
300 / 0.3 / 20 / 63.5
Table S5Calculation parameters of the model
Parameters / Value / Parameters / Valuenp / 0.290 / nv / -0.451
Ea / 35.5 KJ.mol-1 / ARD(%) / 2.56
Fig. S3 Relationship between the DBT HDS conversion and different reaction conditions.