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Article

Tailoring NiMo-Based Catalysts for Production of Low-Viscosity Sustainable Hydrocarbon Bases for Drilling Muds from Secondary Gas Oils

by
Aleksei Iusovskii
,
Roman Boldushevskii
,
Aleksandr Mozhaev
,
Olga Shmelkova
,
Elizaveta Pavlycheva
,
Aleksandr Koklyukhin
and
Pavel Nikulshin
*
All-Russia Research Institute of Oil Refining, 6/1 Aviamotornaya St., 111116 Moscow, Russia
*
Author to whom correspondence should be addressed.
Energies 2023, 16(16), 5859; https://doi.org/10.3390/en16165859
Submission received: 27 June 2023 / Revised: 18 July 2023 / Accepted: 3 August 2023 / Published: 8 August 2023
(This article belongs to the Special Issue High Value-Added Utilization of Fossil Fuels)
Browse Figures
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Abstract

:
This article presents the prospect of using the process of deep hydrodesulfurization and hydrodearomatization of secondary gas oils using highly active NiMo catalysts to obtain hydrocarbon bases for drilling fluids. Catalysts were synthesized using PMo heteropolyanions, citric acid, and diethylene glycol on alumina carriers with different pore volumes. This study showed that the concentration of the impregnating solution affects the composition and morphology of the active phase particles of the prepared catalyst, while the textural characteristics of the carrier influence the physicochemical properties and catalytic activity of the NiMo/Al2O3 catalysts. The catalyst that was synthesized using a carrier with the largest pore volume and an effective diameter of more than 7 nm exhibited the highest activity. It was demonstrated that the use of such a catalyst allows for the procurement of hydrocarbon bases for drilling fluids from mixtures of secondary gas oils at a hydrogen pressure of 15–20 MPa. This study has practical significance for the development of sustainable and economically efficient methods for the utilization of low-quality petroleum gas oils to produce high-margin environmentally friendly non-fuel petroleum products, as well as contributes to the development of economically efficient technologies for the utilization of petroleum raw materials.

