正构烷烃临氢异构化催化剂研究进展

doi:10.16085/j.issn.1000-6613.2021-1406

摘要/Abstract

摘要：

随环保法规和燃料质量要求逐步严格，作为生产高辛烷值汽油、低凝点柴油和高黏度指数润滑油的重要工艺技术，正构烷烃临氢异构化反应至关重要。本文综述了临氢异构化反应中的双功能催化剂是由提供加氢/脱氢活性的金属中心和用于骨架异构化的酸性载体组成。介绍了双功能催化剂中不同金属中心和酸性载体的贡献，相对于负载贵金属双功能催化剂，双金属、过渡金属磷化物及稀土掺杂催化剂活性相当，抗硫性高，成本低。此外，介微孔分子筛不仅具有易于反应物和产物扩散的较大孔径，还具有适宜酸性，能够促进骨架异构化，用于临氢异构化催化剂的载体而受到广泛关注。最后探讨了影响双功能催化剂异构化性能主要因素取决于金属和酸性载体之间的平衡，即金属中心和酸中心比例及距离。当催化剂存在适宜金属中心/酸中心比例，且金属-酸中心距离处于纳米级范围时，催化活性和异构化产物选择性会更高。

关键词: 正构烷烃, 异构化, 催化剂, 金属, 酸性载体

Abstract:

With the increasing strictness of environmental regulation and fuel quality requirements, the hydroisomerization of n-paraffins for producing high-octane gasoline, low-freezing point diesel and high-viscosity index lubricating oil, becomes more and more important. This review summarizes the bifunctional catalysts for the hydroisomerization reaction, which were mainly composed of a metal center to provide hydrogenation/dehydrogenation activity and an acidic support for skeletal isomerization. The contributions of different metal centers and acidic supports in dual-functional catalysts are introduced. Compared with bifunctional catalysts loaded with precious metals, catalysts doped by bimetallic, transition metal phosphides and rare earth have similar activity, higher sulfur resistance and lower cost. Moreover, mesoporous molecular sieve with large pore size is beneficial to the diffusion of reactants and products, and has high acidity, which promotes the skeleton isomerization. Therefore, it attracts extensive attentions from researchers. Finally, the main factor affecting the isomerization performance of dual-functional catalyst is the balance between the metal and the acidic support, that means, the ratio and distance between the metal center and the acid center. The catalysts with a suitable metal center/acid center ratio and a nano scale metal-acid center distance should have high catalytic activity and isomerization product selectivity.

Key words: paraffins, isomerization, catalysts, metal, acid carrier

中图分类号:

TE624.4

王恩华, 靳丽丽, 高善彬, 迟克彬, 段爱军. 正构烷烃临氢异构化催化剂研究进展[J]. 化工进展, 2022, 41(6): 2967-2980.

WANG Enhua, JIN Lili, GAO Shanbin, CHI Kebin, DUAN Aijun. Development of catalyst for n-paraffins hydroisomerization[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 2967-2980.

