Variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis
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摘要: 将桦甸油页岩分别在300、350、400、450、500和550℃热解得到半焦，对半焦进行逐级抽提和酸洗，得到自由沥青、碳酸盐束缚沥青和硅酸盐束缚沥青，采用柱层析、FT-IR和GC-MS表征不同沥青的化学组成和结构特征，探讨沥青的化学组成变化及与矿物质的相互作用。结果表明，沥青总产率先增大后减小并在400℃取得最大值4.63%，400-450℃大量沥青分解生成页岩油，使沥青产率降至0.98%。350-450℃自由沥青主要发生羧酸脱羧、酯基分解和长链烷烃裂解反应，使羧酸和酯类化合物含量降低、烷烃碳链长度缩短。干酪根分解生成的羧酸与碳酸盐反应生成羧酸盐，使400℃碳酸盐束缚沥青中羧酸含量达78.82%；含氧化合物可与黏土矿物结合，且烷烃可进入蒙脱石层间，使400℃硅酸盐束缚沥青中含氧化合物和烷烃各占80.79%和19.21%。Abstract: The variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis was studied. Spent shale samples obtained by retorting oil shale at 300-550℃ were subjected to sequential Soxhlet extraction-acid pickling-Soxhlet extraction procedures to obtain free bitumen (FB), bitumen bound with carbonates (BB-1) and bitumen bound with silicates (BB-2). The bitumen samples were characterized by liquid chromatography fractionation, FT-IR and GC-MS. The results show that the total bitumen yield first increases and then decreases with increasing temperature from 300 to 550℃, and reached the maximum value of 4.63% at 400℃. Especially, the intense vaporization and decomposition of bitumen occurring at 400-450℃ causes a dramatic decrease in bitumen yield from 4.63% to 0.98%. Decarboxylation of aliphatic acids, decomposition of esters and cracking of long-chain alkanes take place at 350-450℃, which decreases the contents of acids and esters in FB and shortens the chain length of alkanes. The carboxylic acids derived from kerogen pyrolysis can react with carbonates to form carboxylates, leading to a high amount of aliphatic acids in 400℃ BB-1 (78.82%). The contents of oxygenated compounds (acids, esters and phenols) and alkanes of 400℃ BB-2 are 80.79% and 19.21%, respectively, due to the combination between oxygenated compounds and clay minerals, and the insertion of alkanes into the interlayer space of montmorillonite.
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Key words:
- oil shale /
- pyrolysis /
- thermal bitumen /
- chemical composition
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图 2 桦甸油页岩原样和黏土矿物的XRD谱图
Figure 2 XRD patterns of Huadian raw oil shale and its clay mineral concentrate
a: raw oil shale; b: clay mineral concentrate
图 5 以铝甑含油率为基准的沥青和页岩油产率
Figure 5 Total bitumen and shale oil yields on the basis of aluminum retort oil content
图 9 自由沥青样品中各类组分的相对含量(a) 和正构烷烃的碳数分布(b)
Figure 9 Peak area percentage of major components (a) and carbon number distribution of n-alkanes (b) contained in free bitumen samples
图 10 400 ℃时自由沥青和束缚沥青中各类组分的相对含量
Figure 10 Peak area percentage of major components in bitumen samples derived at 400 ℃
表 1 桦甸油页岩的基本性质
Table 1 Basic properties of Huadian oil shale
Proximate analysis wad/% Ultimate analysis wdaf/% Product yield wad/% M A V FC C H N S O* char oil water gases 5.13 68.58 23.52 2.77 75.61 10.09 1.71 3.18 9.41 79.12 9.75 7.61 3.52 *：by difference 
