Synthesis of supported bismuth molybdate catalyst and the application in selective oxidation of propylene to acrolein

Synthesis of supported bismuth molybdate catalyst and the application in selective oxidation of propylene to acrolein Synthesis of supported bismuth molybdate catalyst and the application in selective oxidation of propylene to acrolein luận văn tốt nghiệp thạc sĩ

1 MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF TECHNOLOGY Truong Duc Duc SYNTHESIS OF SUPPORTED BISMUTH MOLYBDATE CATALYST AND THE APPLICATION IN SELECTIVE OXIDATION OF PROPYLENE TO ACROLEIN Tổ ng hợ p vậ t liệ u Bismuth Molybdate chấ t mang ứ ng dụ ng làm xúc tác cho phả n ứ ng oxi hóa chọ n lọ c propylene thành acrolein Major: Chemical engineering MSC THESIS Supervisor: Dr Le Minh Thang Invited supervisor : Assoc Prof Anders Riisager Hanoi, 10/2009 Duc T.D - 2009 Abstract The subject of this thesis is the synthesis of high surface area bismuth molybdate based catalysts Two synthesis directions this leads to the synthesis have been carried out One is based on the idea of reducing the particle size of catalyst, nanometer sized -Bi2MoO6 crystals with dimension of 50nm were synthesized by hydrothemal treatment Another is based on the idea of impregnating bismuth molybdate on high surface area supports, silica supported -Bi2Mo2O9 and zirconia supported -Bi2Mo2O9 catalysts with various percentage of -Bi2Mo2O9 loading contents were therefore synthesized Both works aimed to investigate the influence of surface area of catalyst on their catalytic activities in the selective oxidation of propylene to acrolein In this thesis, bismuth molybdate catalysts and their applications in the selective oxidation of propylene to acrolein were presented very detail The Mars and van Krevelen mechanism as well as the important role of lattice oxygen were also discussed in detail Synthesis of mesoporous ZrO2 support by hydrothermal method was also a studying task since the synthesis of mesoporous ZrO2 ordinary work and requires a special attention in order to obtain a high surface area and a stable pore structure The application of supported bismuth molybdate catalysts in selective propylene oxidation results is provided a better understanding about the role of lattice oxygen and surface area of catalyst Both surface area and lattice oxygen of catalyst play as key roles in the reaction Supported bismuth molybdate samples possess both high surface area and high oxygen mobility resulted in an extraordinary increase of catalytic activities Among supports, ZrO2 is more efficient due to the presence of synergy effect Duc T.D - 2009 Tóm tắ t Nộ i dung củ a luậ n văn tổ ng hợ p vậ t liệ u xúc tác sở bismuth molybdate có diệ n tích bề mặ t riêng cao Hai hư ng tổ ng hợ p vậ t liệ u đư ợ c thự c hiệ n Hư ng thứ nhấ t dự a ý tư ng làm giả m kích thư c hạ t xúc tác, tinh thể - Bi2MoO6 có kích thư c hạ t khoả ng 50nm đư ợ c tổ ng hợ p thành công bằ ng phư ng pháp kế t tinh thủ y nhiệ t Hư ng thứ hai dự a ý tư ng mang bismuth molybdate lên chấ t mang có bề mặ t riêng cao, xúc tác bismuth molybdate ngâm tẩ m silica zirconia đư ợ c điề u chế vớ i hàm lư ợ ng chấ t mang khác Cả hai hư ng đề u nhằ m để khả o sát ả nh hư ng củ a diệ n tích bề mặ t riêng củ a xúc tác đế n hoạ t tính xúc tác củ a phả n ứ ng oxi hóa chọ n lọ c propylene thành acrolein Trong luậ n văn này, hệ xúc tác bismuth molybdate ứ ng dụ ng củ a phả n ứ ng oxi hóa chọ n lọ c propylen thành acrolein đư ợ c đư a rấ t chi tiế t Cơ chế Mars van Krevelen vai trò đặ c biệ t quan trọ ng củ a oxy mạ ng lư i củ a xúc tác đư ợ c thả o luậ n mộ t cách cụ thể Tổ ng hợ p chấ t mang mao n trung bình zirconia bằ ng phư ng pháp kế t tinh thủ y nhiệ t nằ m nộ i dung nghiên u việ c tổ ng hợ p vậ t liệ u mao n trung bình ZrO2 địi hỏ i quan tâm đặ c biệ t để trì diệ n tích bề mặ t cao cấ u trúc mao n ổ n đị nh Kế t nghiên u ứ ng dụ ng vậ t liệ u xúc tác sở bismuth molybdate có diệ n tích bề mặ t riêng cao phả n ứ ng oxi hóa chọ n lọ c propylene cung cấ p thêm nhữ ng hiể u biế t rõ hơ n vai trò củ a oxy mạ ng lư i bề mặ t riêng củ a xúc tác Cả diệ n tích bề mặ t riêng oxy mạ ng lư i củ a xúc tác đề u đóng vai trị quyế t đị nh phả n ứ ng Các mẫ u xúc tác