碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化 试剂的烷基酚、烷氧基酚及其混合物的烷基化转化

doi:10.12034/j.issn.1009-606X.217162

过程工程学报 ›› 2017, Vol. 17 ›› Issue (6): 1239-1248.DOI: 10.12034/j.issn.1009-606X.217162

碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化试剂的烷基酚、烷氧基酚及其混合物的烷基化转化

张少华^1,2，王泽^1,2*，林伟刚^1,2,3，宋文立^1,2，李松庚^1,2

1. 中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190；2. 中国科学院大学化学与化工学院，北京，100049； 3. 丹麦技术大学化学和生化工程系，林格比丹麦 DK-2800

收稿日期:2017-03-06 修回日期:2017-04-11 出版日期:2017-12-20 发布日期:2017-12-05
通讯作者: 王泽 wangze@ipe.ac.cn
基金资助:
国家自然科学基金面上项目：原位供氢条件下生物质水热转化制备液体燃料基础研究;油页岩高效油气炼制与过程节能科学基础973项目

Alkylation of Alkylphenol, Alkoxyphenol and Their Mixture with Methanol under the Catalysis of Alkali and Alkaline-earth Salts Modified Activated Alumina

Shaohua ZHANG^1,2, Ze WANG^1,2*, Weigang LIN^1,2,3, Wenli SONG^1,2, Songgeng LI^1,2

1. State Key Lab of Multi-phase Complex Systems, Inst. Process Eng., Chinese Academy of Sciences, Beijing 100190, China; 2. School of Chemistry and Chemical Engeering, University of Chinese Academy of Sciences, Beijing 100049, China; 3. Department of Chemical and Biochemical Engineering, Technical University of Denmark, Denmark Lyngby DK-2800

Received:2017-03-06 Revised:2017-04-11 Online:2017-12-20 Published:2017-12-05

摘要/Abstract

摘要： 以甲醇为烷基化试剂，考察了碱金属(A)及碱土金属盐(AE)改性的活性氧化铝(AA)催化剂对烷基酚、烷氧基酚及其二元及五元混合体系的烷基化转化反应的影响规律. 结果表明，碱金属盐改性的活性Al2O3 (A/AA)可显著促进苯酚及甲基苯酚的O-烷基化转化，尤其是以Cs2CO3/AA为催化剂时，苯酚转化率最高可达90.4%(?)，且O-烷基化产物苯甲醚的选择性为96.1%(area). 相同反应条件下，邻甲氧基苯酚的转化率和产物的选择性均不理想，调节反应温度、空速及Cs负载量仍不能有效改善. 混合酚混合物体系的烷基化转化过程中存在非常显著的协同效应，烷基酚的转化受到严重抑制而烷氧基酚的转化得到显著促进，且C-烷基化产物显著增加.

关键词: 烷基化, 烷基酚, 烷氧基酚, 催化, 碱金属

Abstract: Using methanol as the alkylation reagent, the alkylations of alkylphenol, alkoxyphenol, and their binary and five-component mixtures were investigated, under the catalysis of alkali (A) and alkaline-earth (AE) salts modified activated alumina (AA). The results showed that phenol and methylphenol can high efficiently be converted to O-alkylation products over A/AA. Specifically, under the catalysis of Cs2CO3/AA, the conversion rate of phenol reached to the highest value of 90.4%(?) with high anisole selectivity of 96.1%(area). However, under the same reaction conditions, neither the conversion rate nor the product selectivity is satisfactory for the alkylation of methoxyphenol, and the adjustment of the reaction temperature, the space velocity, or the Cs loading amount cannot make the results better. There exists a strong synergistic effect for the co-alkylation of the alkylphenol/alkoxyphenol mixture, under this effect, the conversion of alkylphenol is inhibited, while the conversion of alkoxyphenol is promoted, with remarkably enhanced selectivity to C-alkylation products.

Key words: alkylation, alkylphenol, alkoxyphenol, catalysis, alkali metal

张少华王泽林伟刚宋文立李松庚 . 碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化试剂的烷基酚、烷氧基酚及其混合物的烷基化转化[J]. 过程工程学报, 2017, 17(6): 1239-1248.