1. Introduction

Drilling fluids, which are complex colloidal systems, play a crucial role in drilling efficiency pertaining to rock removal, drill bit cooling, wellbore stability, and equipment protection [1,2,3,4]. These fluids, known as drilling muds, consist of a continuous liquid phase called the base fluid, which is modified with dispersed or weighed chemical additives to enhance and optimize their properties [5]. Depending on the physical state of the components, drilling fluids can exhibit characteristics of suspensions, colloidal dispersions, or emulsions [6,7].
The International Association of Oil and Gas Producers classifies drilling fluid systems into two main types: water-based drilling fluids (WBDFs) and non-aqueous-based drilling fluids (NABFs) [5]. WBDFs are the most widely used and cost-effective, while NABFs have an oil or synthetic permanent liquid phase with brine as the dispersed phase. Another classification by Caenn R. et al. [8] introduces a third group of drilling fluids based on natural gas or air with blowing agents.
NABFs are further categorized into three groups based on the content of aromatic and polycyclic aromatic hydrocarbons. Group I NABFs have a high aromatic content (>5 wt%) and PAH concentrations exceeding 0.35 wt%. Group II NABFs have medium aromatic content (0.5–5.0 wt%) with PAH content less than 0.35 wt% but greater than 0.001wt%. Group III NABFs have low to negligible aromatic content (<0.5 wt% total aromatics) and less than 0.001 wt% (10 mg/kg) total PAH [9].
Based on reported data [10], the majority of NABF discharges with cuttings belong to Group III (99.9%), while Group II NABF discharges with cuttings account for 0.1%. No Group I NABF discharges with cuttings were reported, indicating the varying volume of NABF applications among the different groups.
The drilling fluids market was estimated to be $8.87 billion in 2022 [11] and is projected to reach $9.45 billion in 2023 with an average annual growth rate of 4.1 to 8.1% until 2028 [11,12,13,14,15]. Open data from 2020 reveal that WBDFs accounted for 49.4% of the market share, while drilling fluids with an oil base comprised approximately 35% [13].
The hydrocarbon base for drilling fluids is obtained through various technologies, such as hydrocracking, dewaxing, hydrodesulfurization, dearomatization, deep hydrogenation, isodeparaffinization, and hydrotreating. These processes aim to obtain a narrow fraction that meets product requirements [16,17,18,19,20,21,22,23,24,25].
There is growing concern for sustainable development [26]. In light of the increasingly stringent environmental regulations for drilling fluids, it is important to consider research focused on producing the hydrocarbon base of drilling fluids from renewable, biodegradable, and environmentally friendly sources. Vegetable oils and fatty acid esters derived from them [27,28,29,30,31,32] possess ecological compatibility but also have drawbacks, such as excessive viscosity, a high pour point, and low stability of the produced emulsions [32]. To meet the requirements of low viscosity, high flash point, low pour point, and minimal aromatic hydrocarbon content, the desirable components for the drilling fluid base are isoparaffins and naphthenic hydrocarbons. Isoparaffins can be obtained through the isomerization of relatively pure and expensive straight-run diesel fractions and hydrocracking distillates. Naphthenic hydrocarbons can be derived from challenging refinery feedstocks, specifically secondary gas oils that cannot be efficiently processed through traditional diesel hydrotreatment due to their high sulfur and nitrogen content, as well as a significant proportion of aromatic and olefin hydrocarbons [33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48]. Instead, these feedstocks are often directed towards marine fuels. Producing a high-value product, such as base of drilling fluids, from low-quality, highly aromatized feedstock is an attractive option to consider.
The hydrogenation refining of petroleum feedstock is typically carried out over catalysts based on molybdenum and/or tungsten sulfide, promoted with nickel and/or cobalt, and supported on a porous support [49,50]. It is known that CoMo(W) systems exhibit higher activity in hydrodesulfurization, while NiMo(W) systems are more active in hydrogenation and hydrodenitrification [40,51,52].
The hydrogenation of secondary gas oils requires catalysts with a high mass fraction of active components. However, the concentrated impregnation solution for the single impregnation of the support can be unstable. To address this issue, catalysts are prepared by selecting optimal precursors for the active phase, which often include highly soluble heteropoly compounds [53,54,55,56,57,58,59,60], modifiers and stabilizers (such as glycols) [49,61,62,63,64], and chelating agents (commonly organic acids) [65,66,67,68,69,70,71,72,73,74]. These techniques enable the achievement of a controllable high dispersion of the active phase particles and a significant level of promotion with cobalt (or nickel). The choice of the support is also of utmost importance. Internationally recognized aluminum oxide [55] should possess an optimal porous structure tailored [75] to the specific type of raw material [76], ensuring the effectiveness and stability of the catalysts [77].
Aluminum oxides, recommended for middle distillate hydroprocessing, can have different porous structures and a mean pore size larger than 5 nm [76]. However, it is not clear from previous research whether it is suitable for deep dearomatization of FCC.
The objective of this study was to examine the impact of Al2O3 support characteristics on NiMo catalysts prepared using an impregnation solution containing PMo heteropolyanions, nickel citrate, and diethylene glycol on their physicochemical properties and activity in deep hydrodesulfurization of secondary gas oils. Another objective was to determine the conditions for producing low-aromatic NABF on such catalysts. The goal was to obtain high-margin bases for drilling fluids with minimal sulfur and aromatic hydrocarbon content. This study focuses on a one-stage hydrogenation process scheme involving a mixture primarily composed of light catalytic cracking gas oil and light delayed coking gas oil.

2. Materials and Methods

2.1. Catalysts Preparation

NiMo/Al-n catalysts, where n represents the pore volume of the Al2O3 support, were prepared through a single impregnation of the support fraction with a joint impregnation solution of the active components. Three commercial samples of the support with volumes of 0.58, 0.75, and 0.90 cc/g were used. The impregnating solution was prepared to ensure the same mass fraction of active metal oxides in the final catalyst. The solution, containing PMo heteropolyanions, nickel citrate, and diethylene glycol, was prepared by sequentially dissolving citric acid, basic nickel carbonate, phosphoric acid, molybdenum acid, and diethylene glycol in distilled water. Once all the components were completely dissolved, the impregnating solution was cooled to room temperature, and the necessary amount of distilled water was added based on the pore volume of the support used. The molar ratios of phosphorus/molybdenum (P/Mo), citric acid/nickel (CA/Ni), and diethylene glycol/nickel (DEG/Ni) were 0.18, 0.4, and 1.49, respectively [78]. Following the single impregnation, the catalyst was air dried at room temperature for 12 h followed by drying at 120 °C for 5 h.