图/表 10

表1 具有不同金属中心的双功能催化剂的临氢异构化性能

双功能催化剂	制备方法	反应条件	反应性能	文献
Pd@beta、Pd@MOR Pd/beta、Pd/MOR	包埋法浸渍法	反应温度200~250℃，压力4MPa，n(H₂)/n(正庚烷)=6.64，WHSV=2h^-1	包埋法制得Pd@beta和Pd@MOR催化剂表现出更高的异构化选择性，Pd@beta上i-C₇产率达50%以上，而Pd/beta，i-C₇产率为46%；Pd@MOR上i-C₇产率40%左右，Pd/MOR上i-C₇产率仅为28%	［6］
Pd-Pt/H-beta	水溶液喷雾浸渍	反应温度185~230℃，大气压， p(H₂)=1~50bar，LHSV=0~5h^-1，n(H₂)/n(hydrocarbons)=750∶1	温度升高转化率逐渐升高，高达90%；在200℃、1bar、LHSV=3h^-1下，不同Pd/Pt比转化率不同；p(H₂)从1bar增加到50bar，获得类似转化率反应温度需提高20℃；220℃、1bar下LHSV增加，i-C₁₆产率先增加后降低，最高约70%	［7］
Pt/H-beta、Ni/H-betaNi-Pt/H-beta	干法浸渍分步浸渍	反应温度260~300℃，压力10~30bar，n(H₂)/n(原料)=15，WHSV=4~10h^-1	相同条件下，Ni-Pt催化剂中Pt的引入增强异构化选择性，对于Ni-Pt/H-beta，温度升高，转化率24.1%增至92.1%，选择性降低81.3%至33.9%；WHSV升高，转化率从53.7%降至24.1%；压力升高时转化率和选择性均略有升高	［8］
Pd/SAPO-31 Ni₂P/SAPO-31 Pd-Ni₂P/SAPO-31	浸渍法浸渍-程序升温还原法	反应温度280~400℃，压力2MPa，WHSV=3.7h^-1，V(H₂)/V(C₁₆)=500	0.05Pd/S31催化剂表现出最低的n-C₁₆转化率（60%）和i-C₁₆产率（40%）；而4Ni₂P/SAPO-31的n-C₁₆转化率和i-C₁₆产率相对较高；对于0.05Pd-4Ni₂P/SAPO-31具有最高的n-C₁₆转化率（约85%）和i-C₁₆产率（约70%）	［9］
Ni-Mo/SAPO-11 Ni/SAPO-11 Mo/SAPO-11	真空辅助浸渍法	反应温度270~340℃，压力2MPa，WHSV=3.1h^-1，V(H₂)/V(C₁₆)=650	与Ni/SAPO-11相比，3.0Ni-0.5Mo/SAPO-11催化剂裂解产物产率低，在转化率93.0%时裂解产物产率为11.6%，且对异构体选择性可达81%。在315℃反应100h时，3.0Ni-0.5Mo/SAPO-11催化剂对正十六烷异构化转化率和选择性分别约为92%和86%，稳定性好	［10］
MoP/Hbeta	低温自燃法浸渍法	反应温度280~360℃，常压，n(H₂)/n(正庚烷)=4~16，WHSV=1.2h^-1	浸渍法制备30%MoP/Hbeta-Im正庚烷转化率26.9%，异构化选择性85.3%；而自燃法制备MoP/Hbeta-c催化剂表现出较高活性51%和较低异构化选择性68.8%。H₂/正庚烷增加，n-C₇转化率降低，i-C₇选择性增加；反应温度升高，催化活性迅速增强，反应温度超过320℃，i-C₇选择性下降，裂解选择性上升	［11］
Ni-Ce/SAPO-11	浸渍法	反应温度300℃，常压，n(H₂)/n(n-C₇H₁₆)=12，WHSV=3.52h^-1	2%Ce的催化剂活性最高，转化率为28.8%，选择性为82.7%；随反应时间延长，n-C₇转化率略有下降，i-C₇选择性略有上升，稳定性好	［12］

表1 具有不同金属中心的双功能催化剂的临氢异构化性能

双功能催化剂	制备方法	反应条件	反应性能	文献
Pd@beta、Pd@MOR Pd/beta、Pd/MOR	包埋法浸渍法	反应温度200~250℃，压力4MPa，n(H₂)/n(正庚烷)=6.64，WHSV=2h^-1	包埋法制得Pd@beta和Pd@MOR催化剂表现出更高的异构化选择性，Pd@beta上i-C₇产率达50%以上，而Pd/beta，i-C₇产率为46%；Pd@MOR上i-C₇产率40%左右，Pd/MOR上i-C₇产率仅为28%	［6］
Pd-Pt/H-beta	水溶液喷雾浸渍	反应温度185~230℃，大气压， p(H₂)=1~50bar，LHSV=0~5h^-1，n(H₂)/n(hydrocarbons)=750∶1	温度升高转化率逐渐升高，高达90%；在200℃、1bar、LHSV=3h^-1下，不同Pd/Pt比转化率不同；p(H₂)从1bar增加到50bar，获得类似转化率反应温度需提高20℃；220℃、1bar下LHSV增加，i-C₁₆产率先增加后降低，最高约70%	［7］
Pt/H-beta、Ni/H-betaNi-Pt/H-beta	干法浸渍分步浸渍	反应温度260~300℃，压力10~30bar，n(H₂)/n(原料)=15，WHSV=4~10h^-1	相同条件下，Ni-Pt催化剂中Pt的引入增强异构化选择性，对于Ni-Pt/H-beta，温度升高，转化率24.1%增至92.1%，选择性降低81.3%至33.9%；WHSV升高，转化率从53.7%降至24.1%；压力升高时转化率和选择性均略有升高	［8］
Pd/SAPO-31 Ni₂P/SAPO-31 Pd-Ni₂P/SAPO-31	浸渍法浸渍-程序升温还原法	反应温度280~400℃，压力2MPa，WHSV=3.7h^-1，V(H₂)/V(C₁₆)=500	0.05Pd/S31催化剂表现出最低的n-C₁₆转化率（60%）和i-C₁₆产率（40%）；而4Ni₂P/SAPO-31的n-C₁₆转化率和i-C₁₆产率相对较高；对于0.05Pd-4Ni₂P/SAPO-31具有最高的n-C₁₆转化率（约85%）和i-C₁₆产率（约70%）	［9］
Ni-Mo/SAPO-11 Ni/SAPO-11 Mo/SAPO-11	真空辅助浸渍法	反应温度270~340℃，压力2MPa，WHSV=3.1h^-1，V(H₂)/V(C₁₆)=650	与Ni/SAPO-11相比，3.0Ni-0.5Mo/SAPO-11催化剂裂解产物产率低，在转化率93.0%时裂解产物产率为11.6%，且对异构体选择性可达81%。在315℃反应100h时，3.0Ni-0.5Mo/SAPO-11催化剂对正十六烷异构化转化率和选择性分别约为92%和86%，稳定性好	［10］
MoP/Hbeta	低温自燃法浸渍法	反应温度280~360℃，常压，n(H₂)/n(正庚烷)=4~16，WHSV=1.2h^-1	浸渍法制备30%MoP/Hbeta-Im正庚烷转化率26.9%，异构化选择性85.3%；而自燃法制备MoP/Hbeta-c催化剂表现出较高活性51%和较低异构化选择性68.8%。H₂/正庚烷增加，n-C₇转化率降低，i-C₇选择性增加；反应温度升高，催化活性迅速增强，反应温度超过320℃，i-C₇选择性下降，裂解选择性上升	［11］
Ni-Ce/SAPO-11	浸渍法	反应温度300℃，常压，n(H₂)/n(n-C₇H₁₆)=12，WHSV=3.52h^-1	2%Ce的催化剂活性最高，转化率为28.8%，选择性为82.7%；随反应时间延长，n-C₇转化率略有下降，i-C₇选择性略有上升，稳定性好	［12］

