Separation and Characterization of Sulfur Compounds in Ultra-deep

Sulfur compounds in two representative deep crude oils (Ha9, 6598–6710 m; ZS1C, 6861–6944 m) with distinct levels of maturity from Tarim Basin, Ch...
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Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin Meng Wang,† Guangyou Zhu,‡ Limin Ren,† Xuxia Liu,† Suoqi Zhao,† and Quan Shi*,† †

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, People’s Republic of China Research Institute of Petroleum Exploration and Development, PetroChina, Beijing 100083, People’s Republic of China



S Supporting Information *

ABSTRACT: Sulfur compounds in two representative deep crude oils (Ha9, 6598−6710 m; ZS1C, 6861−6944 m) with distinct levels of maturity from Tarim Basin, China, were analyzed by positive-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The thiophenic and sulfidic compounds were selectively separated from the crude oils with high purity and recovery by the methylation/demethylation approach and further characterized in detail by gas chromatography (GC) coupled with a sulfur chemiluminescence detector (SCD) and GC−mass spectrometry (MS). The two crude oils have a large difference in sulfur compound composition, which are both unique compared to common crude oils. A homologue series of 1,1-dimethylhexahydrodibenzothiophenes, which has been found as highly resistant organic sulfur compounds in diesel hydrodesulfurization, was detected in Ha9 crude oil. This is the first time that these biomarker-like compounds have been identified in crude oil. Thiadiamondoids (1−3 cages) with more structural isomers than reported oils as well as various acyclic sulfides, which probably derived from alkyl sulfides, were identified in the sulfidic fraction of the ZS1C crude oil, which indicates that the crude oil has an unusual geological history. The selective separation technique would offer broad prospects for geochemical research on sulfur compounds in crude oils, including their compound-specific 34S and 13C analyses.

1. INTRODUCTION The Tarim Basin is the largest oil-and-gas-bearing basin in China, with an area of 560 × 103 km2, and the Paleozoic stratigraphic interval is the main exploration target.1 The recent discovery of deep (over 6500 m) gas condensate and oils has attracted a great deal of attention and investigation.2−8 In the long geological history, hydrocarbon gas was mostly from organic conversion by bacterial action and thermal genesis or crude oil thermal cracking and accumulated into gas reservoirs.9 The geochemical characteristics of deep oils are quite distinct from the shallow oils, because of complicated secondary alterations.2,3,5,10 The source rock and reservoir in the Tarim marine sedimentary basin are mainly developed in the Palaeozoic formation, which has a relatively deep buried depth, old source rock, high thermal evolution, several structural activities, and complex hydrocarbon accumulation process.11 These features make it hard to predict the oil and gas distribution. Thus, a fine geochemical study of oil and gas in the deep formation is of scientific significance and exploration value to demonstrate petroleum origin and genesis, especially the exploration potential in deep formation. Specifically, the analysis of organic sulfur compounds in crude oils is critical to rationalize the various compositions and properties of oils for geological and geochemical considerations.12 However, because of the complex hydrocarbon matrix and the inherent molecular complexity of sulfur compounds, selective separation of thiophenic and sulfidic compounds from crude oils is critical for their comprehensive characterization.13 During the past few decades, numerous novel organic sulfur compounds have been isolated from sediments and petroleum © XXXX American Chemical Society