2.2. Characterization of the Catalyst

The catalysts’ textural characteristics were investigated using the low-temperature nitrogen adsorption method on the gas-sorption analyzer Quantachrome Autosorb-1.
The average morphological characteristics and composition of the sulfide phase in the synthesized samples were determined after sulfidation of the catalysts using a gas mixture (10 vol% H2S in H2) at 400 °C for 2 h employing a Tencai G2 20 transmission electron microscope, as described in [79]. The dispersity (D) of the active phase particles was calculated based on the Kasztelan hexagonal model [80] by examining 10–15 representative images of each catalyst, which contained at least 500 MoS2 crystallites.
The chemical composition of the surface of the sulfidized laboratory samples was studied using X-ray photoelectron spectroscopy (XPS) on a Kratos Axis Ultra DLD instrument with AlKα radiation (hν = 1486.6 eV). The preliminary calibration of the binding energy scale (E) was conducted based on the positions of the peaks of the Au4f7/2 (84.0 eV) and Cu2p3/2 (932.67 eV) levels. The calibration was performed using the C1s line (284.8 eV) from carbon present on the catalyst surface. Spectra were obtained with a fixed energy step of 1 eV, and individual lines, such as C1s, Al2p, Ni2p, S2p, and Mo3d, were obtained with a step of 0.1 eV. The acquired spectra were analyzed using Casa XPS software version 2.3.16 after subtracting the Shirley background and applying Gauss (30%)–Lorentz (70%) decomposition parameters. The photoelectron spectrum of each particle was decomposed into the main peak and satellites [81,82]. The relative areas of the satellites, binding energy, and the peak width at half maximum were mathematically related to the corresponding characteristics of the main peak. The calculation of relative concentrations was carried out according to the parameters proposed earlier [82,83,84] for determining the fraction of nickel in oxide (Ni2+), sulfide (NiSx), and mixed sulfide (NiMoS); molybdenum in oxide (Mo6+), sulfide (MoS2), and oxysulfide (MoSxOy); and sulfur in sulfide (S2−) and oxysulfide (SOx).

2.3. Catalytic Performance

The evaluation of the catalytic properties of the prepared samples as well as the production of hydrogenates suitable for the preparation of the hydrocarbon base for drilling fluids was carried out on a continuous-flow laboratory hydrogenation unit. All catalysts were loaded as a 0.5–1.0 mm fraction diluted with a 0.3–0.5 mm inert silicon carbide diluent in a volume ratio of 1:1 (catalyst: SiC) to minimize heat and mass transfer limitations.
Prior to testing, the catalysts were sulfidized in the unit reactor using straight-run gas oil (SRGO) boiling at 174–354 °C with 1 wt% DMDS added in terms of sulfur. The low-temperature sulfidation stage was carried out at 230 °C, and the high-temperature stage was carried out at 330 °C.
The catalysts’ activity was evaluated by the hydrogenation (HYD) of a mixture consisting mainly of light catalytic cracking gas oil (LCO) and light delayed coking gas oil (LCGO). The characteristics of the feed components and the blended feedstock are shown in Table 1. After the sulfidation stage, a straight-run gas oil was used as the feed for 48 h in order to stabilize the catalysts’ activity.
Catalytic tests were conducted under the following conditions: temperature ranging from 340 to 380 °C, pressure between 10.0 and 18.0 MPa, H2/feed ratio of 1500 NL/L feed, and feed volume rate of 0.5–3.0 h−1. The time on stream for each specific condition set was no less than 48 h. When transitioning to another temperature condition, the catalysts underwent a stabilization period of approximately 24 h. During the subsequent 24 h of operation under the condition, six product samples were taken. The sulfidation and testing conditions were identical for all samples, allowing for a reliable estimation and comparison of their catalytic activity.
The sulfur content and density were determined in alkaline-washed and dried samples of the hydrogenated product according to ASTM D2622 and ASTM D4052, respectively. For average samples of the hydrogenated product at each temperature condition, the aromatic hydrocarbon content (including mono-, bi-, and tricyclic distribution with HPLC-RID (ASTM D6379)) as well as boiling range (ASTM D7345) were also analyzed.
The aromatics hydrogenation rate and specific aromatics hydrogenation rate were taken as activity indicators. The aromatics hydrogenation rate was estimated according to Equation (1):
H Y D = C A r 0 − C A r C A r 0 · 100 % ,
where H Y D is the aromatics hydrogenation rate, %; C A r 0 is the feed aromatics content, wt%; and C A r is the product aromatics content, wt%.
The specific aromatics hydrogenation rate (specific activity) was calculated according to Equation (2):
H Y D S p e c = H Y D η M o ,
where H Y D S p e c is the specific aromatics hydrogenation rate, %/mmol Mo; H Y D is the aromatics hydrogenation rate, %; and η M o is the amount of molybdenum in the loaded catalyst in the reactor, mmol.

