ĐẠI HỌC QUỐC GIA THÀNH PHỐ HỒ CHÍ MINH TRƯỜNG ĐẠI HỌC BÁCH KHOA NGUYỄN HOÀNG VIỆT PHÚC NGHIÊN CỨU CHẤT XÚC TÁC PtAl-MCM41, PtAlMCM41 CHO PHẢN ỨNG ĐỒNG PHÂN HÓA CONDENSATE DẦU MỎ VIỆT NAM Chuyên ngành : Công nghệ hóa học Mã ngành : 60 52 75 LUẬN VĂN THẠC SĨ Thành phố Hồ Chí Minh, tháng năm 2007 TRƯỜNG ĐẠI HỌC BÁCH KHOA CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM PHÒNG ĐÀO TẠO SĐH ĐỘC LẬP- TỰ DO- HẠNH PHÚC Tp HCM, ngày 24 tháng 05 năm 2007 NHIỆM VỤ LUẬN VĂN THẠC SĨ Họ tên học viên: NGUYỄN HOÀNG VIỆT PHÚC Ngày, tháng, năm sinh: 26/10/1982 Chuyên ngành: CÔNG NGHỆ HÓA LÝ I Phái : Nam Nơi sinh: Bà Rịa-Vũng Tàu MSHV: K2005.110 TÊN ĐỀ TÀI : NGHIÊN CỨU CHẤT XÚC TÁC PtAl-MCM41, PtAlMCM41 CHO PHẢN ỨNG ĐỒNG PHÂN HÓA CONDENSATE DẦU MỎ VIỆT NAM II III IV V NHIỆM VỤ VÀ NỘI DUNG: Tổng hợp chất xúc tác MCM41 (ký hiệu SiMCM41) Tiến hành trao đổi với Al3+ đưa Al vào mạng tinh thể SiMCM41 Nghiên cứu đặc trưng hóa lý bề mặt chất xúc tác Tiến hành lắp ráp thiết bị phản ứng hoàn chỉnh phương pháp phân tích sản phẩm Tiến hành nghiên cứu phản ứng đồng phân hóa condensate dầu mỏ Việt Nam NGÀY GIAO NHIỆM VỤ: 03/07/2006 NGÀY HOÀN THÀNH NHIỆM VỤ: CÁN BỘ HƯỚNG DẪN: PGS.TS TRẦN KHẮC CHƯƠNG CÁN BỘ HƯỚNG DẪN CN BỘ MÔN QL CHUYÊN NGÀNH PGS.TS TRẦN KHẮC CHƯƠNG Nội dung đề cương luận văn thạc só Hội đồng chuyên ngành thông qua TRƯỞNG PHÒNG ĐT- SĐH Ngày … tháng… năm 2007 TRƯỞNG KHOA QL NGÀNH CÔNG TRÌNH ĐƯC HOÀN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA ĐẠI HỌC QUỐC GIA TP HỒ CHÍ MINH Cán hướng dẫn khoa học : PGS.TS TRẦN KHẮC CHƯƠNG Cán chấm nhận xét :·············································································· Cán chấm nhận xét :·············································································· LUẬN VĂN THẠC SĨ ĐƯC BẢO VỆ TẠI HỘI ĐỒNG CHẤÙM BẢO VỆ LUẬN VĂN THẠC SĨ TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA , ngày … tháng … năm …… LỜI CẢM ƠN Trước tiên xin bày tỏ biết ơn sâu sắc đến PGS.TS Trần Khắc Chương, người thầy hướng dẫn tận tình thời gian làm luận văn thạc só phòng thí nghiệm nghiên cứu xúc tác, thầy xa bỏ thời gian sửa chữa, giúp hoàn thành tốt luận văn Tôi xin gởi lời cảm ơn đến TS Nguyễn Hữu Lương, Th.Só Ngô Thanh An, Th.Só Hoàng Khoa Anh Tuấn, Th.Só Nguyễn Quang Long có góp ý q báu cho nội dung luận văn Tôi xin cảm ơn thầy cô hội đồng bảo vệ đọc có ý kiến đóng góp q giá Tôi xin cảm ơn bạn học viên cao học đại học, đặc biệt Trần Thị Mỹ Chi, Lạc Kiến Triều, Đoàn Kim Hồng… nhiệt tình giúp đỡ, hỗ trợ thực luận văn Gia đình điểm tựa vững chắc, xin cảm ơn người thân yêu: ba mẹ, chị hai… bên động viên, giúp đỡ hoàn thành tốt luận văn TÓM TẮT MCM41, vật liệu mao quản trung bình thuộc họ M41S, sở hữu hệ thống mao quản đồng đều, kích thước mao quản nằm khoảng [15-100A0], bề mặt riêng lớn ứng dụng ngày rộng rãi nhiều lónh vực, đặc biệt ngành công nghiệp dầu khí Vật liệu mao quản trung bình MCM41,biến tính việc đưa nguyên tử Al lên xúc tác hai phương pháp khác đồng thời với việc tẩm Pt, đóng vai trò chất xúc tác lưỡng chức cho phản ứng đồng phân hóa Độ axit xúc tác tăng thêm việc khảo sát trộn với HZSM5 với tỷ lệ khác Đặc trưng xúc tác phương pháp : phổ XRD, phổ IR, phương pháp BET, phương pháp nghiên cứu ảnh SEM nghiên cứu độ axit TPD-NH3 Hoạt tính xúc tác kiểm tra phản ứng hydroisomer hóa condensate Bạch Hổ, Việt Nam hệ thống phản ứng dòng vi lượng Độ chọn lọc phản ứng hydroisomer hóa condensate đạt tối đa 66.15% ABSTRACT MCM41, the mesoporous material in M41S family, possesses well ordered pores of diameter about [15-100Ao] with large specific surface area It has been applied widely in various fields, especially in petroleum refining industry Aluminum is introduced into mesoporous material MCM41 with two different methods as well as platinum is impregnated on MCM41 The role of these modified catalysts is bifunctional