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Athabasca油砂沥青焦化蜡油中富氮组分的分离与表征_英文_

Athabasca油砂沥青焦化蜡油中富氮组分的分离与表征_英文_
Athabasca油砂沥青焦化蜡油中富氮组分的分离与表征_英文_

Petroleum Science

2004 V ol.1 No.3

Separation and Characterization of Nitrogen-Rich Components

in Coker Gas Oils from Athabasca Bitumen

Xu Zhiming1, Zhao Suoqi1, J. R. Woods2, L. S. Kotlyar2 and K. H. Chung3

(1 State Key Lab. of Heavy Oil Processing, University of Petroleum, Beijing 102200, China)

(2 Institute for Chemical Process and Environmental Technology of NRC, Canada, K1A 0R6)

(3 Edmonton Research Centre, Syncrude Canada Ltd., Canada, T6N 1)

Received November 20, 2003

Abstract: It is well known that gas oils from oilsands bitumen are difficult to hydrotreat. In order to develop the most

appropriate flow sheet and operating conditions, a thorough knowledge of the molecular structure and behaviour of

bitumen and its gas oil products is needed. In this work, the gas oil samples are fractionated in an attempt to isolate and

identify the problematic molecular species for hydrotreating. It is found that the major nitrogen sources in coker gas oils

are associated with relatively small pentane insoluble species and an even smaller, highly polar, hexane insoluble species.

Structural information obtained for these fractions indicates that they are formed during the cracking of resin molecules.

Nitrogen speciation shows that the pyrroles are the primary nitrogen type, with pyridines also being an important species.

Both nitrogen species are undesirable in the hydrotreating process. Pyrroles in particular are subject to polymerisation,

producing gums and sediments that foul filters and other equipment while pyridines can directly deactivate the

hydrotreating catalyst.

Key words: Coker gas oil, pentane insoluble, hexane insoluble, separation, characterization

1. Introduction

The primary products from Athabasca bitumen coking are light and heavy gas oils. Although significant amounts of metals, sulfur and nitrogen are removed during coking, the heteroatom content of gas oils is unacceptably high and must be lowered in subsequent processing. It is well known that gas oils from bitumen are difficult to hydrotreat. Conventional catalysts in particular are degraded much more than expected owing to poisoning and difficulty of coking to hydrogenate nitrogen-bearing components. Nitrogen heterocycles may also contribute to processing problems through the formation of insoluble sediments and gums (Mushrush and Speight, 1995). Consequently, the amount and role of nitrogen-bearing components are of a special interest in the design of bitumen upgrading processes.

Gas oils are first treated with pentane to remove pentane insolubles quantitatively from each sample. A high performance liquid chromatography (HPLC) allows a further fractionation based on molecular polarity. Each fraction is characterized by several complementary analytical techniques and compared with similar data for other bitumen upgrading streams. Benchmarking samples include the insoluble end-cuts from Supercritical Fractionation & Extraction (SFE) of virgin bitumen pitch and fluid coking pitch ( Zhao, et al., 2001A; 2001B) together with the solubility class fractions (SARA) of the front-cuts derived from these pitch samples. The results are discussed in terms of the role played by nitrogen-rich components during bitumen upgrading.

2. Experimental

2.1 Samples

The samples used in this work were obtained from the bitumen upgrading plant at Syncrude Canada Ltd. Table 1 summarizes the source and identification for each sample.

Bitumen pitches are produced as the bottom fractions from atmospheric and vacuum distillation towers. Together, these pitches provide feedstock to a fluid coker. In this work, the Atmospheric-distillation Tower Bottom (ATB) fraction is used. In a one-time test, a coker is run in a once-through mode. The slurry formed during vapour washing in the coker is removed immediately instead of being recycled. After removal of volatiles the heaviest fraction from this operation is identified as Once-Through-Slurry-Bottom (OTSB). The major coker products are light and heavy gas oils that are blended to produce coker combined gas oil. Combined gas oils are mixed with vacuum heavy gas

Separation and Characterization of Nitrogen-Rich Components

73

V ol.1 No.3 oil and stored in a surge tank before passing through a Pall mesh filter (25 μm), just prior to hydrotreating. Since the syncrude upgrading process configuration was changed in 1999, these filters have been subject to severe plugging or fouling by gummy residues.

