Luận án tổng hợp, đặc trưng tính chất xúc tác acis trên cơ sở carbon từ sinh khối và graphene oxide ứng dụng cho phản ứng este hóa acid lactic

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 ngô 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 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 Hình 3.4 nh SEM c a m u xúc tác CS t ngu n sinh kh i 74 ng ngo Hình 3.6 Gi 75 XRD c a xúc tác CS t ngu n sinh kh i 76 Hình 3.7 nh SEM c a m u CS.Mc t Hình 3.8 Gi nhi t h p ph NH3 nhi sulfo hóa 81 Calorimetry c a xúc tác CS.Mc 83 Hình 3.9 Gi TPD-NH3 c a xúc tác carbon sulfo hóa t sinh kh i 85 ng chu ng ethyl lactate 87 Hình 3.11 Hi u su t t o thành ethyl lactate sau gi ph n ng 88 Hình 3.12 Hi u su t t o thành ethyl lactate sau gi ph n ng 89 Hình 3.13 Hi u su t t o thành ethyl lactate theo th i gian v ng xúc tác khác sau gi ph n ng 90 Hình 3.14 Hi u su t t o thành ethyl lactate sau chu k ph n ng 92 Hình 3.15 Hi u su t t o thành ethyl lactate c a xúc tác CS.Mc tái sinh sau chu k ph n ng 93 Hình 3.16 Ph h ng ngo i c u (CS.Mc) sau tái sinh (CS.Mc.TS) 94 Hình 3.17 nh SEM c Hình 3.18 Gi u (a) sau tái sinh (b) 94 XRD c a than ho t tính (AC); graphene oxide (GO); GO/AC 96 Hình 3.19 nh SEM- EDX c a GO (a), SEM c a AC (b), GO/AC (c) 97 Hình 3.20 Ph FT-IR c a AC (a), GO (b), GO/AC (c) 97 Hình 3.21 Hi u su t t o thành ethyl lactate theo th i gian than ho t tính (a), CS.Mc (b), graphene oxide (c), GO/AC (d) 99 Hình 3.22 Ho t tính c a xúc tác GO/AC sau chu k ph n ng 100 Hình 3.23 Ho t tính c a xúc tác CS.Mc sau chu k ph n ng 101 Hình 3.24 Mơ hình s este hóa gi a than ho t tính v i graphene oxide 102 Hình 3.25 Ph h ng ngo i c a xúc tác GO/AC GO/AC6 sau chu k ph n ng 102 M U Ethyl lactate m t nh ng dung môi sinh h c có kh thay th dung mơi truy n th ng có ngu n g c d u m d ng công nghi th c v ng n xu t ch t t y r a, pha ch thu c b o v c tính t cháy, r t t n s c kh h y sinh h c, s d ng ngu n nguyên li u tái t o ozone c bi ng x ng c t o thành t ph n ng cân b ng nhi ng gi a acid lactic ethanol Bên c nh bi n pháp nh m c i thi n hi u su t thu i b ng phí v i m c liên t c b ng cách c k t h p s d ng xúc tác acid gi i pháp hi u qu c n thi t nh ph n ng t o thành s n ph m ethyl lactate Xúc tác hi u qu cho q trình este hóa acid lactic thành ethyl lactate pha l ng thi t b ng c tách kh i h n h p sau ph n n ng l n ch t th zeolite, nh /ZrO2 ng th ng Do v y, xúc tác acid d th i ion Amberlyst 15, Nafion NR 50, H3PW12O40, SO42- c nghiên c u s d ng thay th dàng tách kh i h n h p sau ph n ch n l ph n ng ph , có kh m ch n l c th p, t o d ng m i s d ng th d n ch c tb.G n carbon sulfo hóa cho q trình t ng h p ethyl lactate t acid lactic ethanol Xúc tác v i b n ch t carbon thân thi ng, khơng b hịa tan h u h t ng acid, base hay dung môi h c m nh v i ch t h u a nhóm ch c phenolic ( OH), carboxylic ( COOH) nhóm ch c acid m nh sulfonic ( SO3 ch c ch t o t ngu n nguyên li u c bi t t sinh kh i ph ph ph m nông, lâm nghi c t n d ng hi u qu V acid r t này, xúc tác carbon sulfo hóa h a h n xúc tác hi u qu cho ph n ng este hóa Bên c t lo i v t li u carbon ch a nhóm ch c acid m nh sulfonic ( SO3H) u ch b i trình oxy hóa graphite b s nhà khoa h c b c s quan tâm c a n hình, cịn mang tính ch u trúc x p d ng màng m ch c ch a oxy, kh n t nhanh, phân tán t Do v y, v t li T nh u ki n phù h p, có nhóm c xem xúc tác acid r nh trên, m c y ti m t cho lu n án nghiên c u tìm t ng h p acid r carbon t sinh kh i graphene oxide làm xúc tác cho ph n ng este hóa acid lactic thành ethyl lactate, ng