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表 2 不同类型沥青的族组成特征
Table 2 SARA fractions of different bitumen samples
Sample SARA fraction w/% saturates aromatics resin asphaltene 350 ℃ FB 22.53 19.44 48.15 9.88 BB-1 25.86 7.33 28.45 38.36 BB-2 7.49 3.45 12.28 76.78 400 ℃ FB 21.24 19.24 46.74 12.78 BB-1 17.00 7.91 21.73 53.36 BB-2 6.91 3.46 14.04 75.59 450 ℃ FB 7.03 13.63 46.33 33.01 BB-1 19.24 9.36 23.45 47.95 BB-2 6.41 8.60 24.38 60.61
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表 3 不同沥青样品的主要成分
Table 3 Main compounds identified in bitumen samples
Peak no. 350 ℃ FB 400 ℃ FB 400 ℃ BB-1 400 ℃ BB-2 450 ℃ FB formula CAS no. formula CAS no. formula CAS no. formula CAS no. formula CAS no. 1 C14H30 629-59-4 C7H8O 108-39-4 C7H8O 108-39-4 C13H28 629-50-5 C7H8O 108-39-4 2 C16H34 544-76-3 C11H24 1120-21-4 C8H10O 526-75-0 C16H34 544-76-3 C11H24 1120-21-4 3 C17H36 629-78-7 C12H26 112-40-3 C8H16O2 124-07-2 C16H34 6165-40-8 C13H28 629-50-5 4 C18H38 593-45-3 C13H28 629-50-5 C9H18O2 112-05-0 C18H38 593-45-3 C14H30 629-59-4 5 C14H28O2 544-63-8 C14H30 629-59-4 C10H20O2 334-48-5 C18H38 6418-44-6 C15H32 629-62-9 6 C19H40 629-92-5 C15H32 629-62-9 C11H22O2 112-37-8 C14H28O2 544-63-8 C16H34 544-76-3 7 C20H42 112-95-8 C16H34 544-76-3 C12H24O2 143-07-7 C16H22O4 17851-53-5 C16H34 6165-40-8 8 C16H32O2 57-10-3 C16H34 6165-40-8 C13H26O2 638-53-9 C20H42 112-95-8 C17H36 629-78-7 9 C32H54O4 2432-90-8 C17H36 629-78-7 C14H28O2 544-63-8 C16H32O2 57-10-3 C18H38 593-45-3 10 C21H44 629-94-7 C18H38 593-45-3 C15H30O2 1002-84-2 C32H54O4 2432-90-8 C18H38 6418-44-6 11 C22H46 629-97-0 C14H28O2 544-63-8 C16H22O4 17851-53-5 C21H44 629-94-7 C14H28O2 544-63-8 12 C17H34O2 506-12-7 C19H40 629-92-5 C16H32O2 57-10-3 C24H50 646-31-1 C19H40 629-92-5 13 C23H48 638-67-5 C20H42 112-95-8 C32H54O4 2432-90-8 C23H32O2 119-47-1 C20H42 112-95-8 14 C18H36O2 57-11-4 C16H32O2 57-10-3 C17H34O2 506-12-7 C17H34O3 110-37-2 C20H42 1560-86-7 15 C24H50 646-31-1 C32H54O4 2432-90-8 C18H36O2 57-11-4 C26H42O4 14103-61-8 C16H32O2 57-10-3 16 C19H38O2 646-30-0 C21H44 629-94-7 C19H38O2 646-30-0 - - C32H54O4 2432-90-8 17 C25H52 629-99-2 C22H46 629-97-0 C23H32O2 119-47-1 - - C21H44 629-94-7 18 C23H32O2 119-47-1 C23H48 638-67-5 C26H42O4 14103-61-8 - - C21H44 1560-84-5 19 C17H34O3 110-37-2 C24H50 646-31-1 - - - - C24H50 646-31-1 20 C26H42O4 14103-61-8 C25H52 629-99-2 - - - - C23H32O2 119-47-1 21 C26H54 630-01-3 C23H32O2 119-47-1 - - - - C17H34O3 110-37-2 22 C27H56 593-49-7 C17H34O3 110-37-2 - - - - C26H42O4 14103-61-8 23 C25H40O2 55130-16-0 C26H42O4 14103-61-8 - - - - C28H58 630-02-4 24 C18H36O3 109-37-5 C26H54 630-01-3 - - - - - - 25 C28H58 630-02-4 C27H56 593-49-7 - - - - - - 26 - - C25H40O2 55130-16-0 - - - - - - 27 - - C18H36O3 109-37-5 - - - - - - 28 - - C28H58 630-02-4 - - - - - -
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