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Mục đích của luận án nhằm nghiên cứu một cách hệ thống quá trình tổng hợp và đặc trưng tính chất xúc tác trên cơ sở carbon sulfo hóa từ các nguồn sinh khối phổ biến; Tổng hợp, đặc trưng tính chất chất xúc tác trên cơ sở graphene oxide;...
B GIÁO D O T T VI T NAM VI N HĨA H C CƠNG NGHI P VI T NAM NGUY N M NH HÀ T NG H TÍNH CH T XÚC TÁC ACID S CARBON T SINH KH I VÀ GRAPHENE OXIDE NG D NG CHO PH N NG ESTE HÓA ACID LACTIC LU N ÁN TI HÀ N I -2019 C M CL C DANH M C KÝ HI U VÀ CH VI T T T DANH M C B NG DANH M C HÌNH M U NG QUAN u ch ethyl lactate 1.1.1 Tính ch t ng d ng c a ethyl lactate 1.1.2 Dung môi sinh h c c a ph n ng 1.1.4 Các y u t n trình este hóa acid lactic 1.1.5 Xúc tác acid r n cho trình este hóa acid lactic 11 1.2 Xúc tác acid r carbon sulfo hóa 14 1.2.1 Gi i thi carbon sulfo hóa 14 u ch carbon sulfo hóa 15 1.2.2.1 Nhi t phân polymer ch a ti n ch t sulfonic 15 1.2.2.2 T ng h p b c bi t 15 1.2.2.3 Sulfo hóa than hóa h p ch 16 1.2.2.4 Sulfo hóa v t li c t trình nhi t phân saccharide 17 1.2.2.5 Sulfo hóa v t li c t nhi t phân sinh kh i 17 1.3 Nguyên li u sinh kh i lignocellulose trình nhi t phân sinh kh i 21 1.3.1 Thành ph n hóa h c c a sinh kh i 21 1.3.2 Quá trình nhi t phân sinh kh i 23 1.3.3 Ti 1.4 Xúc tác acid r n ng ngu n sinh kh i t i Vi t Nam 25 graphene oxide 27 1.4.1 Than ho t tính 27 1.4.2 Gi i thi u ng d ng c a graphene oxide 28 u ch graphene oxide 31 1.5 Tình hình nghiên c c 32 1.6 Nh ng k t lu n rút t t ng quan tài li u 34 C NGHI M 36 2.1 Nguyên li u, hóa ch t thi t b 36 2.1.1 Nguyên li u, hóa ch t 36 2.1.2 H thi t b nhi t phân sinh kh i 38 u ch xúc tác acid r carbon sulfo hóa 38 n nhi t phân sinh kh i 39 t phân 39 2.2.3 Tái s d ng tái sinh xúc tác carbon sulfo hóa 40 u ch xúc tác acid r graphene oxide 40 u ch xúc tác graphene oxide 40 u ch xúc tác graphene oxide mang than ho t tính 40 nh thành ph ch t c a v t li u 41 nh thành ph n hóa h c c a nguyên li u sinh kh i 41 t c a xúc tác 43 t 43 u x tia X (XRD) 44 n t quét (SEM) 45 ng nhi t h p ph - gi i h p ph (BET) 45 h ng ngo i (IR) 47 Raman 48 49 acid-base 49 i h p ph NH3 nhi (TPD-NH3) 51 nh di n tích b m t riêng s l p c a graphene oxide 53 t tính xúc tác ph n ng este hóa acid lactic 57 2.5.1 Xây d ng chu ng ethyl lactate b pháp GC-FID 57 t tính xúc tác ph n ng este hóa acid lactic 59 2.6 ng d ng dung môi sinh h c gia công thu c b o v th c v t 59 2.6.1 Pha ch dung môi sinh h c 59 ng dung môi sinh h c 59 2.6.3 Gia công thu c b o v th c v t 60 u qu ng d ng c a dung môi sinh h c pha ch thu c b o v th c v t 60 ng thu c b o v th c v t 60 2.6.4.2 Kh o nghi m s n ph m thu c BVTV deltamethrin 2.5EC di n r ng 60 T QU VÀ TH O LU N 62 3.1 Xúc tác acid r 3.1.1 T ng h carbon sulfo hóa 62 t xúc tác carbon sulfo hóa 62 3.1.1.1 