Shaohua ZHANG Ze WANG Weigang LIN Wenli SONG Songgeng LI. Alkylation of Alkylphenol, Alkoxyphenol and Their Mixture with Methanol under the Catalysis of Alkali and Alkaline-earth Salts Modified Activated Alumina[J]. Chin. J. Process Eng., 2017, 17(6): 1239-1248.

参考文献

1. Bridgwater, A.V., Review of fast pyrolysis of biomass and product upgrading. Biomass and Bioenergy, 2012. 38: p. 68-94.
2. Hicks, J.C., Advances in C–O Bond Transformations in Lignin-Derived Compounds for Biofuels Production. The Journal of Physical Chemistry Letters, 2011. 2(18): p. 2280-2287.
3. Huber, G.W., S. Iborra, and A. Corma, Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering. Chemical Reviews, 2006. 106(9): p. 4044-4098.
4. Demirbas, A., Biorefineries: Current activities and future developments. Energy Conversion and Management, 2009. 50(11): p. 2782-2801.
5. Czernik, S. and A.V. Bridgwater, Overview of Applications of Biomass Fast Pyrolysis Oil. Energy & Fuels, 2004. 18(2): p. 590-598.
6. Effendi, A., H. Gerhauser, and A.V. Bridgwater, Production of renewable phenolic resins by thermochemical conversion of biomass: A review. Renewable and Sustainable Energy Reviews, 2008. 12(8): p. 2092-2116.
7. Kim, J.-S., Production, separation and applications of phenolic-rich bio-oil – A review. Bioresource Technology, 2015. 178: p. 90-98.
8. Lehto, J., et al., Review of fuel oil quality and combustion of fast pyrolysis bio-oils from lignocellulosic biomass. Applied Energy, 2014. 116: p. 178-190.
9. Sharma, R.K. and N.N. Bakhshi, Catalytic upgrading of fast pyrolysis oil over HZSM-5. Canadian Journal of Chemical Engineering, 1993. 71(3): p. 383-391.
10. Imran, A., et al., High quality bio-oil from catalytic flash pyrolysis of lignocellulosic biomass over alumina-supported sodium carbonate. Fuel Processing Technology, 2014. 127: p. 72-79.
11. Veses, A., et al., Production of upgraded bio-oils by biomass catalytic pyrolysis in an auger reactor using low cost materials. Fuel, 2015. 141: p. 17-22.
12. Veses, A., et al., Catalytic upgrading of biomass derived pyrolysis vapors over metal-loaded ZSM-5 zeolites: Effect of different metal cations on the bio-oil final properties. Microporous and Mesoporous Materials, 2015. 209: p. 189-196.
13. Wang, Z., et al., Composition of the liquid product by pyrolysis of dried distiller's grains with solubles. Journal of Analytical and Applied Pyrolysis, 2012. 98: p. 242-246.
14. Wang, Z., et al., Pyrolysis of the lignocellulose fermentation residue by fixed-bed micro reactor. Energy, 2012. 43(1): p. 301-305.
15. Yu, M.J., et al., Hydrodeoxygenation of guaiacol over Pt/Al-SBA-15 catalysts. Journal of Nanoscience and Nanotechnology, 2015. 15(1): p. 527-531.
16. Sanna, A., T.P. Vispute, and G.W. Huber, Hydrodeoxygenation of the aqueous fraction of bio-oil with Ru/C and Pt/C catalysts. Appl. Catal., B, 2015. 165: p. 446-456.
17. Ausavasukhi, A., et al., Hydrodeoxygenation of m-cresol over gallium-modified beta zeolite catalysts. Journal of Catalysis, 2012. 290: p. 90-100.
18. Guo, X.-Y. and Y.-J. Yan, Analysis of the coke precursor on bio-oil refining catalyst and the regeneration of the deactivated catalyst. Gao Xiao Hua Xue Gong Cheng Xue Bao/Journal of Chemical Engineering of Chinese Universities, 2006. 20(2): p. 222-226.
19. Sad, M.E., C.L. Padro, and C.R. Apesteguia, Phenol methylation on acid catalysts: Study of the catalyst deactivation kinetics and mechanism. Applied Catalysis A: General, 2014. 475: p. 305-313.
20. Wang, Z., et al., Catalytic Upgrading of Phenolic‐oil by Etherification with Methanol. Chemical Engineering & Technology, 2016. 39(10): p. 1797-1803.
21. Shen, H.-Y., et al., Comparative studies on alkylation of phenol with tert-butyl alcohol in the presence of liquid or solid acid catalysts in ionic liquids. Journal of Molecular Catalysis A: Chemical, 2004. 212(1-2): p. 301-308.