catalyst for isomerisation The acidity of catalysts have been obviously increased by studying the various different ratios of HZSM5 blending with catalysts The characterization of catalysts are studied via modern physicochemical analyzed methods such as: XRD, IR, SEM, BET, TPD-NH3 Catalytic performances of prepared catalysts are tested by hydroisomerisation condensate Bach Ho, Viet Nam, on micro-stream reaction system The best selectivity value of this reaction is 66.15% i MỤC LỤC MỤC LỤC BẢNG ···································································································· iii MỤC LỤC HÌNH ······································································································ iv MỤC LỤC SƠ ĐỒ····································································································· vi Phần I: Tổng quan tài liệu ······················································································ 01 Quá trình isomer hóa công nghiệp lọc dầu ·············································· 01 1.1 Vai trò trình hydroisomer ······························································· 01 1.2 Xúc tác cho phản ứng hydroisomer hóa ······················································ 01 1.3 Cơ chế phản ứng hydroisomer hóa ······························································ 03 1.4 Vấn đề condensate dầu mỏ Việt Nam yêu cầu cần thiết nghiên cứu đồng phân hóa ··········································································································· 07 Tổng hợp biến tính vật liệu mao quản trung bình MCM41 ·························· 08 2.1 Giới thiệu vật liệu mao quản trung bình ················································ 08 2.1.1 Nguyên nhân đời vật liệu mao quản trung bình ···················· 08 2.1.2 Tính chất vật liệu mao quản trung bình ····································· 09 2.1.3 Phân loại vật liệu mao quản trung bình ············································· 13 2.1.4 Cơ chế hình thành cách tổng hợp vật liệu mao quản trung bình · 13 2.1.5 Các yếu tố ảnh hưởng đến trình tổng hợp MCM41 ··················· 21 2.1.6 Những ứng dụng chất xúc tác mao quản trung bình ··················· 24 2.2 Biến tính vật liệu MQTB dùng làm xúc tác cho phản ứng đồng phân hóa ···································································································· 26 2.2.1 Biến tính MCM41 trao đổi ion Al3+ với modun Si/Al khác ········································································································ 27 2.2.2 Biến tính MCM41 cách đưa Al vào mạng tinh thể MCM41 với modun Si/Al khác ····································································· 27 Phần II: Phương pháp thực nghiệm ········································································ 28 Qui trình tổng hợp Si-MCM41 ··········································································· 28 1.1 Nguyên liệu cho trình tổng hợp ····························································· 28 1.2 Qui trình tồng hợp ························································································· 28 Biến tính vật liệu mao quản trung bình MCM41 ··············································· 30 2.1 Biến tính xúc tác cách trao đổi ion nhôm silic với mun khác ·················································································································· 30 2.2.Biến tính xúc tác cách đưa nhôm vào mạng với mun khác ················································································································ 31 Các phương pháp đặc trưng xúc tác ··································································· 34 3.1 Phương pháp quang phổ nhiễu xạ tia X························································ 34 ii 3.2 Phương pháp đo hồng