ngâm tẩ m bismuth molybdate có diệ n tích bề mặ t riêng lớ n oxy mạ ng lư i linh độ ng dẫ n đế n hoạ t tính xúc tác tăng đáng kể Trong hai loạ i chấ t mang ZrO2 có hiệ u hơ n bở i xuấ t hiệ n củ a hiệ u ứ ng hiệ p trợ xúc tác giữ a chấ t mang vớ i pha phả n ứ ng Duc T.D - 2009 Preface This thesis is submitted in candidacy for Master degree from project “Prj.104.DAN.8.L.1604 - Attractive routes for selective catalytic oxidation of hydrocarbons” cooperated between Hanoi University of Technology (HUT) and Technical University of Denmark (DTU) The work presented herein has been carried out at Lab of Petrochemicals and Catalysis Materials, Adsorption, Faculty of Chemical Engineering, Hanoi University of Technology under the supervision of Dr Le Minh Thang The work is also performed in the cooperation with Center for Sustainable and Catalysis Chemistry, Technical University of Denmark (DTU), Denmark First and foremost, I would like to thank my supervisor Dr Le Minh Thang for her exceptional patience with me At the beginning, I was “clumsy” and made a lot of my own mistakes, but in spite of this, she always gives me a patience and provides valuable guidance and support But the most valuable thing I have learnt from her is “how to science” I also would like to thank Dr Nguyen Hong Lien, director of Lab of petrochemicals and catalysis, adsorption materials for her support and patience as well as the great opportunity which she offered me to work in her lab during the last two years During my master study, I also have a chance to be trained for six months at Center for Sustainable and Catalysis Chemistry, Denmark On this period, I learned many things about Supported Ionic Liquid Phase Catalysts (SILP) for the hydroformylation of ethylene, a new research area, which provided very useful complimented knowledge for my research direction I am deeply grateful to Prof Rasmus Fehrmann in the DTU Kemi Centre for Catalysis and Sustainable Chemistry for giving me the opportunity to work at his lab and his kindly guidance, support and patience to me during my stay in Denmark I am also thankful to Associate Prof Anders Riisager who gave me invaluable thoughtful insights, advice, support, discussions and encouragements from the first days I came to DTU I am very gratefully for the kindness and help from all my colleagues and partners I must thank Msc Nguyen Ha Hanh for her friendly guidance and support in the time I joined the project I would especially thank Post Doc Olivier Nguyen Duc T.D - 2009 Van Buu, Post Doc Eduardo García Suárez, Post Doc Jianmin Xiong from CSC lab for their friendship and generous help during the time I stayed in Denmark Special gratitude must be given to all the graduate students with whom I have collaborated in this project at Hanoi University of Technology for their great assistance and cooperation Vo Hoang Tung, Ho Si Dang, Le The Duy, Nguyen Hoang Hai I enjoyed working together with all of you! I am also grateful to the Danida Fellowship Centre (DSC) for financial support I especially want to express my sincere gratitude to Prof Vu Dao Thang, Prof Le Van Hieu for their support, encouragement and useful discussions To my mother, father, mother-in-law, father-in-law, brothers and my best friends my warmest thanks for their love, encouragement and support during all the years of my education I sincerely thank my best friends Christian Juel Adamsen, his wife Marie Lahn ‫ ج‬lgaard and their little angel daughter Alberte for their true love, warm friendship and encouragements The most important of all, I would like to thank my wife, Thanh Thuy, with all my love Her endless love, support, understanding and patience to me were immeasurable More than anything else, her love has carried me through the many challenges I faced during my graduate years Truong Duc Duc Hanoi, 10.2009 Duc T.D - 2009 Index of Tables Table 1.1 Thermodynamic parameters of the formation of other propylene oxidation products Table 1.2 Some examples of multi-component BiMo based catalysts Table 1.3 Apparent Activation Energies of Partial Oxidation of Propylene to Acrolein over Bismuth Molybdate Catalysts [98] Table 2.1 Raw chemicals for synthesis of unsupported and supported