2.4. Physico-Chemical Studies of the Hydrocarbon Bases for Drilling Muds

The target fraction 200–270 °C was separated with conventional laboratory distillation with a dephlegmator; the fraction below 200 °C was distilled at atmospheric pressure, and the fraction 200–270 °C was distilled at a residual pressure of 5 mmHg to avoid any significant thermal transformations during distillation.
The density and kinematic viscosity of the separated target fraction were measured using an Anton Paar SVM 3001 viscometer according to ASTM D4052 and ASTM D445. The closed cup flash point was determined using a Tanaka AMP-8 automatic apparatus according to ASTM D93. The pour point temperature was determined using a Tanaka MPC-102 apparatus according to ASTM D6749. The total content of aromatic hydrocarbons was analyzed using HPLC-RID according to ASTM D6379. The aniline point was determined using a Tanaka AAP-6 instrument according to ASTM D611.

3. Results and Discussion

3.1. Investigation of Catalyst Characteristics

The concentration of MoO3 in the prepared impregnating solutions as well as the textural characteristics of the support samples used and the synthesized NiMo/Al-n catalysts based on them are presented in Table 2.
The N2 adsorption–desorption isotherms as well as the pore size distribution of the synthesized NiMo/Al-n catalyst samples are shown in Figure 1, representing the pore structure of the catalysts.
The pore volume of the applied supports varied from 0.58 cc/g to 0.90 cc/g. From the presented data, it can be observed that the sample of the Al-0.75 support was characterized by pores with the largest effective diameter as well as the largest volume of pores with an effective diameter of more than 7 nm. The deposition of oxide precursors on the support led to a decrease in the specific surface area and pore volume by 31–33%. This is consistent with the amount of deposited components and thus indicates that excessive coking of the pores did not occur during sulfidation.
Examples of TEM images of the sulfided NiMo/Al-n catalyst samples are shown in Figure 2.
The black thread-like bands correspond to the layers of MoS2 crystallites. The interlayer spacing is approximately 0.62 nm, which is a characteristic value for the basal planes of MoS2 crystallites [54,80,85]. The results of processing the obtained TEM images are presented in Table 3.
The morphological characteristics of the active phase particles depend on the pore volume of the catalyst support used in the synthesis. The average length of the active phase particles ranged from 3.8 to 4.3 nm, and the average stacking number of the MoS2 crystallites decreased from 2.9 to 1.9. From the presented data, a linear inverse relationship between the dispersity of the active phase particles and the concentration of the active phase precursors in the impregnating solution can be observed (Figure 3).
The dispersity of the active phase particles decreases from 0.31 to 0.28 with an increase in the concentration of MoO3 in the impregnating solution from 0.37 g MoO3/mL to 0.59 g MoO3/mL. With an increase in the precursor sulfide phase concentration in the pores, the probability of particle segregation increases, resulting in the formation of a smaller number of larger particles.
XPS was performed for all sulfided NiMo/Al-n catalyst samples to obtain detailed information about the composition of the particles on the catalyst surfaces. Examples of the Mo 3d and Ni 2p spectra for the synthesized catalyst samples are shown in Figure 4.
The presented spectra contain characteristic peaks for MoS2 in the range of 220–240 eV. The main binding energies of the molybdenum peaks for the NiMo/Al-n catalysts correspond to the literature [86,87,88,89]. Characteristic peaks were also observed for oxysulfide particles (MoSxOy) and Mo particles in the Mo6+ oxide environment. In the Ni 2p3/2 spectrum, three main states are observed: peaks at 852.3–853.1 eV correspond to Ni in the active phase (NiMoS), peaks at 851.2–852.0 eV correspond to Ni in individual sulfides (NiSx), and signals at 855.2–855.8 eV indicate the presence of Ni in the Ni2+ oxide state [63,88,89,90].
The relative content of nickel and molybdenum particles on the surface of the sulfided NiMo/Al-n catalyst samples, according to the XPS data, is presented in Table 4.
The degree of promotion of crystallites of the active phase and their edges decreased from 0.28 to 0.15 and from 0.91 to 0.56, respectively, with an increase in the concentration of MoO3 in the impregnating solution. The graphical representation of this dependence is shown in Figure 5.
This correlation can be explained by the increase in the size of the molybdenum sulfide particles and the inability to incorporate nickel atoms into them. The effect can also be associated with too low dispersity of nickel precursors and the formation of their agglomerates, which are not fully sulfided, as confirmed with the XPS data.