Nghiên c u trình nhi t phân sinh kh i 62 3.1.1.2 Nghiên c u q trình sulfo hóa than nhi t phân 71 3.1.2 Ho t tính xúc tác carbon sulfo hóa ph n ng este hóa acid lactic 87 ng chu ng ethyl lactate h n h p ph n ng 87 3.1.2.2 Ho t tính c a xúc tác carbon sulfo hóa ph n ng este hóa 88 3.1.3 ng c 3.1.4 Kh n hi u su t ph n ng este hóa acid lactic 90 d ng tái sinh xúc tác 91 3.2 Xúc tác acid r graphene oxide 95 graphene oxide 95 3.2.2 Ho t tính c graphene oxide ph n ng este hóa acid lactic 99 3.2.3 Kh tính d ng c a xúc tác graphene oxide mang than ho t 100 3.3 Dung môi sinh h c gia công thu c b o v th c v t 103 3.3.1 Nghiên c u ch h DMSH gia công thu c b o v th c v t d ng EC 103 3.3.1.1 Nghiên c u t l FAME EL DMSH 103 3.3.1.2 ng ch b a s n ph m thu c BVTV 106 tiêu k thu t c a DMSH 106 ng thu c BVTV deltamethrin 2.5EC chloropyrifos ethyl 20EC ch a DMSH 107 3.3.4 Th nghi m ho t tính sinh h c c a s n ph m Biosol-D2.5EC di n r ng 108 K T LU N 109 NH I C A LU N ÁN 111 DANH M C CÁC CƠNG TRÌNH KHOA H 112 TÀI LI U THAM KH O 113 PH L C 113 127 DANH M C KÝ HI U VÀ CH CS VI T T T Carbon sulfo hóa Mc Ro Bm Bã mía Vt V tr u Be Bèo l c bình Tn Thân ngơ Ts Thân s n GO Graphene oxide AC Than ho t tính GO/AC Graphene oxide mang than ho t tính MeOH Metanol EtOH Ethanol LA Acid lactic EL Ethyl lactate HMF Hydroxymethylfurfural HPA Acid 12- phosphotungstic (H3PW12O40) MB Methylene blue (Xanh methylen) UV-Vis Ultraviolet-Visible (Ph T ngo i-kh ki n) TG-DTA Thermalgravimetry- Differential Thermal Analysis ( phân tích nhi t tr ng vi sai) XRD X-Ray Diffraction (Ph nhi u x tia X) SEM Scanning Electron Microscopy (Kính hi EDX EDX : Energy-dispersive X-ray (Ph tán x FT-IR Fourier Transform Infrared Spectroscopy (Quang ph h ng ngo i bi i) n t quét) ng tia X) BET Brunauer-Emmett-Teller ( ng nhi t h p ph - gi i h p ph N2) SBET Di n tích b m t riêng TKPT Tinh t phân tích %v Ph %kl Ph DMSH Dung môi sinh h c FAME Fatty acid methyl esters (Methyl este c a acid béo) Ho tích ng ng b m t NK 2010 New Kagel 2010 BVTV B o v th c v t EC u (Emunsifiable concentrates) TCVN Tiêu chu n Vi t Nam TCCS Tiêu chu DANH M C B NG B ng 1.1 M t s cơng trình nghiên c ng h c c a ph n ng este hóa gi a acid lactic ethanol 11 B ng 1.2 Xúc tác acid r n cho ph n ng este hóa acid lactic thành ethyl lactate 12 B ng 1.3 Xúc tác carbon sulfo hóa t ng h p h B ng 1.4 Ti i ph ph m nông nghi 19 26 B ng 2.1 Danh m c nguyên v t li u, hóa ch t 36 B ng 2.2 Ký hi u s n ph m nhi t phân xúc tác CS t sinh kh i 39 B ng 2.3 N B MB cân b ng ph thu c n ng MB h p ph 1g GO u 54 n cân b ng 55 B ng 3.1 Thành ph n hóa h c c a sinh kh i 62 B ng s n ph m than nhi c t ngu n sinh kh i 67 B ng 3.3 Di n tích b m t riêng c a than nhi t phân xúc tác CS t ngu n nguyên li u 68 B ng 3.4 Di n tích b m t riêng c a than nhi nhi B ng 3.5 S phân