微纳尺度气液传质强化油品催化加氢反应

doi:10.16085/j.issn.1000-6613.2023-1627

摘要/Abstract

摘要：

相比于经典的滴流床加氢技术，液相加氢技术由于其一次性投资成本和运行能耗低，受到了企业界和学术界的广泛关注。但如何进一步强化氢油相界面的传质速率来提高液相加氢效率，仍是一个重要的难题。近年来快速发展的微纳尺度气泡或液滴的气液传质强化技术有助于油品催化加氢反应。本文以微纳气泡为例，首先总结了微纳气泡特点及产生方式，简述了微纳尺度气液传质强化液相加氢过程可行性判别，回顾了微纳尺度气液传质强化在油品液相加氢工艺中的相关研究及工业应用。最后分析了微纳尺度气液传质强化在油品液相加氢中面临的挑战以及发展方向，即微纳尺度传质与本征反应的匹配、工况条件微纳气泡在反应器中的流动以及含微纳气泡混合物的气液分离等。

关键词: 微纳尺度, 气泡, 加氢, 传递过程, 过程强化

Abstract:

Compared with the conventional hydrogenation process in trickle bed reactors, liquid-phase hydrogenation with low investment and energy consumption has attracted the attention in industrial and academic community. But how to further intensify the mass transfer rate at the hydrogen-oil interface to improve the efficiency of liquid-phase hydrogenation is still a challenge. In recent years, the gas-liquid mass transfer intensification by micro and nano bubbles or droplets has been rapidly developed, which is helpful for the catalytic hydrogenation of oil products. Taking micro and nano bubbles as an example, this paper firstly summarized the characteristics, and main generation methods of micro and nano bubbles. And the feasibility analysis of micro and nano scale gas-liquid mass transfer to intensify hydrogenation process was briefly described. Current research on the application of micro and nano scale gas-liquid mass transfer intensification in hydrogenation of oil products was reviewed. Finally, the challenges and future research directions of the application of micro and nano scale gas-liquid mass transfer intensification in hydrogenation of oil products were analyzed, including matching the mass transfer rate and intrinsic reaction rate at micro and nano scale, the flow of micro and nano bubbles inside reactor and the gas-liquid separation of the mixture containing micro and nano bubble.

Key words: micro and nano scale, bubble, hydrogenation, transfer process, process intensification

中图分类号:

TQ032

王立华, 蔡苏杭, 江文涛, 罗倩, 罗勇, 陈建峰. 微纳尺度气液传质强化油品催化加氢反应[J]. 化工进展, 2024, 43(1): 19-33.

WANG Lihua, CAI Suhang, JIANG Wentao, LUO Qian, LUO Yong, CHEN Jianfeng. Research progress of micro and nano scale gas-liquid mass transfer to intensify catalytic hydrogenation of oil products[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 19-33.

图/表 13

图1 不同加氢工艺对比

表1 泉州石化柴油液相加氢技术与滴流床加氢技术的能耗对比 (MJ/t)

项目	水	电	蒸汽	燃料气	热输入	合计
液相加氢	38.5	168.9	-153.4	201.1	-25.5	229.6
滴流床加氢	29.7	199.4	22.2	182.2	-31.8	401.7

图2 微纳气泡的气液接触面积大

表2 微纳气泡传质实验研究

研究人员	研究手段	研究体系	气泡特征尺寸范围/μm	传质关联式
Tanaka等^[50]	可视化法	Air-水/表面活性剂溶液	10~100	$S h = 2 + 0.6 R e 1 / 2 S c 1 / 3$
Olsen等^[54]	可视化法	N₂/CO₂/CH₄-海水	200~800	$k L = 2 + 0.95 R e 1 / 2 S c 1 / 3 D d b$
Zeng等^[56]	化学反应法	O₂-亚硫酸铵溶液	200~2500	$S h = 7.28 × 10 - 10 R e 0.8758 S c 0.7045 B o 2.4721 F r - 0.7186$
Bai等^[57]	动态溶氧法	O₂-氯化钠溶液	10~100	$k L a = 1.358 × 10 - 15 Z - 9.243 P e 0.756 σ L μ L a$
Muroyama^[58]	动态溶氧法	O₂-脱氧水	32~40	$k L a = P 0 + ρ L g h 1 - ε G M O 2 U G R T C L * h$

表2 微纳气泡传质实验研究

研究人员	研究手段	研究体系	气泡特征尺寸范围/μm	传质关联式
Tanaka等^[50]	可视化法	Air-水/表面活性剂溶液	10~100	$S h = 2 + 0.6 R e 1 / 2 S c 1 / 3$
Olsen等^[54]	可视化法	N₂/CO₂/CH₄-海水	200~800	$k L = 2 + 0.95 R e 1 / 2 S c 1 / 3 D d b$
Zeng等^[56]	化学反应法	O₂-亚硫酸铵溶液	200~2500	$S h = 7.28 × 10 - 10 R e 0.8758 S c 0.7045 B o 2.4721 F r - 0.7186$
Bai等^[57]	动态溶氧法	O₂-氯化钠溶液	10~100	$k L a = 1.358 × 10 - 15 Z - 9.243 P e 0.756 σ L μ L a$
Muroyama^[58]	动态溶氧法	O₂-脱氧水	32~40	$k L a = P 0 + ρ L g h 1 - ε G M O 2 U G R T C L * h$

图3 单微纳气泡传质实验装置[50]

图4 微纳气泡群传质实验装置[57]

图5 超重力微气泡发生器气泡尺寸观测实验流程示意图[72]1—氮气钢瓶；2—减压阀；3—氮气质量流量计；4—远程智能化控制系统；5—平板光源；6—蓝宝石视镜；7—高速摄像系统；8—背压阀；9—气液分离罐；10—废液罐；11—原料罐；12—液体往复进料泵