22. Rueping, M. and B.J. Nachtsheim, A review of new developments in the Friedel-Crafts alkylation - From green chemistry to asymmetric catalysis. Beilstein J Org Chem, 2010. 6: p. 6.
23. Wu, Y.-C., et al., TFA-mediated tandem Friedel-Crafts alkylation/cyclization/hydrogen transfer process for the synthesis of flavylium compounds. Journal of Organic Chemistry, 2007. 72(24): p. 9383-9386.
24. Dang, D., et al., Synthesis of anisole by vapor phase methylation of phenol with methanol over catalysts supported on activated alumina. Chinese Journal of Catalysis, 2016. 37(5): p. 720-726.
25. Wang, Y., et al., Vapor phase ortho-selective alkylation of phenol with methanol over silica-manganese mixed oxide catalysts. Chemical Engineering Journal, 2012. 181-182: p. 630-635.
26. Grabowska, H., L. Syper, and M. Zawadzki, Vapour phase alkylation of ortho-, meta- and para-cresols with isopropyl alcohol in the presence of sol–gel prepared alumina catalyst. Applied Catalysis A: General, 2004. 277(1–2): p. 91-97.
27. Velu, S. and C.S. Swamy, Alkylation of phenol with methanol over magnesium-aluminium calcined hydrotalcites. Applied Catalysis A: General, 1994. 119(2): p. 241-252.
28. Yadav, G.D. and P. Kumar, Alkylation of phenol with cyclohexene over solid acids: Insight in selectivity of O- Versus C-alkylation. Applied Catalysis A: General, 2005. 286(1): p. 61-70.
29. Kirumakki, S.R., et al., A facile O-alkylation of 2-naphthol over zeolites Hβ, HY, and HZSM5 using dimethyl carbonate and methanol. Journal of Catalysis, 2004. 221(2): p. 549-559.
30. García, L., et al., Phenol alkylation with methanol: effect of sodium content and ammonia selective poisoning of an HY zeolite. Catalysis Letters, 1996. 37(1-2): p. 121-123.
31. Marczewski, M., et al., Alkylation of aromatics. Part I. Reaction network of the alkylation of phenol by methanol of USHY zeolite. Journal of molecular catalysis, 1989. 50(2): p. 211-218.
32. Bautista, F.M., et al., Alkylation of phenol with dimethyl carbonate over AlPO4, Al2O3 and AlPO4-Al2O3 catalysts. Reaction Kinetics and Catalysis Letters, 1998. 63(2): p. 261-269.
33. Chen, B., et al., Mechanism study of anisole synthesis from o-methylation of phenol with DMC over KBr catalyst. Ranliao Huaxue Xuebao/Journal of Fuel Chemistry and Technology, 2011. 39(2): p. 144-148.
34. Ono, Y., Dimethyl carbonate for environmentally benign reactions. Catalysis Today, 1997. 35(1): p. 15-25.
35. Velu, S. and C.S. Swamy, Effect of substitution of Fe3+/Cr3+ on the alkylation of phenol with methanol over magnesium-aluminium calcined hydrotalcite. Applied Catalysis A: General, 1997. 162(1-2): p. 81-91.
36. Grabowska, H., et al., Catalytic alkylation of phenol with methanol over zinc aluminate. Research on Chemical Intermediates, 2001. 27(3): p. 305-313.
37. Agayev, A.A. and D.B. Tagiyev, Alkylation of phenol by methanol on type-Y zeolites. Petroleum Chemistry, 1992. 32(2): p. 101-105.
38. Samolada, M.C., et al., Selective O-Alkylation of Phenol with Methanol over Sulfates Supported on γ-Al2O3. Journal of Catalysis, 1995. 152(1): p. 52-62.
39. Bautista, F.M., et al., Anion treatment (F- or SO42-) of AlPO4-Al2O3 (25 wt.-% Al2O3) catalysts. IV. Catalytic performance in the alkylation of phenol with methanol. Applied Catalysis A: General, 1993. 99(2): p. 161-173.
40. Sarala Devi, G., D. Giridhar, and B.M. Reddy. Vapour phase O-alkylation of phenol over alkali promoted rare earth metal phosphates. 2002. Elsevier.
41. Sarala Devi, G., D. Giridhar, and B.M. Reddy, Vapour phase O-alkylation of phenol over alkali promoted rare earth metal phosphates. Journal of Molecular Catalysis A: Chemical, 2002. 181(1–2): p. 173-178.
42. Wang, Z., et al., Wood-Tar Fractionation by Column Chromatography with an Adsorbent of Acidic Al2O3. International Journal of Green Energy, 2014. 11(3): p. 320-328.