t bèo nhi t phân 69 ng c a th i gian nhi ng s n ph m than nhi t 70 B ng 3.6 Thành ph n nguyên t c a xúc tác CS.Mc t l ch t ph n ng 71 B ng 3.7 ng t l ch t ph n ng c n tính ch t acid c a xúc tác 72 B ng 3.8 ng c a nhi n tính ch t acid c a xúc tác 77 B ng 3.9 ng c a nhi SO3H c a xúc tác CS 79 B ng 3.10 ng c a nhi n thành ph n nguyên t c a m u xúc tác t B ng 3.11 80 ng c a nhi n di n tích b m t riêng c a m u xúc tác CS.Mc t nguyên li B ng 3.12 ng c a th 81 ng tâm acid SO3H 82 B ng 3.13 Tính ch t acid c acid-base 83 B ng 3.14 Tính ch t acid c B ng 3.15 L -NH3 86 ng tâm acid c a xúc tác CS.Mc sau tái sinh 94 B ng 3.16 Di n tích b m t riêng tâm acid SO3H c graphene oxide 98 B ng 3.17 S ph thu c kh t ch t vào thành ph n c a DMSH 104 B ng 3.18 Nhi ch p cháy c a DMSH v i t l thành ph n khác 105 B t b c a deltamethrin 2.5EC chloropyrifos ethyl 20EC 105 B ng 3.20 ng c b gi c a s n ph m deltamethrin 2.5EC chloropyrifos ethyl 20EC 106 B ng 3.21 K t qu ch tiêu k thu t c a DMSH 107 B ng 3.22 K t qu ch tiêu k thu t c a thu c BVTV Biosol-D2.5EC Biosol-Ch20EC 107 B ng 3.23 M sâu cu n hi u l c c a thu c BVTV th i gian kh o nghi m 108 DANH M C HÌNH Hình 1.1 Cơng th c c u t o c a ethyl lactate Hình 1.2 ph n ng este hóa acid lactic ph n ng th Hình 1.4 ph n ng este hóa b i xúc tác sulfated zirconia Hình 1.5 C xu t c a xúc tác carbon sulfo hóa 14 t ng h p xúc tác carbon sulfo hóa v i tác nhân 4-benzene diazonium sulfonate 16 Hình 1.7 C Hình 1.8 xu t acid r carbon c a Hara 16 u ch xúc tác carbon sufo hóa t saccharide 17 Hình 1.9 C u trúc phân t c a sinh kh i 22 Hình 1.10 C u trúc phân t c a monome h p ph n c a lignin 23 chuy n hóa thành ph n sinh kh i t q trình nhi t phân 24 xu t c u trúc màng graphene oxide 28 Hình 1.13 t ng h p graphene oxide t b t than chì 32 Hình 2.1 H thi t b nhi t phân sinh kh i 38 Hình 2.2 S ph n x b m t tinh th 44 Hình 2.3 th s ph thu c c a Hình 2.4 P theo P/Po 46 W(Po - P) thi t b máy phân tích nguyên t 49 Hình 2.5 Ph UV-Vis c a m u so sánh (ref 50 mg.L-1) m u MB sau h p ph cân b ng 54 ng MB h p ph Hì Hình 3.1 Gi n cân b ng khác 55 th bi u di n s ph thu c c a Ceq/a vào Ceq 56 phân tích nhi t TGA c a m u nguyên li u môi ng N2 63 Hình 3.2 Ph Raman c a than nhi Hình 3.3 Gi nhi 64 XRD c a m u than nhi t phân sinh kh i 66 DANH MỤC CÁC CƠNG TRÌNH KHOA HỌC ĐÃ CÔNG BỐ Nguyễn Mạnh Hà, Bùi Ngọc Quỳnh, Nguyễn Minh Đăng, Hoàng Trọng Hà, Nguyễn Đăng Quang, Vũ Thị Thu Hà, Ứng dụng phương pháp chuẩn độ axit-bazơ định lượng tâm axit xúc tác cacbon sulfonat hóa, Tạp chí Xúc tác Hấp phụ số T5, N2, 2016, 146-151 Nguyễn Mạnh Hà, Nguyễn Minh Đăng, Hoàng Trọng Hà, Nguyễn Đăng Quang, Vũ Thị Thu Hà, Nghiên cứu tổng hợp xúc tác axit rắn sở carbon sulfo hóa từ sinh khối, ứng dụng phản ứng este hóa axit 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