图6 3D打印文丘里微气泡发生器[79]

图7 旋流文丘里气泡发生器及性能对比[80]

图8 喷射流气泡发生器结构[64]

图9 多孔膜型气泡发生器产生微气泡[83]

图10 多相催化加氢反应相间传递步骤示意图[90]

表3 不同液相加氢技术对比

项目	Iso Therming技术	SRH技术	SLHT技术	CLTH技术	C-NUM技术
研发单位	美国Process Dynamics	中国石化抚顺石油化工研究院和洛阳石油化工工程公司	中国石化工程建设有限公司和石油化工科学研究院	中国石化长岭石化	中国石油华东设计院和中国石油大学（华东）
操作方式	下行式	下行式	上行式	上行式	上行式
反应器内氢气存在形式	溶解氢	溶解氢+氢气泡	溶解氢+氢气泡	溶解氢+氢气泡	溶解氢+氢气泡
循环泵	有	有	有	无	无
特点	优点：取消了氢气循环压缩机及循环氢净化系统，投资与能耗低；缺点：反应压力高于滴流床工艺，系统压降大，循环泵能耗增加，反应深度不足	优点：油品与氢气直接在管道内混合，对原料的适应性比较强；缺点：与Iso Therming技术相同	优点：保证了反应过程中所需的氢气量，能加工含较多氮、硫、重金属等的柴油原料；缺点：大比例二次加工油生产10mg/kg以下柴油产品时催化剂易结焦	优点：取消了循环油，简化了工艺流程；缺点：产品氧化安定性不合格，需要调整工艺参数，来满足产品要求	优点：通过反应器内构件和床层多点补氢的方式来提高溶氢和补氢能力，保证了反应深度；缺点：与CLTH技术相同
应用情况	中化泉州石化375万吨/年柴油加氢装置^[17]，中石油长庆石化60万吨/年柴油加氢装置^[10]，中海油惠州石化260万吨/年蜡油加氢装置^[115]等	中石化长岭分公司20万吨/年柴油加氢装置^[116]，中石化九江石化150万吨/年柴油加氢装置^[117-118]，湛江东兴化工200万吨/年柴油液相加氢装置^[119]，镇海炼化70万吨/年航煤加氢装置^[120]，胜利石化100万吨/年柴油加氢装置^[121]，长庆石化140万吨/年柴油加氢装置^[122]等	中石化石家庄炼化公司260万吨/年柴油加氢装置^[13]，北京东方石油化工有限公司60万吨/年柴油加氢装置^[123]，中石油哈尔滨石化公司100万吨/年柴油加氢装置^[124]，中石化安庆石化220万吨/年柴油加氢装置^[125]等	中石化北海炼化50万吨/年喷气燃料加氢装置^[126]，中石油格尔木炼油厂15万吨/年航煤加氢装置^[127]，中石油大庆炼化36万吨/年航煤加氢装置^[10]等	中石油庆阳石化公司40万吨/年航煤液相加氢装置^[128]等

表3 不同液相加氢技术对比

项目	Iso Therming技术	SRH技术	SLHT技术	CLTH技术	C-NUM技术
研发单位	美国Process Dynamics	中国石化抚顺石油化工研究院和洛阳石油化工工程公司	中国石化工程建设有限公司和石油化工科学研究院	中国石化长岭石化	中国石油华东设计院和中国石油大学（华东）
操作方式	下行式	下行式	上行式	上行式	上行式
反应器内氢气存在形式	溶解氢	溶解氢+氢气泡	溶解氢+氢气泡	溶解氢+氢气泡	溶解氢+氢气泡
循环泵	有	有	有	无	无
特点	优点：取消了氢气循环压缩机及循环氢净化系统，投资与能耗低；缺点：反应压力高于滴流床工艺，系统压降大，循环泵能耗增加，反应深度不足	优点：油品与氢气直接在管道内混合，对原料的适应性比较强；缺点：与Iso Therming技术相同	优点：保证了反应过程中所需的氢气量，能加工含较多氮、硫、重金属等的柴油原料；缺点：大比例二次加工油生产10mg/kg以下柴油产品时催化剂易结焦	优点：取消了循环油，简化了工艺流程；缺点：产品氧化安定性不合格，需要调整工艺参数，来满足产品要求	优点：通过反应器内构件和床层多点补氢的方式来提高溶氢和补氢能力，保证了反应深度；缺点：与CLTH技术相同
应用情况	中化泉州石化375万吨/年柴油加氢装置^[17]，中石油长庆石化60万吨/年柴油加氢装置^[10]，中海油惠州石化260万吨/年蜡油加氢装置^[115]等	中石化长岭分公司20万吨/年柴油加氢装置^[116]，中石化九江石化150万吨/年柴油加氢装置^[117-118]，湛江东兴化工200万吨/年柴油液相加氢装置^[119]，镇海炼化70万吨/年航煤加氢装置^[120]，胜利石化100万吨/年柴油加氢装置^[121]，长庆石化140万吨/年柴油加氢装置^[122]等	中石化石家庄炼化公司260万吨/年柴油加氢装置^[13]，北京东方石油化工有限公司60万吨/年柴油加氢装置^[123]，中石油哈尔滨石化公司100万吨/年柴油加氢装置^[124]，中石化安庆石化220万吨/年柴油加氢装置^[125]等	中石化北海炼化50万吨/年喷气燃料加氢装置^[126]，中石油格尔木炼油厂15万吨/年航煤加氢装置^[127]，中石油大庆炼化36万吨/年航煤加氢装置^[10]等	中石油庆阳石化公司40万吨/年航煤液相加氢装置^[128]等

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