Luận án Nghiên cứu tổng hợp xúc tác dị thể lưỡng chức năng trên cơ sở silicat chứa canxi, ứng dụng để chuyển hóa dầu nhiều axit tự do thành biodiesel

ng xúc tác lên tới 26 lần. Việc nghiên cứu trạng thái của xúc tác MCS sau sử dụng cho thấy, quá trình giảm hoạt tính xúc tác có nguyên nhân chủ yếu là sự che phủ của các phân tử dầu sau mỗi lần phản ứng, làm bề mặt riêng và sự tiếp xúc của các tâm axit – bazơ với chất phản ứng không còn cao nhƣ ban đầu. Lực axit-bazơ của xúc tác MCS sau sử dụng giảm không đáng kể chứng tỏ tính ổn định cao của các tâm axit – bazơ trên bề mặt xúc tác, mặc dù lƣợng tâm giảm mạnh do kết quả của sự che phủ bề mặt xúc tác. Kết quả tái sử dụng và tái sinh xúc tác cũng là bằng chứng mạnh mẽ khẳng định sự hiệu quả của việc sử dụng xúc tác lƣỡng chức MCS cho dầu vi tảo họ Botryococcus nói riêng và các loại dầu có chỉ số axit cao nói chung. 108 NHỮNG ĐIỂM MỚI CỦA LUẬN ÁN 1. Chế tạo thành công hai hệ xúc tác lƣỡng chức axit – bazơ theo phƣơng pháp đồng ngƣng tụ, ứng dụng cho quá trình tổng hợp biodiesel từ dầu vi tảo họ Botryococcus nói riêng và các loại dầu có chỉ số axit cao nói chung. Xúc tác CS và MCS là hai hệ xúc tác mới, có cấu trúc và tính chất đặc biệt khi sở hữu cả hai loại tâm axit – bazơ có lực mạnh, thúc đẩy chọn lọc hai phản ứng chính là este hóa các axit béo tự do và trao đổi este các triglyxerit, giúp quá trình chuyển hóa nguyên liệu có thể đƣợc thực hiện trong những điều kiện êm dịu hơn so với các xúc tác axit, và hiệu quả hơn so với các xúc tác bazơ khác; 2. Sử dụng phƣơng pháp phổ kỹ thuật cao nghiên cứu sâu vào cấu trúc xúc tác CS và MCS, đó là phổ hấp thụ tia X (XAS), bao gồm hai thành phần là phổ hấp thụ tia X gần ngƣỡng (XANES) và phổ hấp thụ tia X cấu trúc tinh vi mở rộng (EXAFS). Kết quả cho thấy, xúc tác CS và MCS chứa các tâm Ca với số phối trí 6, bao quanh bởi hệ liên kết –O-Si- đặc trƣng cho hệ thống oxit phức hợp CaO-SiO2. Thông qua cấu trúc mô phỏng xác định từ phổ XAS, giải thích đƣợc sự xuất hiện tính axit và bazơ trong hai xúc tác CS và MCS: các tâm axit sinh ra từ sự chênh lệch điện tích dọc theo các liên kết Ca-O-Si, các tâm bazơ xuất hiện tại các khuyết tật chứa các phần tử O2-; cả hai loại tâm này đều định vị trên bộ khung xúc tác, nên có tính chất ổn định, bền vững trong môi trƣờng phản ứng. Giải thích phù hợp tốt với các kết quả định lƣợng độ axit – bazơ theo phƣơng pháp thực nghiệm; 3. Sử dụng nguyên liệu dầu vi tảo họ Botryococcus làm nguyên liệu chính cho quá trình tổng hợp biodiesel trên xúc tác MCS. Đây là loại nguyên liệu mới, thuộc thế hệ thứ 3, ít đƣợc nghiên cứu tại Việt Nam, cho năng suất thu dầu rất cao và rất có tiềm năng làm nguyên liệu chính cho việc sản xuất biodiesel trên quy mô lớn; 4. Xây dựng đƣợc phƣơng pháp đồ thị nhằm xác định nhanh hiệu suất tạo biodiesel từ dầu vi tảo họ Botryococcus theo độ nhớt động học tại 40oC của sản phẩm biodiesel sau tinh chế, gọi là phƣơng pháp hiệu suất – độ nhớt. Phƣơng pháp này dựa trên hai phƣơng trình chính: Y = -5,5112X + 122,34, áp dụng trong khoảng tuyến tính khi hiệu suất cao hơn 67,9%, tƣơng ứng với độ nhớt thấp hơn 9,93 cSt; và Y = 222,65X-0,523, áp dụng trong khoảng phi tuyến khi hiệu suất thấp hơn 67,9%, tƣơng ứng với độ nhớt cao hơn 9,93 cSt; trong đó Y là hiệu suất tạo biodiesel (%) và X là độ nhớt động học của biodiesel tại 40oC (cSt). 