using ligand-exchange chromatography or oxidation−reduction derivatizations, followed by identification using mass spectrometry (MS) and nuclear magnetic resonance (NMR).14−21 These studies led to a wider understanding of the origin and formation mechanisms of the sulfur compounds in the geosphere. Besides, the distribution of conventional thiophenic compounds, primarily benzothiophenes (BTs) and dibenzothiophenes (DBTs), in oils have been proposed as source and maturity indicators for source rocks and petroleum.5,22−25 The compound-specific carbon and sulfur isotope analyses were widely employed as powerful tools in research of the oil source, maturity, and migration.7,10,26,27 Moreover, the compound-specific sulfur isotope analysis could also provide a tracer for molecular-level formation mechanisms of sulfur biomarkers.28−30 Although there has been an automating compound-specific 34S analysis technique requiring no pretreatment for crude oils, co-elution of non-sulfur compounds would significantly decrease the analytical precision. The unambiguous identification of the complex sulfur compounds still faces some difficulties, especially when reference materials are not available.29,31 Hence, elaborate separation of thiophenic and sulfidic compounds would enable and facilitate sulfur compound-specific 13C and 34S isotopic analyses. Recently, a novel approach for selective separation of highpurity thiophenic and sulfidic compounds from petroleum in one procedure was established in our group.13 The technique was verified by a vacuum distillation petroleum fraction that Received: April 22, 2015 Revised: June 27, 2015

A

DOI: 10.1021/acs.energyfuels.5b00897 Energy Fuels XXXX, XXX, XXX−XXX

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Energy & Fuels Table 1. Bulk Properties of Crude Oil from Ha9 and ZS1C Wells

a

well

depth (m)

reservoir temperature (°C)

Ha9 ZS1C

6598−6710 6861−6944

162 169

sulfur (wt %) density at 20 °C (g/cm3) 0.62 2.06

0.920 0.791

asphaltenesa (wt %) H2S content (in associated gas) (vol %) 6.67 0.18

0.41 8.27

Hexane asphaltenes, according to the Chinese Standard analytical method for petroleum and natural gas industries: SY/T 5119-2008.32

showed rare discrimination among sulfur compounds with ranging molecular weights and degrees of unsaturation. In our attempt to apply this technique to crude oils, it was found that, despite of numerous studies about the deep formation oils from Tarim Basin, sulfur compounds in them have not been well characterized.6−8 In this paper, we characterized in detail the sulfur compounds in Ha9 and ZS1C crude oils, using the established method.

2. MATERIALS AND METHODS 2.1. Samples and Reagents. The crude oils were obtained from Ha9 and ZC1C discovery wells of Tarim Basin, northwest China. Ha9 crude oil is a heavy oil, while ZS1C is a light oil, which was occasionally sprayed from the gas well (see Figure S-1 of the Supporting Information). The Ha9 crude oil with a relatively low thermal maturity and the ZS1C crude oil with a high thermal maturity are considered from Ordovician and Cambrian source rocks, respectively.6,8 Bulk properties of the crude oils are shown in Table 1. Silver tetrafluoroborate (AgBF4), methyl iodide (MeI), 4dimethylaminopyridine (DMAP), and 7-azaindole were purchased from J&K Chemical, Ltd. High-performance liquid chromatography (HPLC)-grade n-hexane (n-C6), dichloromethane (DCM), and acetonitrile (MeCN) (obtained from Scharlau Chemic S.A., Spain) were used as received. 2.2. Selective Separation of Thiophenic and Sulfidic Compounds from Crude Oils. The scheme for sulfur compound separation from crude oils was illustrated in Figure 1 and a detailed procedure description could be found elsewhere.13 A total of 500 mg of each crude oil was used. A total of 10 and 30 mol equiv of AgBF4 and MeI (on the basis of the sulfur content and weight of the raw crude oil) were used to ensure the high methylation conversion. AgBF4 feeding should be quickly because of its hydroscopicity, and the vial where the methylation reaction occurred should be sealed tightly in case the volatile MeI escapes. The crude oils were subjected to gas chromatography (GC) coupled with a sulfur chemiluminescence detector (SCD); two separated sulfur fractions of each crude oil were subjected to GC−SCD and and GC−mass spectrometry (MS) analyses, respectively. The methyl derivatization products of two crude oils were analyzed by electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). 2.3. FT-ICR MS, GC−SCD, and GC−MS Analyses. Bruker apexultra FT-ICR MS equipped with a 9.4 T actively shielded superconducting magnet was used for the molecular characterization of crude oils. Methyl derivatization products of each crude oil was dissolved in MeCN at a final concentration of 0.005 mg/mL for ESI FT-ICR MS analysis. ESI source potentials were all set as follows: −3.5 kV spray shield voltage, −4.0 kV capillary entrance voltage, and 320 V capillary column end voltage. Ions generated from the ESI source were accumulated for 0.001 s in a hexapole with 2.4 V direct-current (DC) voltage and 300 Vp−p radio-frequency (RF) amplitude. The ions were introduced into a quadrupole (Q1), which was optimized at 150 Da to obtain a broad range for ion transfers. An argon-filled hexapole collision cell was operated at 5 MHz and 300 Vp−p RF amplitude, in which ions accumulated for 0.001 s. The extraction period for ions from the hexapole to the ICR cell was set to 0.9 ms. The RF excitation was attenuated at 16.00 dB and used to excite ions over the range of 110−600 Da. Spectra comprising 4 MW data points were collected. The signal-to-noise ratio (S/N) was enhanced by summing 64 time domain transients. FT-ICR MS was internally calibrated with the S1 class homologous series. Mass spectrum peaks with a relative abundance greater than 6