ngoại IR ···································································· 35 3.3 Phương pháp đo bề mặt riêng BET······························································· 36 3.4 Phương pháp giải hấp theo chương trình nhiệt độ TPD-NH3······················· 37 3.5.Nghiên cứu hoạt tính chất xúc tác phản ứng hydroisomer hóa condensate Bạch Hổ ································································································· 42 3.5.1 Nguyên liệu condensate ··········································································· 43 3.5.2 Chuẩn bị xúc tác ống phản ứng ··························································· 43 3.5.3 Hoạt hóa làm xúc tác ··································································· 43 3.5.4 Trộn dòng, tiến hành phản ứng lấy mẫu ·············································· 44 Hoàn chỉnh hệ thống phân tích sắc ký khí·························································· 45 4.1 Tổng quan sắc ký khí ·············································································· 45 4.1.1 Quá trình tónh (nhiệt động học) sắc ký khí ··································· 46 4.1.2 Quá trình động (động lực học) sắc ký khí ···································· 47 4.2 Các phận máy sắc ký ····································································· 47 4.2.1 Bộ phận bơm mẫu ( injector ) ······························································ 48 4.2.2 Cột sắc kyù ( capilary column) ······························································ 48 4.2.3 Detector ································································································ 49 4.2.4 Detector ion hóa lửa ( FID )························································ 50 4.3 Lắp ráp phận máy sắc ký khí ·························································· 52 4.3.1 Cột mao quản ························································································· 52 4.3.2 Lưu lượng kế ························································································· 53 4.3.3 Lò điều nhiệt ························································································· 55 Phần III : Kết thực nghiệm ·············································································· 56 Kết thực nghiệm tổng hợp MCM41 ····························································· 56 Kết nghiên cứu ảnh hiển vi điện tử quét SEM ············································ 61 Kết đo bề mặt riêng BET ············································································· 62 Kết đo axit mẫu xúc tác theo phương pháp TPD-NH3 ································ 62 Khảo sát hoạt tính chất xúc tác phản ứng hydroisomer hóa condensate mỏ Bạch Hổ, Việt Nam ······················································································· 65 5.1 Ảnh hưởng nhiệt độ đến sản phẩm ························································ 65 5.2 Kết với mẫu xúc tác khác ················································· 71 5.3 Kết luận ·········································································································· 74 Kết luận chung········································································································· 75 iii MỤC LỤC BẢNG Bảng 1: Cấu trúc vật liệu mao quản trung bình không chứa Si ················· 14 Bảng 2: Tẩm phụ gia kim loại lên họ vật liệu M41S ········································· 21 Bảng 3: Dao động đặc trưng phổ IR cấu trúc xúc tác ······················ 36 Bảng 4: Độ dẫn điện độ nhớt chất khí sử dụng sắc ký khí ······························································································································· 49 Bảng 5: Kết độ axit mẫu xúc tác xác định phương pháp TPD-NH3.