Table 1 Sample description and identification list

Streams Description IDs for

Separated

Fractions

Coker Heavy Gas Oil (GO-1) PI-1 Hydrotreater feed before filter (GO-2)

PI-2

Hydrotreater feed after filter (GO-3) PI-3

Coker Combined Gas Oil from Coker 1 (GO-4)

PI-4

Coker Gas Oils Coker Combined Gas Oil from Coker 2 (GO-5)

PI-5

Coking Pitch Fluid coking pitch from once through slurry mode (OTSB) OTSB-EC

Bottom fractions from atmospheric and distillation tower (A TB) ATB-EC SARA fractions: Saturates Aromatics Bitumen Pitch Resins 2.2 Sample separation

Pentane insolubles (PI) contents of gas oils were measured by dissolving the samples in equal volumes of toluene, followed by dilution with 40 volumes of n -pentane. This procedure is conducted at room temperature over a period of 8 hours. Precipitates are separated by filtration and the collected solids washed repeatedly with fresh pentane until the filtrates are colourless. Any toluene insoluble, or inorganic matter, is removed from the PI samples by a procedure described elsewhere ( Xu, et al .). The separated PI material amounts to only 0.2 to 0.4wt% of the parent gas oil samples.

The insolubles, or end-cut fractions from SFE of ATB and OTSB (Chung, et al ., 1997; Chung and Xu, 2001) are designated as ATB-EC and OTSB-EC. The inorganic minerals usually associated with these heavy fractions are quantitatively separated by an ultra- centrifugation procedure also described elsewhere (Kotlyar, et al., 1999). The soluble front-cuts from SFE are divided into saturates, aromatics and resins (SARA) by means of adsorption chromatography on alumina (The asphaltene fraction has been removed during SFE). HPLC group separation is carried out on the GO-1 using a preparative column (20mm ×250mm NH 2, from

Waters Ltd.) at a temperature of 40°C with hexane (5

mL/min) as the mobile phase. After 25 minutes, methyltertiarybutylether is introduced as a second solvent. The photodiode array detector collects UV signal data for wavelengths ranging from 240 to 400nm. Retention times for aromatic group separation are estimated from the chromatograph of a standard mixture containing each of the saturate, monoaromatic, diaromatic and polyaromatic compounds. It becomes apparent that, apart from saturates, mono- and diaromatics, the HPLC separation is based on molecular polarity rather than the number of aromatic rings.

2.3 Analyses Bulk elemental concentrations (carbon, hydrogen, nitrogen and sulfur) are determined with a CHNS analyser. A LECO VTF-900 analyser attachment provides oxygen contents. Gel Permeation Chromatography (GPC) provides number (MW n ) and weight (MW w ) average molecular weights based on calibration with polystyrene standards. Heteroatom

speciations (sulfur and nitrogen) are provided by X-ray

Photo-Electron Spectroscopy (XPS). Structural analysis data are obtained from Proton Nuclear Magnetic Resonance (1H-NMR) measurements. The average structural parameters are calculated

from the results of 1H-NMR, molecular weight and elemental analyses based on methods described elsewhere (Zhao, et al ., 2001A).

3. Results and discussion

Elemental analyses for the coker gas oils, ATB and OTSB are summarised in Table 2. The results for the five gas oil samples are similar and cover relatively narrow ranges. Compared with bitumen pitches, the gas oils have lower heteroatom contents but higher H/C ratios.

Table 2 Elemental analysis of gas oils and pitch samples Composition (w/w%)

Streams

C H N S

H/C

GO-1 84.71 11.26 0.53 4.45 1.60GO-2 82.59 10.39 0.34 4.19 1.51GO-3 80.72 11.05 0.36 4.02 1.64GO-4 81.15 10.10 0.33 4.23 1.49GO-5 82.76 10.18 0.39 3.97 1.48OTSB 83.90 8.40 0.80 5.60 1.20ATB 80.40 9.30 0.90 6.50 1.39

Petroleum Science

2004

74 3.1 Bitumen pitch fractions

The molecular weights, elemental analyses and average structural parameters for ATB-EC and SARA fractions from bitumen pitch are presented in Table 3. In terms of weight (MW w ) and number (MW n ) average molecular weights, the values for the aromatic and resin classes are similar. The resin fractions have slightly lower H/C atomic ratios but higher f a values; a comparison of the H au /C A ratios for the class members indicates that the resin samples are somewhat more condensed than the aromatics. Also, the δ parameter values show that aromatic rings in the resins are less substituted than those in the corresponding aromatic fractions. For both resins and aromatics the number of repeating units (n) in each molecule falls in the range of 1 to 1.4. On the other hand, the resins have a slightly higher number of aromatic rings (R a ) per unit than the corresponding aromatic fractions.

