高温固定流化床费托合成技术及其产物加工路线

doi:10.16085/j.issn.1000-6613.2019-2000

摘要/Abstract

摘要：

与采用低温费托合成主产油品技术相比，产品更为多元化和高值化的高温费托合成技术在目前市场环境下显示出非常明显的优势。本文综述了高温费托合成技术的发展历程及其最新进展，重点介绍了高温费托合成过程中的核心问题，主要包括高温费托合成工艺、固定流化床反应器、费托合成催化剂；介绍了高温费托合成产物分布与特性，讨论了高温费托合成产物的加工路线，并对高温费托合成煤间接液化的工业应用前景和产业化方向进行了展望。结果表明：高温费托合成技术具有产物附加值高、兼顾油品和化学品、技术发展成熟等优势，产物中轻组分含量高、碳数分布较窄、高附加值的α-烯烃含量高；精细化、高端化、差异化加工是实现高温费托合成产物高值化利用的关键。

关键词: 高温费托合成, 煤间接液化, α-烯烃, 固定流化床反应器, 催化剂

Abstract:

Compared with low temperature Fischer-Tropsch synthesis technology with oil as main product，high temperature Fischer-Tropsch technology which produces the more diversified and high-value products, has obvious advantages during the current market environment．In this paper，the development and recent advance of high temperature Fischer-Tropsch synthesis technology are reviewed. The critical issues, including high temperature Fischer-Tropsch synthesis process, fixed-fluidized bed reactor and catalyst of high temperature Fischer-Tropsch synthesis are also discussed. The product distribution and characteristics of high temperature Fischer-Tropsch synthesis are introduced. The products processing route is also discussed, and the industrial application prospect and industrialization direction are prospected. The analysis shows that the high-temperature Fischer-Tropsch synthesis technology has the advantages of high added value of products, consideration of oil products and chemicals, and mature technology. The products have high light component content, narrow carbon number distribution and high added value α-olefin content. Fine, high-end, and differential processing are the key to achieving high-value utilization of high-temperature Fischer-Tropsch synthesis products.

Key words: high temperature Fischer-Tropsch synthesis, indirect coal liquefaction, α-alkene, fixed-fluidized bed reactor, catalyst

中图分类号:

TQ 529.2

吴建民, 孙启文, 董满祥, 张宗森, 刘继森, 孙燕. 高温固定流化床费托合成技术及其产物加工路线[J]. 化工进展, 2020, 39(S1): 12-20.

Jianmin WU, Qiwen SUN, Manxiang DONG, Zongsen ZHANG, Jisen LIU, Yan SUN. High temperature fixed-fluidized bed Fischer-Tropsch synthesis technology and its products processing route[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 12-20.

图/表 9

图1 SAS固定流化床费托合成工艺流程

图2 上海兖矿固定流化床高温费托合成工艺流程

表1 10万吨/年高温费托合成工业示范装置的产物质量选择性

组分	典型工况产物选择性（质量分数）/%
CH₄	8.82
C₂H₄	3.37
C₂H₆	2.59
C₃H₆	8.21
C₃H₈	1.16
C₄H₈	8.61
C₄H₁₀	1.26
C₂～C₄烯烃	20.19
总烯烃	53.30
重质油	3.19
轻质油	50.68
总含氧化合物	9.21

图3 上海兖矿固定流化床高温费托合成反应器

表2 不同还原气氛下熔铁（Fe3O4）催化剂的还原程度（400℃还原8h）

还原气氛	还原度/%	物相组成
100% H₂	80	α-Fe、Fe₃O₄
98% H₂+ 2% CO	20	Fe₅C₂、Fe₃O₄
100% CO	4	Fe₅C₂、Fe₃O₄

表3 上海兖矿高温熔铁催化剂与高温沉淀铁基催化剂的反应性能比较

反应性能	高温熔铁催化剂工业化数据	高温沉淀铁基催化剂中试数据
温度/℃	330~345	330~345
压力/MPa	2.0~2.7	2.0~2.3
（H₂ + CO）转化率/%	93.79	85.59
（CO + CO₂）转化率/%	95.69	87.51
H₂转化率/%	91.02	80.58
CO转化率/%	99.63	98.72
CH₄选择性/%	8.82	9.87
C₂～C₄烯烃选择性/%	20.19	25.35
C₅₊选择性/%	56.77	48.86
含氧化合物选择性/%	9.21	12.06
C₄₊产率/g· $m - 3$ $(H 2 + C O)$	130	119

表3 上海兖矿高温熔铁催化剂与高温沉淀铁基催化剂的反应性能比较

反应性能	高温熔铁催化剂工业化数据	高温沉淀铁基催化剂中试数据
温度/℃	330~345	330~345
压力/MPa	2.0~2.7	2.0~2.3
（H₂ + CO）转化率/%	93.79	85.59
（CO + CO₂）转化率/%	95.69	87.51
H₂转化率/%	91.02	80.58
CO转化率/%	99.63	98.72
CH₄选择性/%	8.82	9.87
C₂～C₄烯烃选择性/%	20.19	25.35
C₅₊选择性/%	56.77	48.86
含氧化合物选择性/%	9.21	12.06
C₄₊产率/g· $m - 3$ $(H 2 + C O)$	130	119

图4 高温费托合成产物碳数分布

表5 高温费托合成反应水组成

种类	质量分数/%
含氧化合物	8.4754
醛类组分	0.8772
酯类组分	0.0365
酮类组分	1.7463
醇类组分	5.1931
酸类组分	0.6222
水	91.5246

图5 高温费托合成产物加工路线

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