bismuth molybdates Table 2.2 Equivalent amounts of chemicals corresponding to different samples Table 2.3 Strong lines corresponding to different phase of bismuth molybdates and cubic phase zirconia Table 2.4 : IR bands (cm-1) of bismuth molybdates Table 2.5: Raman frequencies in cm-1 of molybdate species Table 2.6: Raman frequencies of bismuth molybdates Table 2.7 Retention time of some products and related compounds Table 3.1 Summary of synthesized zirconia samples Table 3.2 Summary of synthesized bismuth molybdate samples Table 3.3 Specific surface area (SBET) of support and supported samples Index of Figures Figure 1.1 Bismuth vacant sites in α -Bi2Mo3O12 along b axis projection The solid lines show the α -Bi2Mo3O12 unit cell while the dashed line is a unit cell of scheelite Large solid circles represent occupied Bi sites while the small circles are the empty Bi sites (Adapted from van den Elzen and Rieck [11]) Duc T.D - 2009 Figure 1.2 The unit cell structure of α -Bi2Mo3O12 (left figure) and atom map of the unit cell (right figure) (Adapted from van den Elzen and Rieck) Figure 1.3 A unit cell of β -Bi2Mo2O9 (right figure) and atom map of the unit cell (left figure) (Adapted from H.-Y Chen and A.W Sleight [16]) Figure 1.4 Representation of the β -Bi2Mo2O9 structure projected along (010) [17] The figure shows clusters of MoO4 tetrahedral to form Mo4O16 The small circle represents a bismuth atom Figure 1.5 From left to right, a unit cell of γ -Bi2MoO6 and its atom map The figure is adapted from Teller et al [21] Figure 1.6 Phase equilibrium diagram of the bismuth molybdate system Figure 1.7 Molecule structure of acrolein Figure 1.8 The reaction paths of the partial oxidation of deuterium-labelled propylene, Z=kD/kH, while and are the numbers of carbon atoms where hydrogen is abstracted [46] Figure 1.9 The reaction paths of the formation of side products [46] Figure 1.10 A schematic of the Mars and van Krevelen mechanism on bismuth molybdate catalysts [88] Figure 1.11 A schematic of bridges and doubly bonded oxygen ions on bismuth molybdate catalysts [72] Figure 1.12 A schematic of steps in propylene oxidation into acrolein over bismuth molybdate catalyst [82] Figure 1.13 A reaction mechanism of propylene oxidation into acrolein, showing acid-base and redox steps [72] Figure 1.14 Schematic P-T phase diagram of ZrO2 [105] Figure 1.15 Three phases of ZrO2 Figure 1.16 Schematic diagram of the mechanism of preparation of mesoporous ZrO2 (suggested by Guorong Duan et al [108]) Duc T.D - 2009 Figure 1.17 Mechanism for mesoporous zirconia synthesis by hydrothermal method suggested by Bao-Lian Su et al [109] Figure 2.1 Diagram of preparation of bismuth molybdate by hydrothermal methods Figure 2.2 Diagram of soxhlet extraction Figure 2.3 A X-ray generated tube (a) theory diagram (b) a real tube Figure 2.4: illustrates how diffraction of X-rays by crystal planes allows one to derive lattice by using Bragg relation (a) and real XRD partten (b) Figure 2.5: Principle of infrared absorption Figure 2.6: Principle of Raman scattering Figure 2.7 Some typical types of isotherm Figure 2.8 The BET model of multilayers adsorption Figure 2.9: The BET plot Figure 2.10 The interaction between the primary electron beam and the sample in an electron microscope leads to a number of detectable signals Figure 2.11 Schematic diagram of a tranmission electron microscope Figure 2.12 Diagram of reactor setup Figure 3.1 Influence of H2O/Zr in gel on surface area of products Figure 3.2 XRD partten of zirconia prepared by hydrothermal (Z6) Absorption – desorption curve and pore distribution curve of synthesized ZrO2 sample (Z6) Figure 3.3 Figure 3.4 XRD pattern of ZrO2 sample at different calcination temperatures Figure 3.5 Influence of calcinations temperature on surface area of samples Figure 3.6 SEM image of zirconia calcinated at 580oC (Z7) Figure 3.7 XRD patterns of samples (M2 – M6) at various crystallizing temperatures Figure 3.8 SEM images of samples at various crystallizing temperatures Duc T.D - 2009 Figure 3.9 XRD patterns of samples (M4, M7, M8, M9) at various calcination temperatures Figure 3.10 SEM images of samples at various calcination temperatures Figure 3.11 FT-Raman