Table 3 Yield and characteristics of end-cut and SARA

fractions from bitumen pitch

In terms of heteroatoms, the aromatic fractions have higher sulfur contents than the corresponding resin class; in each case, thiophenic sulfur is the dominant type (see Table 3). A significant difference is that the nitrogen contents for the resin components are much higher than those found in the corresponding aromatic fractions. Only trace amounts of nitrogen are present in saturates.

The molecular units, or core structures, in the SARA fractions and ATB-EC show major differences in molecular weight, the number of repeating units (n), the number of aromatic rings (R a ) and the degree of aromatic ring condensation (H au /C A ). For the ATB-EC, these same parameters are significantly higher than those found in any of the SARA fractions. The ATB-EC, representing 40wt% of bitumen pitch, also accumulates most of the heteroatoms, i.e., 55wt% of nitrogen and 47wt% of sulfur, respectively. Another important observation is that the nitrogen concentrations in the resin class are even greater than those determined for the end-cut. In fact, the resins, representing only 18wt% of the original pitch, account for more than 30wt% of the total nitrogen.

3.2 Coker streams fractions

The results given in Table 4 demonstrate that there is little difference in MW n , MW w and H/C values for the pentane insolubles from five coker gas oils. Also, the

values for nitrogen and sulfur are similar, falling within the ranges of 1.7 to 2.4wt% and 5 to 5.7wt%,

respectively. These samples also have similar aromaticities (f a = 0.5 to 0.52) and are best represented by a single primary unit (n = 1). Each molecule in the

pentane insoluble (PI) fractions comprises approximately two naphthenic and three aromatic rings with a similar degree of ring condensation (H au /C A ).

The δ parameter values for these samples also show that

the aromatic rings are substituted to a similar extent by alkyl groups with comparable chain lengths (L).

Table 4 Characteristics of pentane insolubles separated

from coker streams

Pentane insolubles from coker gas oil Sample characteristics OTS

B-EC PI-1 PI-2 PI-3PI-4PI-5MW w 2328

660 802 753917925MW n 1014

384 425 398459479H/C 0.79

1.15 1.14 1.02 1.18

1.17N (wt%) 1.00 1.85

2.00 2.4 1.65 1.76O (wt%) 4.11

3.17 3.73 3.87 3.28 3.81Total S (wt%) 6.50

4.98

5.49 5.56 5.28

5.65Thiophenic sulfur (wt%)

6.0 3.3 3.8 3.6

3.7

4.0f a 0.670.51 0.51 0.520.50.52H au /C A 0.380.7 0.68 0.70.650.71δ 0.500.45 0.47 0.470.47

0.47

n 1 1 1 1 1 1

R a 15.4

3 3.3 3 3.7 2.8

Rn 4.3 2.4 2.5 2.5 2.4

1.9

L 3.7 3.3 3.6 3 4 4.3

SARA fractions from ATB front-cuts Sample

characteristics

Saturates Aromatics Resins

A TB-EC Overall yields (% of original

pitch)

6 36 18 40

M w 827 601-1720 587-1855 10890 M n 745 512-1079 493-1065 3137 H/C (atomic) 1.80 1.37-1.48 1.30-1.34 1.22 N (w%) 0.02 0.26-0.36 1.30-1.70 1.10 N (% of total N in pitch) <0.5 13 32 55 S (w%)

0.30 5.56-7.72 3.70 -5.98 7.2

S (% of total S in pitch) <0.5 39 14

47

Thiophenic sulfur (w%)