Figure 1. Reaction analytical scheme for selective separation of thiophenic and sulfidic compounds from Ha9 and ZS1C crude oils. times the standard deviation of the baseline noise were exported to a spreadsheet. Data analysis was performed using custom software. The detail of data processing could be found elsewhere.32,33 GC−SCD analysis was performed using Agilent 7890A GC equipped with a SCD (Agilent 355). The detector was set at 250 °C, with a hydrogen flow rate of 46 standard-state cubic centimeters per minute (sccm) and an air flow rate of 66 sccm. The burner temperature was set at 800 °C with a pressure of 377 Torr. The ozone reaction cell pressure was at 5.5 Torr, and the ozone oxidant flow was set at 6.0 psi. A HP-5 column (30 m × 0.25 mm × 0.25 μm) was used for GC−SCD analysis. Thermo Trace DSQ GC−MS (Thermal Electron) was used for MS analysis. The mass spectrometer was operated under electron impact (EI) at 70 eV ionization energy and a mass range of 35−500 Da at 2 s scan cycle. The temperature of the injector in GC−SCD and GC−MS was set at 280 °C. A DB-35 MS column (30 m × 0.25 mm × 0.25 μm) and a HP-5MS column (30 m × 0.25 mm × 0.25 μm) were used for GC−MS analysis.

3. RESULTS AND DISCUSSION 3.1. Molecular Composition of Sulfur Compounds Characterized by FT-ICR MS. As shown in Table 1, two crude oils were both buried to over 6500 m with reservoir temperatures above 160 °C; however, their properties were different. The density and asphaltene content of Ha9 crude oil B

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Figure 2. DBE versus carbon number distribution of S1 class species detected by positive-ion ESI FT-ICR MS for sulfonium salts derived from Tarim Basin crude oils.

two crude oils. Crude oils and their sulfidic and thiophenic fractions were characterized by GC−SCD and GC−MS, respectively, and chromatograms are shown in Figures S-2 and S-3 of the Supporting Information. This is the first time applying the methylation/demethylation method on crude oils. 3.2. Sulfur Compounds in Ha9 Crude Oil. Figure 3 shows the GC−SCD chromatogram of the Ha9 crude oil and GC−MS total ion chromatograms of its thiophenic and sulfidic fractions. Two of the most common sulfur compound series, BTs and DBTs, are obviously presented on the SCD chromatogram of the crude oil. The result was generally consistent with that from FT-ICR MS, except that the low-mass BTs exhibited high relative abundance. This difference can be explained because the low-mass BTs were discriminated in the FT-ICR MS by ESI efficiency and/or the ion transformation efficiency of MS. GC−SCD results (see Figure S-2 of the Supporting Information) shows that the crude oil and its thiophenic fraction have identical chromatograms, indicating that the methylation/demethylation process rarely discriminated against homologues of the thiophenic compounds. Although the compositional information on major sulfur compounds derived from the crude oil (SCD) and the thiophenic fraction (MS) are identical, the separation is of great significance: the selective separation of thiophenic and sulfidic compounds with high purity allows for 13C and 34S isotopic analysis of individual sulfur compounds, even if they are present in a low