3.2. Catalytic Tests

The activity of the synthesized catalysts was evaluated based on the degree of aromatics hydrocarbon hydrogenation at a pressure of 10 MPa, LHSV—1.0 h−1, H2/feed ratio 1500 NL/L, and optimum process temperature of 370 °C [78]. The results of the catalytic tests are presented in Table 5.
The aromatics hydrogenation rate ranged from 48.2% for NiMo/Al-0.58 to 71.3% for NiMo/Al-0.75. The sample NiMo/Al-0.75 also demonstrated the highest specific aromatics hydrogenation rate of 2.31%/mmol Mo. The variation in the specific aromatics hydrogenation rate correlates with the content of the NiMoS phase, as shown in Figure 6. The described variations in the active phase morphology and composition lead to the presence of an observable dependence between HYD activity and the support volume of pores with a diameter larger than 7 nm, as also shown in Figure 6.
The aromatics hydrogenation rate decreased from 71.3% to 48.2% with a decrease in the content of the mixed NiMoS phase as well as with an increase in the pore volume of the support with an effective diameter greater than 7 nm at the same amount of introduced active phase. This can be explained by better accessibility of active centers for feed components that resulted from the better active phase volume distribution, higher promotion rate, and higher proportion of mixed sulfide phase.

3.3. Production of Sustainable Hydrocarbon Bases for Drilling Muds

Analysis of the results presented in Table 5 indicates the impossibility of achieving, under the reasonable technological conditions and a pressure of 10 MPa, a product with an aromatic hydrocarbon content of less than 5.0 wt%, which is one of the key requirements for hydrocarbon-based drilling fluids [9].
A one-stage process implies the use of only a NiMo/Al-0.75 catalyst, a temperature range of 360–390 °C, a high hydrogen pressure of 15–20 MPa, and a low feedstock volumetric flow rate of 0.4–0.6 h−1, which enables the production of a liquid product with an aromatic content of 1.4 wt% instead of 30.8 wt% at a hydrogen pressure of 10 MPa. A further increase in pressure allows for the procurement of a product with even lower aromatic content.
The properties of the obtained liquid products are presented in Table 6.
The properties of the obtained hydrocarbon base samples for drilling fluids (200–270 °C fraction) in comparison with industrial references are presented in Table 7.
A one-stage process using a NiMo/Al-0.75 catalyst allows for the production of a hydrocarbon base for Group II drilling fluids according to the OGP classification comparable in quality to industrial samples. Increasing the pressure will enable the production of a hydrocarbon base for Group III drilling fluids according to the OGP classification.

4. Conclusions

A series of highly active NiMo catalysts with a high metal content (up to 30.0 wt%) was synthesized using PMo heteropolyanions, citric acid, and diethylene glycol on alumina carriers with varying pore volumes (0.58–0.90 cc/g). Achieving the same catalyst composition in a single impregnation requires increasing the concentration of the impregnation solution in accordance with the decrease in the carrier’s pore volume. The concentration of the impregnation solution, in turn, affects the composition and morphology of the active phase particles in the prepared catalyst, resulting in an increase in the length of the active phase particles and a decrease in the degree of nickel promotion of MoS2 edges.
Based on the test results of the catalyst samples in the hydrogenation of a mixture of secondary gas oils at 10 MPa, LHSV = 1.0 h−1, 360–390 °C, and an H2/feed ratio of 1500 NL/L, the maximum degree of aromatics hydrogenation of 71.3% was achieved on the NiMo/Al-0.75 catalyst as well as the highest specific degree of hydrogenation of 2.31%/mmol. These results are fully consistent with the amount of the mixed sulfided NiMoS phase and the pore volume of the carrier with an effective diameter of more than 7 nm, which can be explained by the better accessibility of active sites that resulted from the better active phase volume distribution, higher promotion rate, and higher proportion of the mixed sulfide phase.
The possibility of using the NiMo/Al-0.75 catalyst, which exhibited the highest activity, was demonstrated for obtaining Group II drilling fluids according to the OGP classification suitable for separating low-sulfur content (less than 1 ppm) and low-aromatic hydrocarbon content (less than 1.4 wt%) from a mixture of secondary distillates (mainly LCO) at a pressure of 15–20 MPa with a one-stage process.
The obtained result has practical value in terms of developing sustainable and economically efficient methods for incorporating low-quality petroleum gas oils into high-margin environmentally friendly, non-fuel petroleum products.