of samples (M4, M7, M8, M9) at various calcination temperatures Figure 3.12 TG/DSC diagram of -Bi2MoO6 sample (M4) Figure 3.13 XRD parttens of samples at various pH value in gel Figure 3.14 X-ray diffraction patterns of samples synthesized by sol-gel and hydrothermal methods Fig 3.15 FT-Raman spectra of samples synthesized by sol-gel and hydrothermal methods Figure 3.16 FE-SEM images of samples synthesized by sol-gel and hydrothermal methods Figure 3.17 Specific surface area (SBET) of samples prepared by solo-gel and hydrothermal methods Fig 3.18 Conversion of propylene (a) and rate of acrolein formation (b) over samples synthesized by sol-gel and hydrothermal methods Figure 3.19 XRD patterns of zirconia supported -Bi2Mo2O9 samples (a) and silica supported -Bi2Mo2O9 samples (b) Figure 3.20 FT-Raman diagrams of zirconia supported -Bi2Mo2O9 samples (a) and silica supported -Bi2Mo2O9 samples (b) Figure 3.21 FT-IR spectra of silica supported -Bi2Mo2O9 samples Figure 3.22 SEM images of SiO2 support (a) 10%beta/SiO2 sample (b) and 40%beta/SiO2 sample (c) Figure 3.23 SEM image of 40%beta/SiO2 sample Figure 3.24 TEM image of 10%beta/SiO2 Figure 3.25 Mechanism of -Bi2Mo2O9 formation on the surface of SiO2 support Duc T.D - 2009 10 Figure 3.26 SEM images of 10%beta/ZrO2 (a) and 40%bete/ZrO2 (b) Figure 3.27 A -Bi2Mo2O9 formation on ZrO2 support mechanism Figure 3.28 The absorption – desorption curve and pore distribution curve of 10%beta/SiO2 Figure 3.29 The absorption – desorption curve and pore distribution curve of 40%beta/SiO2 Figure 3.30 conversion of propylene in selective oxidation of propylen over silica supported beta bismuth molybdates and pure beta bismuth molybdate Figure 3.31 rate of acrolein formation in selective oxidation of propylen over silica supported beta bismuth molybdates and pure beta bismuth molybdate Figure 3.32 TPRO diagrams of pure SiO2, 10%beta/SiO2, 40%beta/SiO2 and pure Bi2Mo2O9 Figure 3.33 Conversion of propylene in selective oxidation of propylen over zirconia supported beta bismuth molybdates samples and pure beta bismuth molybdate Figure 3.34 Rate of acrolein formation in selective oxidation of propylen over zirconia supported beta bismuth molybdates and pure beta bismuth molybdate Figure 3.35 Comparison of conversion of propylene (a) and rate of acrolein formation (b) in selective oxidation of propylene between 40%beta/SiO2 and 40%beta/ZrO2 samples at different temperature Figure 3.36 Reaction rate for propylene consumption at 500oC of samples with different percentage of beta mixing with ZrO2 and SiO2 supports Figure 3.37 Comparison of activation energy of pure impregnated on SiO2 and ZrO2 samples Duc T.D - 2009 -Bi2Mo2O9, -Bi2Mo2O9 119 bismuth molybdate from 10% to 40%wt Increasing bismuth molybdate loading content resulted in an aggregation of catalytic particles which happened on SiO support On the contrary, the phase transition of ZrO2 during calcination led to all beta/ZrO2 samples have lower surface area than those of beta/SiO2 All supported bismuth molybdate samples possessed high BET surface area which were suitable to apply as catalyst for selective oxidation of propylene to acrolein Catalytic activities of supported bismuth molybdate samples increased significantly in comparison with that of pure bismuth molybdate sample if oxygen reservoir of catalyst was efficient In case of SiO and ZrO2 support, the impregnation was efficient with percentage of bimusth molybdate loading content higher than 30% The use of ZrO2, one kind of good conductivity material, as a support results in great increase in catalytic activities Beside increasing the catalytic activities, ZrO results in a synergy effect with beta bismuth molybdate Duc T.D - 2009 120 CONCLUDING REMARKS In the present thesis, the focus has been on the enlarging the surface area of bismuth molybdates Synthesis of gama bismuth molybdates as nanometer sized particles and impregnation of beta bismuth molybdates on high surface area SiO2 and ZrO2 supports were discussed The obtained samples were investigated as catalysts for selective oxidation of propylene to acrolein Which have resulted in better understanding in the effect of specific surface area on catalytic