0.28 3.23-4.66 2.42-4.27 5.1

f a 0.11

0.31-0.37 0.39-0.41 0.45 H au

/C A

1.03 0.62-0.78 0.6-0.7 0.45 δ 0.87 0.52-0.62 0.52-0.54 0.55

n 1 1-1.4 1-1.4 2.9

R a 0 2.2-4.2 3-4.7 10.0 R n 3.4 2.4-2.7 2.5 3.1 L 4.1 4.3-6.1 4.3-5.8 6.3

Separation and Characterization of Nitrogen-Rich Components

75

V ol.1 No.3 There are obvious differences between bitumen pitch end-cut (ATB-EC) and coking pitch end-cut (OTSB-EC), when Tables 3 is compared with Table 4. The latter has a lower molecular weight, H/C atomic ratio and number of repeating units (n) per molecule. Compared with ATB-EC, the repeating units in OTSB-EC have a greater number (R a >15) of highly condensed (lower H au /C A ) aromatic rings with shorter alkyl substituents (lower L).

Preparative, chromatographic separation of GO-1 produces saturate and aromatic fractions plus three highly polar sub-fractions (POL-1, POL-2 and POL-3), where POL-2 and POL-3 are insoluble in hexane when separated from the parent sample. The yields, molecular weights and elemental analyses for these fractions are given in Table 5.

Table 5 Yields and analyses for HPLC fractions

HPLC fractions

Polars

Properties

Saturates Aromatics

POL-1 POL-2POL-3

Yield, wt% 23.5 40.2 22.5 11.5 2.3MW w 450 315 254 261 266MW n 330 216 187 212 226

H/C (atomic) 1.8 1.43 1.15 1.18 1.17

N (wt %) 0.1 0.12 0.64 2.22 2.95N (% of total N in pitch) 4 9 26 48 13 Pyrrolic nitrogen

(w%)

b.d.l. b.d.l. 0.3 1.9 2.4Pyridinic nitrogen (w%)

b.d.l. b.d.l. 0.3 0.2 0.2O (wt%) 0.4 0.6 1.0 2.5 2.9

O (% of total O in pitch) 8 27 25 32 8 S total (wt%) 0.20 4.12 7.60 5.00 4.48S (% of total S in pitch)

1 41 41 15 2

Thiophenic sulfur (wt%) b.d.l. 3.1 5.9 3.3 2.9b.d.l. = below detection limit

Here, we see that the saturate and aromatic fractions are associated with insignificant amounts of heteroatoms (nitrogen, oxygen and sulfur). However, both nitrogen and oxygen contents increase rapidly for samples POL-1 through POL-3. In fact, the combined POL-2 and POL-3 samples, representing only 14wt% of the parent gas oil, contain more than 60wt% of the total nitrogen and 40wt% of the oxygen. Results from XPS measurements on these samples point to pyrroles as the primary nitrogen species with pyridines also being significant. In each case, sulfur is mostly thiophenic in nature; the first polar sub-fraction (POL-1) had the highest sulfur content.

A comparison of the polar sub-fractions from coker heavy gas oil shows only marginal differences in molecular weights and average structural parameters (see Tables 5 and 6). In essence, each of the molecules has an average of two aromatic rings (R a ) with virtually the same aromaticity (f a ) and H/C atomic ratio. Also, the aliphatic chain lengths (L), the degree of aromatic ring substitution (δ) and condensation (H au /C a ) are similar.

Table 6 Average structural parameters for HPLC fractions HPLC fractions from KHGO Polars

Molecular parameter

Aromatics

POL-1 POL-2 + POL-3

f a 0.36 0.55 0.53 H au /C A 0.91 0.86 0.87

δ

0.57 0.47 0.48 n 1 1 1

R a 1.3 1.6 1.6 Rn 2 1.7 1.7 L 4.5 3.4 3.7

4. Origin of the nitrogen-rich components and their roles during bitumen upgrading It is well known that the pentane insoluble, or end-cut fraction, is the most problematic component of Athabasca bitumen pitch. This fraction is the major source for coke formation under thermal cracking conditions. Carry-over of this component from the coker may also be partly responsible for fast catalyst deactivation during hydrotreating. An average molecule in the end-cut fraction comprises polyaromatic “core” structures and associated heteroatoms (N, thiophenic S) in three repeating units. Aliphatic sulfides, n-alkanes or metals act as bridges between these units (Speight, 1991). Pentane soluble resin material, with a high nitrogen content, is another potentially troublesome fraction present in bitumen pitch. Compared with molecules in the end-cut

fraction, resins are smaller and contain fewer repeating units, each with less condensed aromatic rings. Although the results of structural analysis point to a high degree of aromatic ring condensation, especially for end-cut molecules, a more open structure, visualized as a collection of interconnected smaller units, cannot be ruled out (Speight, 1991). The thermal reactions occurring during coking involve the cracking of side chains, bridges and sulfide linkages together with an aromatisation of aliphatic structures. Although the aromatic rings are fairly stable at moderate cracking temperatures (350-500oC), condensed aromatics