are much higher than those of ZS1C crude oil, while the later bears much higher sulfur in oil and hydrogen sulfide in gas than the former. Figure 2 shows the iso-abundance map of double-bond equivalent (DBE) as a function of the carbon number for the S1 class species from the positive-ion ESI FT-ICR mass spectra of the methyl derivatization products of Ha9 and ZS1C crude oils. Like their clear difference in color (see Figure S-1 of the Supporting Information), the two crude oils have significant differences in the sulfur compound molecular composition. For Ha9 crude oil, the S1 class species distribution pattern is generally common in the published result of crude oils.5,34−38 The most abundant series are with DBE values of 9 and 6, corresponding to dibenzothiophenes (DBTs) and benzothiophenes (BTs), respectively. For ZS1C, the most abundant S1 compounds have a DBE value of 9, corresponding to DBTs, which are mainly short alkyl substitute homologues. It should be noted that the second abundant series is with DBE = 5, and this distribution pattern is rarely found in previous studies. FTICR MS results just provide accurate molecular composition information, while GC−MS is a practicable approach for a structural study of these small molecules once the sulfur compounds are separated from the complex hydrocarbon matrix. To investigated the detail molecular composition of the sulfur compounds, the novel selective separation approach based on methylation/demethylation was performed on these C

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Figure 3. GC−SCD chromatogram of the Ha9 crude oil and GC−MS total ion chromatograms of thiophenic and sulfidic fractions separated from the Ha9 crude oil. HP-5 and HP-5MS columns (both at 30 m × 0.25 mm × 0.25 μm, Agilent) were used for GC−SCD and GC−MS analyses, respectively. The column oven programs for both GC−SCD and GC−MS analyses were as follows: kept at a constant temperature of 40 °C for 1 min, followed by a ramp of 10 °C/min to 300 °C, and then holding for 10 min.

Figure 4. GC−SCD chromatogram of the ZS1C crude oil and GC−-MS total ion chromatograms of thiophenic and sulfidic fractions separated from the ZS1C crude oil. HP-5 and HP-5MS columns (both at 30 m × 0.25 mm × 0.25 μm, Agilent) were used for GC−SCD and GC−MS analyses, respectively. The column oven programs for both GC−SCD and GC−MS analyses were as follows: kept at a constant temperature of 50 °C for 1 min, followed by ramps of 15 °C/min to 100 °C and 3 °C/min to 300 °C, and then holding for 10 min.

D

DOI: 10.1021/acs.energyfuels.5b00897 Energy Fuels XXXX, XXX, XXX−XXX

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Figure 5. Mass chromatograms of thiaadamantanes and thiadiamantanes. Mass spectra of labeled peaks can be found in the Supporting Information. The GC operation condition is the same as that in Figure 4.