Author Contributions

Conceptualization, R.B. and P.N.; investigation, A.I., A.M., E.P. and A.K.; data curation, O.S.; writing—original draft preparation, A.I.; writing—review and editing, R.B. and P.N.; visualization, E.P.; supervision and project administration, P.N. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Textural characteristics of alumina supports.
Figure 1. Textural characteristics of alumina supports.
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Figure 2. Examples of TEM images of the sulfided NiMo/Al-n catalysts.
Figure 2. Examples of TEM images of the sulfided NiMo/Al-n catalysts.
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Figure 3. Dependence of the dispersion of NiMoS active phase particles on the concentration of MoO3 in the impregnating solution.
Figure 3. Dependence of the dispersion of NiMoS active phase particles on the concentration of MoO3 in the impregnating solution.
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Figure 4. Decomposed spectra of Ni 2p and Mo 3d for the sulfided NiMo/Al-0.75 catalyst sample.
Figure 4. Decomposed spectra of Ni 2p and Mo 3d for the sulfided NiMo/Al-0.75 catalyst sample.
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Figure 5. The promotion rate of crystallites and their edges as a function of MoO3 concentration in the impregnating solution.
Figure 5. The promotion rate of crystallites and their edges as a function of MoO3 concentration in the impregnating solution.
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Figure 6. Dependence of aromatics hydrogenation rate on the content of NiMoS phase and pore volume of the support with an effective diameter > 7 nm.
Figure 6. Dependence of aromatics hydrogenation rate on the content of NiMoS phase and pore volume of the support with an effective diameter > 7 nm.
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Table 1. The characteristics of the feed components and the blended feedstock.
Table 1. The characteristics of the feed components and the blended feedstock.
PropertiesLCOLCGOLCO
(Major Proportion)
+ LCGO
Density at 15 °C (kg/m3)950.6914.2945.1
Total sulfur content (wt%)1.1081.0081.093
Distillation
Temperature (°C):
IBP189218194
10 vol%210263215
50 vol%254308262
90 vol%323352326
96 vol%338364342
yield at 340 °C98--
yield at 360 °C-94-
Total aromatics content (wt%):77.744.375.1
Mono-aromatics26.014.725.1
Bi-aromatics44.017.741.5
Tri-aromatics+7.711.98.5
Iodine number (I2 g/100 g)17.036.521.2
Table 2. Textural characteristics of the supports and NiMo/Al-n catalysts and concentration of MoO3 in the impregnating solutions used for their preparation.
Table 2. Textural characteristics of the supports and NiMo/Al-n catalysts and concentration of MoO3 in the impregnating solutions used for their preparation.
PropertiesAl-0.90NiMo/Al-0.90 *Al-0.75NiMo/Al-0.75 *Al-0.58NiMo/Al-0.58 *
Concentration of MoO3 in impregnating solutions (g/mL)-0.37-0.45-0.59
Textural characteristics:
S (m2/g)309208254175271187
Vp (cm3/g)0.900.610.750.500.580.39
Def (nm)7.0
(bimodal max at 7.0 and 9.5)		5.013.09.46.05.0
* The content of active metal oxides in all catalyst samples was equal.
Table 3. Morphology of active phase particles in the NiMo/Al-n catalysts.
Table 3. Morphology of active phase particles in the NiMo/Al-n catalysts.
PropertiesNiMo/Al-0.90NiMo/Al-0.75NiMo/Al-0.58
L ¯ 3.84.04.3
N ¯ 2.92.61.9
D0.310.290.28
(fe/fc)NiMo4.03.12.9