d u ch dung môi sinh h c gia công thu c b o v th c v t th c hi n m ra, lu n án d ki n s th c hi n n i dung sau: - Nghiên c u m t cách h th ng trình t ng h ch g tính carbon sulfo hóa t ngu n sinh kh i ph bi n - T ng h - graphene oxide t tính c a xúc tác t ng h c ph n ng este hóa acid lactic thành ethyl lactate - Nghiên c u kh d ng xúc tác - Nghiên c u ng d ng s n ph sinh h c gia công thu c b o v th c v t u ch dung môi NG QUAN 1.1 Q trình este hóa acid u ch ethyl lactate 1.1.1 Tính ch t ng d ng c a ethyl lactate Các este h nhi t quan tr ng có ng d ng c cơng nghi c ph m, ch t d o, dung môi ch t trung gian ph n ng [1] a acid h ch ng n tiêu bi u ethyl lactate có th thay th dung mơi truy n th ng có ngu n g cd um ng d ng [2] Ngày nay, v i vi s n xu t xanh s b i kh t tiêu chu n u este tr nên quan tr ng y sinh h c c s n xu t t ngu n nguyên li u tái t o Ethyl lactate s n ph m este hóa c a acid lactic ethanol ki u ng, ethyl lactate m t ch t l ng không màu ho c ph t ánh vàng, i th p c a nó, ethyl lacta c s d ng ch ph ng c ph m, ph gia th c ph c hoa Hình 1.1 minh h a công th c c u t o c a ethyl lactate Hình 1.1 Cơng th c c u t o c a ethyl lactate c tìm th y t nhiên v i s m t lo t lo i th c ph Ethyl lactate có th ng nh , u vang, th t gà, nhi u lo i trái c s n xu t t ngu n sinh h c, có th t n t i ng phân quang h c (L) ho c (D), tùy thu c ngu n g c sinh h c c a acid lactic H u h t, ethyl lactate sinh h c ethyl (-) - L-lactate (ethyl (S)c s n xu t cơng nghi p t q trình hóa d ng h n h p c ng phân (L) (D) C ng ph i c tìm th y t nhiên ethyl lactate có th d dàng phân h y sinh h c coi m t dung môi xanh (green solvent) Ethyl lactate m c bi t h p d xu i v i ngành s n m sôi cao, áp su b m t th p v i ng d p s n hình t o l p ph t t cho g , polyeste kim lo tt t cách hi u qu Các ng d ng khác c a ethyl lactate làm ch t làm s ch công nghi p polyuretan cho b m t kim lo lo i m t cách hi u qu m , d u, keo dán nhi n li u r n M kh i ta cịn nh n ethyl lactate có th lo t b ô nhi m [3] ng c s d ng ngành c làm ph gia hòa tan ho c phân tán công th c bào ch c a nhi u lo i thu i ho ch t H p ch t tác nhân hi u qu c lý c a ho t hòa tan h p ch t có ho t tính sinh h ng [4] 1.1.2 Dung môi sinh h c H u h t dung môi h r c, ng n g c hóa th ch d b t cháy n s c kh ng (phá h y t ng ozone, gây ô nhi c), v d ng ngu n nguyên li u s n xu vi c s n c n ki t [5] Trong nh ng th p k tr l an toàn s c kh e môi n s phát tri n c a dung mơi sinh h c, dung mơi có ngu n g c t nhiên Các lo i dung mơi sinh h c có ngu n g c t th c v t có kh ng th i kh c ph ch uh dung mơi có ngu n g c hóa th khơng hóa gây có kh mc a t cháy, n s c kh e, không tham gia vào trình ozone quang ng c bi t có kh o Nh y sinh h c c s d ng ph bi n este DANH MỤC CÁC CƠNG TRÌNH KHOA HỌC ĐÃ CƠNG 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 lactic tạo thành etyl lactat, Tạp chí Hóa học, 55(5E 1,2), 2017, 178-183 Nguyễn Mạnh Hà, Nguyễn Minh Đăng, Nguyễn Quang Minh, Nguyễn Đăng Quang, Vũ Thị Thu Hà, Tổng hợp, đặc trưng xúc tác axit rắn từ mùn cưa, ứng dụng phản ứng este hóa axit lactic, Tạp chí Xúc tác Hấp phụ số T7, N1, 2018, 86-92 Phạm Thị Nam Bình, Hồng Thân Hoài Thu, Cao Thị Thúy, Nguyễn Mạnh Hà, Vũ Thị Thu Hà, Đánh giá hiệu dung môi sinh học gia công thuốc bảo vệ thực vật chứa hoạt chất deltamethrin, Tạp chí Hóa học ứng dụng, Giấy chứng nhận đăng số 35/2018/GCN, ngày 20 tháng 06 năm 2018 Vũ Thị Thu Hà, Vũ Văn Hà, Nguyễn Mạnh Hà, Lâm Thị Tho, Nguyễn Văn Chúc, Nguyễn 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