DBTs were successfully separated from the crude oil, and the identical distribution patterns of its homologues illustrate no structural discrimination for DBT isomers. BT and its C1−C3 homologues were identified in the thiophenic fractions, which were submerged by other sulfur compounds in the SCD chromatogram. Almost all of the sulfur compounds in the sulfidic fraction were identified as thiadiamondoids, including 1−3 cage cyclic sulfides, namely, thiaadamantanes, thiadiamantanes, and thiatriamantanes, respectively, which are wellconsistent with the sulfur species with DBE = 3, 5, and 7 in the bottom panel of Figure 2. The complete separation of the thiophenic and sulfidic compounds with high purity would allow for 13C and 34S isotopic analyses of individual sulfur compounds and other geological studies. Thiaadamantanes were first identified in crude oil in 1952;40 however, it is rarely reported in crude oils. Wei et al. have systemically characterized 1−6 cage thiadiamondoids in crude oils from the Gulf of Mexico and studied the geochemical significance of these unusual compounds.41,42 Like adamantanes presented in crude oils,9,43,44 thiadiamondoids were considered to have relations with thermal maturity, which are most likely generated by sulfurization of their adamantine precursors by thermal sulfate reduction (TSR), a hightemperature process in which hydrocarbons were oxidized by sulfates in the reservoirs.9,41,42,45 Thiadiamondoids were also found in TZ83 crude oil from Tarim Basin,46 which also has abundant adamantanes and similar geological history to ZS1C crude oil.11,46,47 The ZS1C crude oil was buried under the conditions of high temperature (169 °C), which is conditional for TSR occurrence. The high concentration of H2S in natural gas (8.27 vol %) is another conditional evidence for TSR. Figure 5 shows mass chromatograms of thiaadamantanes and thiadiamantanes. Mass spectra of labeled peaks are shown in Figures S-7−S-10 of the Supporting Information. In comparison to the results by Wei et al. from crude oils from the Gulf of Mexico, 41,42 more isomers of C 3 - and C 4 -substituted thiaadamantanes and C1- and C2-substituted thiaadamantanes were presented in ZS1C crude oil but the unsubstituted thiaadamantane (more volatile than its higher counterparts) is absent, maybe due to natural and production-induced phase

concentration. Despite the general similarity between the total ion chromatogram and the SCD chromatogram of the thiophenic fraction, two non-sulfur compounds (labeled as A and B) were tentatively identified as diisopropylmethylbenzene and hexamethylbenzene, respectively. Compound B was also presented in the sulfidic fraction. These two unexpected compounds may be byproducts generated in methylation/ demethylation; however, the reaction pathways are not clear. The composition of the sulfidic fraction is more interesting: the most abundant compounds in it were identified as 1,1dimethylhexahydrodibenzothiophenes (H6DBTs). As shown in Figure 2, peaks 1, 2, 3, and 4 correspond to a homologue series with H, methyl, ethyl, and propyl on the benzene ring, respectively. Mass chromatograms and mass spectra can be found in Figures S-4 and S-5 of the Supporting Information. H6DBTs were first isolated and identified as their sulfone derivatives by Charrié-Duhau et al.20 in hydrotreated diesels. Andersson et al.39 enriched these compounds in a desulfurized heating oil by ligand-exchange chromatography and extended the range of the homologue series; more isomers were identified and confirmed by a synthetic standard. H6DBTs were considered to be even more refractory than 4,6dimethyldibenzothiophene to hydrodesulfurization processing.20 These molecules were proposed to be derived from terpenoid precursors under a specific geological environment.20 Nevertheless, this speculation has not been firmly evidenced because they were all determined in processed petroleum fractions. The finding of this study is the first time providing evidence that H6DBTs do exist in crude oil with a clear geological source. Although the marker concentrations should be very low, their molecular-level formation mechanisms and the geochemical significance, including as potential source indicators, should be investigated in a future study. 3.3. Sulfur Compounds in ZS1C Crude Oil. Besides the FT-ICR MS result, the characteristic that the oil contains a very high content of short alkyl chain DBTs can be easily detected from the total ion chromatogram, which is shown in Figure S-6 of the Supporting Information. The GC−SCD chromatogram of the ZS1C crude oil and GC−MS total ion chromatograms of its thiophenic and sulfidic fractions are shown in Figure 4. E