Petroleum Science 2004 76

may undergo ring destruction (Speight, 1991). Thermolysis of aryl-alkyl bonds can be enhanced by the presence of nickel, vanadium, heterocyclic nitrogen and other heteroatoms. Free radical formation during the cracking is accompanied by condensation reactions. When such reactions involve the heavy “core” molecules in a pitch, like A TB-EC, the result is coke formation.This view is consistent with the observed accumulation of nitrogen and sulfur species in bitumen coke.Even though some condensation products are still soluble in toluene, they remain with the residue. An example is the highly aromatic, single-unit, OTSB-EC material.

Under thermal cracking conditions, the majority of cracked resin molecules report the product stream, i.e., as a coker gas oil component. The thermal reactions, including fragmentation of polyaromatic structures, cause a decrease in overall molecular weight and size, average number of aromatic rings and chain length of aliphatic substituents. These reactions produce a concomitant increase in aromaticity. Because nitrogen functional groups tend to be more stable to thermolysis, the nitrogen content of the cracked molecules increases, compared to the parent resin molecules. Based on this logic, the resin fraction must be the primary source of the pentane insoluble and hexane insoluble, polar HPLC fractions (POL-2 and POL-3). The most remarkable feature of these fractions is their high nitrogen content. For example, POL-2 and POL-3 constitute only 14wt% of the gas oil but are associated with more than 60wt% of the total nitrogen.

The presence of nitrogen-rich species in gas oil has important implications for industrial processes. Pyrroles may be the key factor in the formation of insoluble sediments and gums in coker gas oils during downstream processing (Mushrush and Speight, 1995). The solubility of this polar material may be further decreased by adsorption onto a small amount of iron and clay minerals also present in gas oil. These minerals are known for their ability to interact with polar crude oil components (Wang, et al., 1998; Cosultchi, et al., 2001). This combination of polar nitrogen-rich species and mineral solids is believed to be the problematic foulant observed on filters and other equipment during hydrotreating. In addition to the problems associated with neutral pyrroles, the presence of basic pyridines will deactivate the hydrotreating catalyst by neutralizing acid sites.

5. Conclusions

Coker gas oils contain a significant amount of nitrogen-rich material with a relatively low molecular weight. Structural information indicates that these molecules are formed in the cracking of the resin fraction originally present in bitumen. Nitrogen speciation shows that pyrroles are the primary nitrogen species followed by pyridines. Both of these nitrogen species are undesirable in hydrotreating processes. Pyrroles in particular, polymerize to produce filter-fouling gums and sediments while pyridines may directly deactivate the hydrotreating catalyst. References

Chung, K., Xu, C. and Hu, Y. (1997) “Super-critical Fluid Extraction Reveals Resid Properties ”, Oil and Gas Journal, 95(3): 66

Chung, K. H. and Xu, C. (2001) “Narrow-cut Characterization Reveals Resid Process Chemistry”, Fuel, 80, 1165 Cosultchi, A., Garciafigueroa, E., Carcia-Borquez, A., Reguera, E., Y ee-Madeira, H., Lara, V. H., Bosch, P. (2001) “Petroleum Solid Adherence on Tubing Surface”, Fuel, 80, 1963-1968

Kotlyar, L. S., Sparks, B. D., Woods, J. R. and Chung, K. H.