performance of bismuth molybdates and kinetics The preparation of mesoporous zirconia by hydrothermal method using Brij56 as template has been also studied in this thesis The influence of some parameters like H2O/Zr ratio, crystallizing temperature, calcination temperature on phase composition and surface area of zirconia were investigated Mesoporous zirconia with surface area of 242.5 m2.g-1 was synthesized successfully The suitable conditions for synthesis of mesoporous ZrO2 were H2O/Zr(OC3H7)4 ratio of 6/10, hydrothermal treatment at 80oC and days at pH of Soxhlet extraction was suggested to remove surfactant out of samples which could help to remain mesoporous structure of zirconia Nanometer sized -Bi2MoO6 particles with dimension of 50nm were successfully synthesized by hydrothermal treatment under stirring and ultrasonic conditions The suitable conditions for synthesis of nanometer sized -Bi2MoO6 were: pH = 4; o hydrothermal treatment at 120 C for hours It revealed that the particle size, phase composition, crystallinity of powder products could be controlled by synthesized conditions like: crystallizing temperature, pH value, calcination temperature Using ultrasonic and stirring conditions combined with hydrothermal crystallization could help to prevent the crystalline aggregation The results showed a extraordinary high surface area -Bi2MoO6 was obtained Application of this nanometer sized -Bi2MoO6 as catalyst for selective oxidation of propylene to acrolein seems not be effective in improving catalytic activities It is once again confirmed that lattice oxygen plays a very important role in the selective oxidation of propylene, therefore, when oxygen reservoir of catalyst is not efficient (e.g nanometer sized particles) the catalytic activity decrease significantly Supported bismuth molybdate on high surface area SiO2 and ZrO2 supports at the loading content of bismuth molybdate from 10% to 40%wt have been prepared Duc T.D - 2009 121 successfully Highly dispersed state of -Bi2Mo2O9 on supports were confirmed by many physico-chemical techniques The results showed that catalytic activities over 30%beta/SiO2, 40%beta/SiO2, 30%beta/ZrO2 and 40%beta/ZrO2 samples increased significantly It was described how the high surface area of supported -Bi2Mo2O9 samples enhances the catalytic activities of catalysts In case of SiO2 support, high surface area of catalyst just only plays as a positive role if oxygen reservoir of catalyst is enough The layer of -Bi2Mo2O9 on SiO2 support should be thick enough to guarantee the oxygen reservoir of catalysts which results in a increase of catalytic activities In case of ZrO2 support, the good oxygen reservoir of catalyst was not a prerequisite for the selective oxidation, implying that both active sites and oxygen reservoir of catalyst played as the important role in this reaction A synergy effect between phase bismuth molybdate and cubic phase zirconia support was discribed A combination between this synergy effect and high surface area of zirconia supported -Bi2Mo2O9 results in a high increase of catalytic performance of these samples Duc T.D - 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2009 133 Appendix Paper 1: “Bismuth molybdate/ZrO2 catalyst for the selective oxidation of propylene to acrolein” TRƯ Ơ NG DỰ C ĐỨ Ca, NGUYỄ N THỊ HÀ HẠ NHa, LÊ MINH THẮ NGb Paper 2: “Synthesis of nano bismuth molybdate catalyst for the selective oxidation of propylene to acrolein.” Truong Duc Duca, Nguyen Ha Hanha, Le Minh Thangb 5th Vietnam National Conference on Catalysis and Adsorption, Haiphong, Vietnam 2009 Duc T.D - 2009 ... aimed to investigate the influence of surface area of catalyst on their catalytic activities in the selective oxidation of propylene to acrolein In this thesis, bismuth molybdate catalysts and their... as oxidation of acrolein In order to gain further insight into the reaction mechanism and to find out the origin of carbon oxides, Keulks et al [97] undertook a kinetic study on propylene oxidation. .. contains historical background of the reaction discussion in depth of the bismuth molybdates, how they play as catalytic role in selective oxidation of propylene to acrolein and the background of