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Figure 6. Mass chromatograms of acyclic sulfides detected in the sulfidic fraction of ZS1C crude oil. Asterisked peaks were presented as the most likely structure, and other peak are their isomers. The gas chromatographic column used here is a DB-35 MS column (30 m × 0.25 mm × 0.25 μm, Agilent). The column oven was kept at a constant temperature of 50 °C for 1 min, followed by ramps of 15 °C/min to 100 °C and 3 °C/min to 300 °C, and then holding for 10 min.

separation or sample storage.42 Because the separation methods are different for these crude oils with different geology sources, it could not draw a conclusion that the composition difference was caused by the isolation fractionation or special geological alterations. As shown in Figure 4, a cluster of low-intensity peaks was present at the left of the thiaadamantane region on the GC− MS total ion chromatogram of the sulfidic fraction. These compounds were characterized by another GC−MS analysis, and the result was shown in Figure 6. Methyl sulfides with linear, branched, cyclic, and aromatic blocks were identified in the chromatogram. In the methylation/demethylation process, theoretically, mercaptans, non-methyl sulfides, and disulfides48 could also generate methyl sulfides, of which the generation pathway is illustrated in Scheme S-1 of the Supporting Information. The results (not shown) of oxidation experiments of ZS1C crude oil with iodine,49 which is selective to mercaptans, verified that the original sulfur compounds present on the left of the thiaadamantane region are sulfides rather than mercaptans. However, it is still hard to say that the detected methyl sulfides originally exist in ZS1C crude oil. Regardless of the origin, the results at least illustrate that those structural blocks exist in the crude oil. The separation method for noncyclic sulfides together with mercaptans and their geological significance should be investigated in future studies.

thiophenic and sulfidic compounds with high purity allows for C and 34S isotopic analyses of individual sulfur compounds, even if they are present in a very low concentration. Future studies should be modified on the separation of non-cyclic sulfides and the geochemical significance of those sulfur compounds with a typical biological structure and low concentration, which are generally ignored in routine analysis. 13



ASSOCIATED CONTENT

S Supporting Information *

Picture of the two Tarim Basin crude oils (Figure S-1), chromatograms of Ha9 crude oil and its thiophenic fraction (Figure S-2), chromatograms of ZS1C crude oil and its thiophenic fraction (Figure S-3), mass chromatograms of HDDBTs detected in the sulfidic fraction of Ha9 crude oil (Figure S-4), mass spectra of H6DBTs detected in the sulfidic fraction of Ha9 crude oil (Figure S-5), total ion chromatograms of ZS1C crude oil and its sulfur fraction (Figure S-6), mass spectra of peaks 1−9 labeled in Figure 5 (Figure S-7), mass spectra of peaks 10−18 labeled in Figure 5 (Figure S-8), mass spectra of peaks 19−27 labeled in Figure 5 (Figure S-9), mass spectra of peaks 28−39 labeled in Figure 5 (Figure S-10), generation pathway of methyl sulfides starting from non-cyclic sulfides, mercaptans, and disulfides in the methylation/ demethylation process (Scheme S-1), semi-quantitative analysis of total sulfur recovery of thiophenic and sulfidic fractions, GC−SCD chromatograms of separated thiophenic (right) and sulfidic (left) fractions from Ha9 crude oil with d8-DBT internal standard in them (Figure S-11), and GC−SCD chromatograms of separated thiophenic (middle) and sulfidic (bottom) fractions from ZS1C crude oil with d8-DBT internal standard in them (Figure S-12) (PDF). The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.energyfuels.5b00897.

4. CONCLUSION The two ultra-deep formation crude oils from Tarim Basin have a large difference in sulfur compound composition, which are both unique compared to common crude oils. A homologue series of H6DBTs was detected in Ha9 crude oil. This is the first time that these biomarker-like compounds were identified in crude oil. Thiadiamondoids with 1−3 cages were identified in ZS1C crude oil, which present a larger number of structural isomers than other crude oils. The selective separation of F

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (NSFC U1162204, 21236009, and 21376262).



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