[1]	王义源马淑花王晓辉欧彦君高利珍. 高铝粉煤灰负载锰基催化剂的催化氧化NO性能研究[J]. 过程工程学报, 2022, 22(9): 1262-1270.
[2]	徐家明皇甫林史玉婷郭洪范高士秋李长明余剑. 低温烟气脱硝催化剂制备工艺及性能探究[J]. 过程工程学报, 2022, 22(7): 863-872.
[3]	申展江志东张鹏飞张子瑜车海英马紫峰. 低温甲醇水重整制氢催化剂研究进展[J]. 过程工程学报, 2022, 22(5): 573-585.
[4]	王书欢周理龙李正杰韩继龙刘润静 Jimmy Yun. 催化臭氧氧化降解水中有机污染物的研究进展[J]. 过程工程学报, 2022, 22(5): 586-600.
[5]	张凯伦焦念明张莹郝鹏波张国霞王慧李增喜. 双金属改性ZSM-5-USY复合分子筛催化裂解正己烷制备低碳烯烃[J]. 过程工程学报, 2022, 22(4): 458-468.
[6]	李珂曾玺王芳康国俊张建岭许光文. 金属氧化物对生物质半焦气化特性和反应动力学影响[J]. 过程工程学报, 2022, 22(4): 487-498.
[7]	张晟林于佳元王蕾闫瑞一李春山. 磷钼钒酸催化甲基丙烯醛氧化反应机制及过程研究[J]. 过程工程学报, 2022, 22(3): 385-392.
[8]	杜含笑季娟秦辰伟张泽李锋锋沈毅. g-C₃N₄制备方法及其光催化性能提升途径的研究进展[J]. 过程工程学报, 2022, 22(2): 162-175.
[9]	梁锐李明阳高翔鹏于先坤童雄龙红明. 选矿废水中残留黄药光催化处理及降解效率改进方式研究进展[J]. 过程工程学报, 2022, 22(1): 1-13.
[10]	刘彪姚秀颖孟振亮刘梦溪. 高低并列式重油催化裂化汽提器挡板的结构优化[J]. 过程工程学报, 2022, 22(1): 22-31.
[11]	杨建林赵璐马淑花王晓辉王月娇. 莫来石-刚玉催化剂载体制备及其性能研究[J]. 过程工程学报, 2022, 22(1): 79-88.
[12]	杨永徐永张光晋. UiO-66基催化剂的制备及其在CO甲烷化中的应用[J]. 过程工程学报, 2021, 21(9): 1074-1081.
[13]	潘嘉晟王耀锋马爽爽孙瑞仝育婷丁其达张锐. 脂肪伯胺的合成及工业化研究进展[J]. 过程工程学报, 2021, 21(8): 905-917.
[14]	吴秋莹, 孔令凯, 徐骥, 葛蔚, 袁绍军. 气固两相流内中空多孔催化剂性能的数值模拟[J]. 过程工程学报, 2021, 21(7): 774-785.
[15]	郑应俊, 孟海玲, 刘再亮, 周晗, 朱俊杰. 电芬顿体系中铁铈双金属催化剂降解邻苯二甲酸二丁酯研究[J]. 过程工程学报, 2021, 21(7): 857-864.

碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化试剂的烷基酚、烷氧基酚及其混合物的烷基化转化

Alkylation of Alkylphenol, Alkoxyphenol and Their Mixture with Methanol under the Catalysis of Alkali and Alkaline-earth Salts Modified Activated Alumina

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化 试剂的烷基酚、烷氧基酚及其混合物的烷基化转化

Alkylation of Alkylphenol, Alkoxyphenol and Their Mixture with Methanol under the Catalysis of Alkali and Alkaline-earth Salts Modified Activated Alumina

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化试剂的烷基酚、烷氧基酚及其混合物的烷基化转化