109 DANH MỤC CÁC C NG TRÌNH Đ C NG BỐ CỦA LUẬN ÁN 1. Nguyễn Khánh Diệu Hồng, Nguyễn Đăng Toàn, Nguyễn Trung Thành, Lê Thị Hồng Ngân, Đinh Thị Ngọ (2012) Xác định các chỉ tiêu kỹ thuật và phân tích thành phần hóa học dầu vi tảo họ Botryococcus sp làm nguyên liệu cho sản xuất biodiesel, Tạp chí Hóa học, 50(4A), 375-378. 2. Nguyễn Khánh Diệu Hồng, Nguyễn Đăng Toàn (2013) Nghiên cứu tổng hợp và đặc trƣng xúc tác lƣỡng chức phức hợp canxi silicat (CS), ứng dụng cho quá trình tổng hợp biodiesel từ dầu vi tảo, Tạp chí Hóa học 51(2C), 977-982. 3. Nguyễn Đăng Toàn, Nguyễn Khánh Diệu Hồng (2013) Nghiên cứu tổng hợp xúc tác dị thể lƣỡng chức năng meso calcium silicate (MCS), ứng dụng cho phản ứng chuyển hóa dầu vi tảo thành nhiên liệu sinh học biodiesel, Tạp chí Hóa học 51(4AB), 95-101. 4. Nguyễn Đăng Toàn, Vũ Đỗ Hồng Dƣơng, Nguyễn Khánh Diệu Hồng (2013) Nghiên cứu tổng hợp xúc tác dị thể lƣỡng chức năng silicat chứa canxi (MCS) dạng mao quản trung bình, ứng dụng cho quá trình tổng hợp biodiesel từ dầu vi tảo, Tạp chí Xúc tác và Hấp phụ, 2(2), 182-190. 5. Trần Mai Khôi, Nguyễn Đăng Toàn, Nguyễn Chí Công, Nguyễn Khánh Diệu Hồng (2013) Nghiên cứu chuyển hóa dầu thực vật có chỉ số axit cao thành nhiên liệu sinh học trên xúc tác dị thể lƣỡng chức năng thế hệ mới, Tạp chí Dầu khí 8, 36-45. 6. 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Kết quả đo BET và phân bố mao quản của xúc tác MCS 134 135 136 137 138 139 140 141 142 143 144 145 146 147 PHỤ LỤC 2. KẾT QUẢ ĐO TPD-NH3 VÀ TPD-CO2 1. Kết quả đo TPD-NH3 của xúc tác CS 148 149 150 2. Kết quả TPD-CO2 của xúc tác CS 151 152 153 3. Kết quả TPD-NH3 của xúc tác MCS 154 155 156 157 158 4. Kết quả TPD-CO2 của xúc tác MCS 159 160 161 162 163 PHỤ LỤC 3: PHỔ FT-IR 164 1. Phổ FT-IR của xúc tác CS 2. Phổ FT-IR của xúc tác MCS PHỤ LỤC 4. CÁC PHỔ MS CỦA BIODIESEL TỪ DẦU VI TẢO HỌ BOTRYOCOCCUS 4 7 1 .3 7 9 6 .4 8 5 4 .8 8 7 5 .1 1 0 9 4 .0 1 4 9 2 .1 1 6 3 8 .8 3 4 6 0 .6 3 8 5 5 .5 CS 10 20 30 40 50 60 70 80 90 100 % T ra n s m it ta n c e 500 1000 1500 2000 2500 3000 3500 4000 Wavenumbers (cm-1) Number of sample scans: 32 Number of background scans: 32 Resolution: 4.000 Sample gain: 4.0 Mirror velocity: 0.6329 Aperture: 100.00 4 6 4 7 9 1 .5 9 5 5 .0 1 0 8 3 .2 1 6 4 9 .8 2 8 4 7 .2 2 9 2 0 .8 3 4 4 5 .5 *Mau MSC-3 30 35 40 45 50 55 60 65 70 % T ra n s m it ta n c e 500 1000 1500 2000 2500 3000 3500 Wavenumbers (cm-1) Number of sample scans: 64 Number of background scans: 64 Resolution: 4.000 Sample gain: 2.0 Mirror velocity: 0.6329 Aperture: 100.00 165 166 167 168 169 170 171 172 173