表2 工业应用低温、中温型轻烃异构化催化剂

催化剂	开发公司	型号	反应条件	辛烷值（单程转化产品）
低温型异构化催化剂^{［3，36-38］}	UOP	I-8	130~170℃、1.7~1.8MPa、0.8~1.0h^-1、氢油摩尔比1~2	84.5
	UOP	I-82、I-84、I-122	120~180℃、3.0~4.0MPa、1.5h^-1、氢油摩尔比0.3~0.5	83~86
	Axens	IS614A	120~180℃、2.0MPa、2.0h^-1、氢油摩尔比<1	83
	Axens	ATIS-2L	110~170℃、2.0MPa、2.0h^-1、氢油摩尔比<1	84~85
	华东理工大学与金陵石化分公司	Pt-Cl/Al₂O₃	140℃、2.0MPa、1.0h^-1、氢油摩尔比1~2	80.2
中温型异构化催化剂^{［3， 36-38］}	UOP	I-7 0.3Pt/HM	260~280℃、1.5~3MPa、2h^-1、氢油摩尔比4	78~80
	Axens	IP-632	250~270℃、1.5~3MPa、1~2h^-1、氢油摩尔比3~4	80
	RIPP	FI-15 Pt/HM	250~270℃、1.6MPa、1.7h^-1、氢油摩尔比2.6	81
	华东理工大学与金陵石化分公司	CI-50 Pd/HM	260℃、2MPa、2h^-1、氢油摩尔比2.7	80.9

表3 具有形状选择性的沸石结构和酸性

沸石	孔道尺寸/?	拓扑结构	酸性质	文献
丝光沸石	6.5×7.0	MOR（十二元环）	丰富的酸中心、比较温和的酸强度	[30,39]
beta	6.6×6.7	BEA（十二元环）	较强的酸性	[40-41]
ZSM-5	5.5×5.1	MFI（十元环）	强酸量大，L酸与B酸比值高	[4]
ZSM-22	5.7×4.6	TON（十元环）	中等强度的表面酸性	[13,15,21,42-44]
ZSM-23	5.2×4.5	MTT（十元环）	表面酸性较强	[2,44-46]
SAPO-11	3.9×6.3	AEL（十元环）	适中的中强酸	[12,27,19,29]
SAPO-31	5.4×5.4	ATO（十二元环）	温和的酸强度和酸量	[9,14,47]

图1 SO42-在ZrO2表面的作用形式[56]

图2 Me/SAPO-31催化剂上n-C16临氢异构化反应机理[22]

图3 Ni/SAPO-11催化剂上n-C6转化率、和与CNi/CA的关系[64]

表4 具有不同nPt/nA比的PtHY对正癸烷临氢异构化和裂化的影响

n_Pt/n_A	>0.17	0.03<n_Pt/n_A<0.17	<0.03
活性	高	高	低
稳定性	高	一般	低
反应路径	n-C₁₀ $?$ M $?$ B $?$ C	n-C₁₀ $?$ (M, B) $?$ C	$?$ M n-C₁₀ $?$ B $→$ C

表4 具有不同nPt/nA比的PtHY对正癸烷临氢异构化和裂化的影响

n_Pt/n_A	>0.17	0.03<n_Pt/n_A<0.17	<0.03
活性	高	高	低
稳定性	高	一般	低
反应路径	n-C₁₀ $?$ M $?$ B $?$ C	n-C₁₀ $?$ (M, B) $?$ C	$?$ M n-C₁₀ $?$ B $→$ C

图4 Pt在沸石内或外对正庚烷临氢异构化的影响[71]

图5 不同金属-酸中心距离催化剂Pt-A/Y、Pt-Y/A对临氢性能的影响[73]实线和实心符号—异构化产物的产率；虚线和空心符号—裂解产物的产率

图6 具有不同活性位点间的距离（金属-酸距离）的催化剂[74]

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