Influence of inherent carbonates and silicates on pyrolytic products of Tailao oil shale

doi:10.11949/j.issn.0438-1157.20161358

Abstract

Abstract:

Tailao oil shale was subject to step-wise acid washing to eliminate the inherent carbonate and silicate minerals. The pyrolysis experiments of original oil shale and its demineralization products were carried out in an aluminum retort. The composition and property of shale oil and pyrolytic gas were characterized by elemental analysis, chemical class composition, gas chromatography-mass spectrometer (GC-MS) and gas chromatography (GC). The influence of inherent carbonate and silicate minerals on pyrolysis was studied by comparing the product yields and compositions. The results showed that carbonates promoted the formation of shale oil and nitrogen-and oxygen-containing compounds, while silicates inhibited the evolution of oil and oxygenated compounds. Both carbonates and silicates decreased the H/C atomic ratio of shale oil. Furthermore, silicates would catalyze the combination of alkyl free radicals and hydrogen free radicals and cracking of long-chain aliphatic hydrocarbons, which increased the alkanes and short-chain hydrocarbons contents of shale oil, as well as the hydrocarbon gases yields, but decreased the hydrogen yield. On the contrary, carbonates suppressed the combination of free radicals and cracking of long-chain aliphatic hydrocarbons.

Key words: oil shale, pyrolysis, demineralization, shale oil, radical, cracking

摘要：

通过逐级酸洗脱除新疆太姥油页岩中的碳酸盐和硅酸盐矿物，采用铝甑炉对油页岩原样和脱矿样进行热解，分析油气产物的组成性质，基于产物产率和性质考察了固有矿物质对油页岩热解的影响。结果表明，碳酸盐能促进热解生油，且使页岩油中含氮、氧化合物含量增大，硅酸盐则抑制热解生油，并抑制含氧化合物的生成，二者均使页岩油的H/C降低。硅酸盐可促进烷基自由基与氢自由基的结合，使页岩油中烷烃含量升高、烯烃含量降低，且使H₂产率减小，并能催化长链脂肪烃的裂解，使页岩油中长链烃含量降低、短链烃含量升高，且使烃类气体产率增大，而碳酸盐则抑制自由基的结合和长链脂肪烃的裂解。

关键词: 油页岩, 热解, 脱矿物质, 页岩油, 自由基, 裂解

CLC Number:

TK16

CHANG Zhibing, CHU Mo, ZHANG Chao, BAI Shuxia, LIN Hao, MA Liangbo. Influence of inherent carbonates and silicates on pyrolytic products of Tailao oil shale[J]. CIESC Journal, 2017, 68(4): 1582-1589.

畅志兵, 初茉, 张超, 白书霞, 林浩, 马良博. 固有碳酸盐和硅酸盐对太姥油页岩热解产物的影响[J]. 化工学报, 2017, 68(4): 1582-1589.

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