(1999) “Solids Associated with the Asphaltene Fraction of Oilsands Bitumen”, Energy and Fuels, 13, 346-350 Mushrush, G. W. and Speight, J. G. ( 1995 ) “Petroleum Products: Instability and Incompatibility(Applied Energy Technology Series)”, Tailor & Francis, Washington

Speight, J. G. (1991) “The Chemistry and Technology of Petroleum”. Marcel Dekker Inc., New York

Wang, S., Chung, K. H., Masliyah, J. H. and Gray, M. R. (1998) “Toluene-insoluble Fraction from Thermal Cracking of Athabasca Gas Oil: Formation of a Liquid-in-oil Emulsion That Wets Hydrophobic Dispersed Solids”, Fuel, 77(14), 1647-1653

Xu, Z., Wang, Z., Kung, J., Woods, J. R., Chung, K. H., Kotlyar, L.

S., Sparks, B. D. and Wu, X., “Separation and Identification of Suspended Solids in Coker Gas Oil from Athabasca Bitumen”, Fuel, submitted

Zhao, S., Kotlyar, L. S., Woods, J. R., Sparks, B. D. and Chung, K.

H. (2001A) Effect of Thermal and Hydrocatalytic Treatment on

the Molecular Chemistry of Narrow Fractions of Athabasca Bitumen Pitch, Energy and Fuels, 15(1), 113-119

Zhao, S., Kotlyar, L. S., Woods, J. R., Sparks, B. D., Hardacre, K. and Chung, K. H. (2001B) “Molecular Transformation of Athabasca Bitumen End-cuts During Coking and Hydrocracking”, Fuel, 80, 1155-1163

About the first author

Xu Zhiming, male, born in 1969, is

an associate professor at the State Key

Laboratory of Heavy Oil Processing in

the University of Petroleum (Beijing).

He received his MS degree in chemical

engineering from the University of

Petroleum in 1994. His major research interests cover heavy oil processing and supercritical fluid technology. E-mail address: scf@https://www.wendangku.net/doc/0116858381.html,

(Edited by Zhu Xiuqin)

Separation and Characterization of Nitrogen- Rich Components 77 V ol.1 No.3

Athabasca油砂沥青焦化蜡油中富氮组分的分离与表征

许志明1赵锁奇1 J.R. Woods 2 L.S. Kotlyar2 K.H Chung 3

(1 石油大学重质油国家重点实验室, 中国北京昌平 102200)

(2 加拿大国家研究院化工过程与环境技术研究所, 加拿大渥太华K1A 0R6)

(3 加拿大合成油公司埃德蒙顿研究中心,加拿大埃德蒙顿 T6N 1H4)

摘要:油砂沥青焦化蜡油的加氢处理是比较困难的,为了选择合适的加工流程和操作条件,有必

要对油砂沥青及其焦化蜡油的分子结构有更全面的认识。本研究尝试分离和鉴别焦化蜡油中对加

氢过程不利的组分。研究发现,焦化蜡油中主要的富氮组分是较小分子的戊烷不溶物,或者是更

小分子、极性较强的己烷不溶物。组分的结构信息表明它们是由胶质分子裂化反应后形成的。吡

咯类化合物是主要的氮化物类型,其次是吡啶类化合物。这两类氮化物都对加氢过程不利,如吡

咯类化合物容易聚合产生胶质和沉淀,堵塞过滤器和其它设施;而吡啶类物质能直接导致加氢催

化剂失活。

关键词:焦化蜡油戊烷不溶物己烷不溶物分离表征

(continued from page 48)

定量描述非均质油藏化学驱波及效率和驱替效率的作用

沈平平袁士义邓宝荣宋杰沈奎友

(中国石油勘探开发研究院,中国北京 100083)

摘要:本文利用我国自行研制的ASP数值模拟软件,采用正韵律二维剖面地质模型,分别模拟

了水驱、聚合物驱、三元复合驱的驱油过程,分层计算了采收率、剩余油饱和度、波及效率

和驱替效率,进行了指标对比。通过研究表明对于非均质严重的油藏,不同层段的波及效率

和驱替效率所起的作用不同。高渗层以提高驱替效率为主,低渗层以提高波及效率为主,中

等渗透层提高波及效率和提高驱替效率相当。由于水驱后,剩余油大部分集中在上部,低渗

透层是提高采收率主要潜力所在,提高上部低渗透层的波及效率对于提高总体采收率具有重

要的作用。对于非均质严重的油藏,先调剖再注三元复合体系段塞是提高化学驱油效果的重

要途径。

关键词:化学驱驱替效率波及效率提高采收率非均质油藏

数据库信息管理系统简介外文翻译

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