L ¯ —average particle length (nm), N ¯ —average number of layers in the crystallite (stacking number), D—dispersity, (fe/fc)NiMo—the ratio of the number of NiMo atoms located at the edges of the crystallite to the number of NiMo centers located at the corners.
Table 4. Surface composition of the sulfided NiMo/Al-n catalysts.
Table 4. Surface composition of the sulfided NiMo/Al-n catalysts.
CatalystMo Content, % RelNi Content, % Rel.(Ni/Mo)slab(Ni/Mo)edge
MoS2MoSxOyMo6+NiMoSNiSxNi2+
NiMo/Al-0.9081127395560.280.91
NiMo/Al-0.7583116455140.190.65
NiMo/Al-0.5883125316090.150.56
(Ni/Mo)slab, (Ni/Mo)edge—degree of promotion of active phase crystallites and their edges, respectively.
Table 5. Catalytic performance of the synthesized NiMo/Al-n catalysts at 10 MPa, LHSV of 1.0 h−1, 370 °C, and H2/feed ratio of 1500 NL/L.
Table 5. Catalytic performance of the synthesized NiMo/Al-n catalysts at 10 MPa, LHSV of 1.0 h−1, 370 °C, and H2/feed ratio of 1500 NL/L.
PropertiesFeedstock
LCO (Major Proportion)
+ LCGO 		Liquid Product
NiMo/Al-0.90NiMo/Al-0.75NiMo/Al-0.58
Density at 15 °C (kg/m3)945.1857.0855.0869.1
Total sulfur content (wt%)1.0930.00070.00070.0009
Total aromatic content (wt%):75.126.121.638.9
Mono-aromatics25.125.921.137.9
Bi-aromatics41.50.20.50.9
Tri-aromatics+8.50.00.00.1
HYD (%)-65.371.348.2
Specific HYD (%/mmol Mo)-2.092.311.54
Table 6. Characteristics of the hydrogenation liquid products.
Table 6. Characteristics of the hydrogenation liquid products.
PropertiesValues for Total Hydrogenated
Liquid Product
Density at 20 °C (kg/m3)833.8
Total sulfur content (wt%)<0.001
Distillation yield (vol%),
at a temperature:
IBP59
10176
50217
90288
95318
Total aromatic content (wt%):1.9
Mono-aromatics1.8
Bi-aromatics0.1
Tri-aromatics+0.0
Pour Point (°C)–55
Table 7. Characteristics of the hydrocarbon base for drilling fluids compared to industrial references.
Table 7. Characteristics of the hydrocarbon base for drilling fluids compared to industrial references.
PropertiesDistillate 200–270 °C
(Yield 66.7 wt%)		Commonly Used Commercial
NAF Base Fluids [5,20,91]
Colorclearclear
Viscosity at 40 °C (mm2/s)2.451.6 ÷ 3.2
Flash point (°C)84>70
Pour point (°C)−52–18 ÷ –50
Total aromatic content (wt%)1.4<0.2 ÷ 3.0
Total sulfur content (wt%)0.0001
Density (kg/m3) at 15 °C846.4804 ÷ 827
Aniline point (°C)82>72
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Iusovskii, A.; Boldushevskii, R.; Mozhaev, A.; Shmelkova, O.; Pavlycheva, E.; Koklyukhin, A.; Nikulshin, P. Tailoring NiMo-Based Catalysts for Production of Low-Viscosity Sustainable Hydrocarbon Bases for Drilling Muds from Secondary Gas Oils. Energies 2023, 16, 5859. https://doi.org/10.3390/en16165859

AMA Style

Iusovskii A, Boldushevskii R, Mozhaev A, Shmelkova O, Pavlycheva E, Koklyukhin A, Nikulshin P. Tailoring NiMo-Based Catalysts for Production of Low-Viscosity Sustainable Hydrocarbon Bases for Drilling Muds from Secondary Gas Oils. Energies. 2023; 16(16):5859. https://doi.org/10.3390/en16165859

Chicago/Turabian Style

Iusovskii, Aleksei, Roman Boldushevskii, Aleksandr Mozhaev, Olga Shmelkova, Elizaveta Pavlycheva, Aleksandr Koklyukhin, and Pavel Nikulshin. 2023. "Tailoring NiMo-Based Catalysts for Production of Low-Viscosity Sustainable Hydrocarbon Bases for Drilling Muds from Secondary Gas Oils" Energies 16, no. 16: 5859. https://doi.org/10.3390/en16165859

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