原油热裂解过程中的红外光谱演化特征及其主控因素

doi:10.11743/ogg20230112

Abstract

Abstract:

Infrared spectra of crude oils can indicate information of various molecular groups， which is of great potential to identifying the genetic type and thermal evolution degree of crude oil. In this study， pyrolysis experiments are performed on two immature crude oil samples from different organic facies， to preliminarily investigate the infrared spectra evolution of crude oils under pyrolysis and its controlling factors. The results indicate that the infrared spectra evolutions are similar for the two oil samples and can be approximately divided into two stages with the increase in oil cracking extent. At the early stage with experiment temperatures of lower than 370 ℃， the $A C H 3$ / $A C H 2$ value of cracking oil varies slightly， while the A_aro and A_aro/A_sat values progressively decrease. This is due to some compounds with a weak thermal stability undergoing debranching during this stage， which results in an increase in saturated hydrocarbon content and decrease in the ratio of aromatic/saturated hydrocarbons. At the later stage with experiment temperatures of over 370 ℃， the $A C H 3$ / $A C H 2$ ， A_aro and A_aro/A_sat values of oil samples significantly increase mainly due to the compounds with long molecular chain structures significantly cracked into compounds with short molecular chain structures， causing an increase in the $A C H 3$ content. Meanwhile， the aromatization degree of the compounds is significantly enhanced at this stage， which results in an increase in aromatic hydrocarbon content as well as the ratio of aromatic/saturated hydrocarbons. There are still some differences in the infrared spectral parameters between the two oil samples during the oil cracking process， especially at the early stage. Therefore， cross plots of infrared spectral parameters， such as the plot of A_CH3/A_CH2-A_aro/A_sat， can be used to classify the types of crude oils and identify their thermal maturity.

Key words: extent of thermal cracking, infrared spectra, content of aromatics, content of saturates, pyrolysis experiment, crude oil

CLC Number:

TE122.1

Botong LIU, Peng CHENG, Haifeng GAI, Qin ZHOU, Tengfei LI, Hui TIAN. Infrared spectra evolution of crude oil under pyrolysis and its controlling factors[J]. Oil & Gas Geology, 2023, 44(1): 150-163.

Figures/Tables 12

Table 1

Fig. 1

Table 2

The extents of thermal cracking， group compositions and infrared spectral data of the pyrolytic oils at different temperatures"

样品编号	实验温度/℃	EqVR_o/ %	裂解率R_c/%	族组分含量					TNR-1	红外光谱数据
				族组分含量						芳环结构				烷基结构
				饱和烃/%	芳烃/ %	非烃/ %	沥青质/%	芳烃/饱和烃		A_C-H	A_C=C	A_C-C	A_aro	$A C H 2$	$A C H 3$	$A C H 3$ / $A C H 2$	A_sat	A_aro/A_sat
WC191N1	300	0.74	20.93	50.19	13.82	11.45	24.54	0.28	0.74	0.08	0.03	0.03	0.15	1.54	0.77	0.50	2.31	0.06
	330	0.87	23.19	51.97	13.60	9.39	25.04	0.26	0.95	0.08	0.02	0.02	0.13	1.52	0.73	0.48	2.24	0.06
	360	1.06	31.62	53.53	13.48	7.68	25.31	0.25	0.97	0.01	0.02	0.01	0.04	1.40	0.58	0.41	1.98	0.02
	380	1.23	42.84	55.91	13.52	3.98	26.59	0.24	1.22	0.05	0.03	0.02	0.10	1.34	0.64	0.48	1.98	0.05
	400	1.42	60.11	40.21	15.26	3.23	41.30	0.38	1.47	0.15	0.07	0.07	0.28	1.44	0.97	0.67	2.41	0.12
	420	1.65	85.74	10.07	28.17	2.78	58.98	2.80	2.29	1.00	0.23	0.19	1.43	1.37	1.94	1.41	3.31	0.43
QH1811	300	0.74	22.99	50.83	20.07	13.95	15.16	0.39	0.64	0.14	0.05	0.04	0.24	1.32	1.01	0.77	2.33	0.10
	330	0.87	28.34	52.51	17.50	13.20	16.78	0.33	0.70	0.11	0.04	0.03	0.17	1.46	1.13	0.77	2.59	0.07
	360	1.06	34.47	54.63	17.22	10.60	17.55	0.32	0.76	0.07	0.01	0.02	0.10	1.57	1.19	0.76	2.76	0.04
	380	1.23	37.95	55.24	15.65	7.50	21.61	0.28	0.80	0.07	0.02	0.02	0.11	1.56	1.20	0.77	2.76	0.04
	400	1.42	49.12	51.17	19.63	2.57	26.64	0.38	1.48	0.20	0.06	0.06	0.32	1.41	1.26	0.90	2.67	0.12
	420	1.65	80.96	18.88	25.65	2.02	53.45	1.36	1.84	0.53	0.24	0.22	0.98	1.39	1.82	1.31	3.21	0.31

Table 2

Fig. 2

Fig. 3

Fig. 4

Table 3

Infrared spectral data of the aromatic compositions in pyrolytic oils at different temperatures"

样品编号	裂解率 R_c/%	红外光谱数据
		芳环结构				烷基结构				A_aro/A_sat
		A_C-H	A_C=C	A_C-C	A_aro	$A C H 2$	$A C H 3$	$A C H 3$ / $A C H 2$	A_sat	A_aro/A_sat
WC191N	20.93	0.15	0.04	0.05	0.24	1.52	0.99	0.65	2.51	0.10
	23.19	0.14	0.04	0.05	0.23	1.50	1.01	0.67	2.52	0.09
	31.62	0.10	0.03	0.04	0.17	1.49	0.96	0.64	2.45	0.07
	42.84	0.30	0.07	0.08	0.44	1.49	1.14	0.77	2.63	0.17
	60.11	0.75	0.18	0.23	1.17	1.46	1.83	1.25	3.29	0.35
	85.74	1.20	0.27	0.35	1.82	1.43	2.28	1.59	3.72	0.49
QH18	22.99	0.23	0.06	0.07	0.36	1.46	1.25	0.85	2.71	0.13
	28.34	0.22	0.05	0.06	0.34	1.43	1.11	0.78	2.54	0.13
	34.47	0.12	0.04	0.05	0.21	1.46	1.33	0.91	2.79	0.07
	37.95	0.33	0.08	0.10	0.50	1.46	1.45	0.99	2.90	0.17
	49.12	0.56	0.13	0.18	0.87	1.44	1.75	1.21	3.19	0.27
	80.96	1.04	0.21	0.28	1.54	1.42	2.17	1.53	3.59	0.43

Table 3

Fig. 5

Fig. 6

Fig.7

Fig. 8

Fig. 9

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Infrared spectra evolution of crude oil under pyrolysis and its controlling factors

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