·············································································································· 63 iv MỤC LỤC HÌNH Hình 1: Sơ đồ chu trình isomer hóa UOP- Once Though (O-T) ························· 03 Hình 2: Tâm axit Bronsted chất xúc tác ······················································ 10 Hình 3: Cơ chế hình thành mixen ống vật liệu mao quản trung bình ········· 15 Hình 4: Cơ chế hình thành vật liệu mao quản trung bình ································· 16 Hình 5: Cơ chế xếp ống ················································································ 16 Hình : Cơ chế silicate gấp ················································································ 17 Hình 7: Cơ chế phù hợp mật độ điện tích ··························································· 17 Hình 8: Cơ chế độn lớp ······················································································· 18 Hình 9: Cơ chế hình thành pha SLC ···································································· 18 Hình 10: Các kiểu tương tác chất hoạt động bề mặt tiền chất vô ··· 19 Hình 11: Mô tả tương tác chất hoạt động bề mặt tiền chất vô ··· 20 Hình 12: Qui trình giải hấp theo chương trình nhiệt độ ····································· 40 Hình 13: Sơ đồ nghiên cứu phản ứng dòng vi lượng cho phản ứng hydroisomer hóa ··································································································· 42 Hình 14: Sơ đồ hệ thống sắc ký khí.····························································· 47 Hình 15: Hình ảnh phận bơm mẫu ( injector) ········································· 48 Hình 16: Sơ đồ nguyên lý hoạt động detector ion hóa lửa ················ 50 Hình 17: Lưu lượng kế xác định tốc độ dòng hệ thống sắc ký khí··········· 53 Hình 18: Phổ XRD chất xúc tác MCM41····················································· 56 Hình 19: Phổ XRD Al-MCM41 với tỷ lệ khác ······················· 56 Hình 20: Phổ IR chất xúc tác MCM41 ························································· 58 Hình 21: Phổ IR AlMCM41 có modul=5······················································ 59 Hình 22: Phổ IR AlMCM41 có modul=10···················································· 59 Hình 23: Phổ IR AlMCM41 có modul=15···················································· 60 Hình 24: Phổ IR AlMCM41 có modul=20···················································· 60 Hình 25: nh hiển vi điện tử SEM chất xúc tác MCM41 ··························· 61 Hình 26: Độ axit mẫu xúc tác 1.2%Pt-5%HZSM5 + AlMCM41 với modul khác nhau················································································· 63 Hình 27: Độ axit mẫu xúc tác modul 10, khác %HZSM5 ······· 63 Hình 28: Độ chuyển hóa sản phẩm theo biến thiên nhiệt độ················· 65 Hình 29: Hiệu suất sản phẩm theo biến thiên nhiệt độ ·························· 66 Hình 30: Phân bố thành phần sản phẩm theo nhiệt độ nghiên cứu mẫu xúc tác ······················································································································ 67 Hình 31: Phân bố thành phần sản phẩm theo nhiệt độ nghiên cứu mẫu xúc taùc ······················································································································ 68 ... CÔNG NGHỆ HÓA LÝ I Phái : Nam Nơi sinh: Bà Rịa-Vũng Tàu MSHV: K2005.110 TÊN ĐỀ TÀI : NGHIÊN CỨU CHẤT XÚC TÁC PtAl- MCM41, PtAlMCM41 CHO PHẢN ỨNG ĐỒNG PHÂN HÓA CONDENSATE DẦU MỎ VIỆT NAM II III... cứu chế tạo thành công xúc tác cho trình isomer hóa cần thiết 1.2 Xúc tác cho phản ứng hydroisomer hóa Xúc tác pha lỏng : AlCl3 hoạt hóa HCl, xúc tác AlBr3 , AlCl3 + SbCl3 Ưu điểm loại xúc tác. .. loại xúc tác Chất mang cho kim loại oxyt kim loại Xúc tác Ni-Mo MCM41 ứng dụng phản ứng hydrocracking phân đoạn gasoil Chất mang cho xúc tác axit,bazơ Vật liệu mao quản trung bình ứng dụng làm chất