Luận án tiến sĩ về đánh giá technoeconomic quy trình hydrogenation và trireforming CO2 thành metanol

Luận án tiến sĩ phân tích technoeconomic evaluation of co2 utilization processes hydrogenation biand trireforming of co2 into, xây dựng cơ sở lý luận, kiểm chứng thực nghiệm, đóng

• Tác giả: Nguyen Bui Huu Tuan
• Người hướng dẫn: Dr. Uthaiporn Suriyapraphadilok
• Trường học: The Petroleum and Petrochemical College, Chulalongkorn University
• Chuyên ngành: Petroleum Technology
• Đề tài: Techno-Economic Evaluation of CO2 Utilization Processes: Hydrogenation, Bi- and Tri-Reforming of CO2 into Methanol Production
• Loại tài liệu: thesis
• Năm xuất bản: 2015
• Địa điểm: Bangkok

Tóm tắt

I. Đánh giá technoeconomic quy trình sản xuất metanol từ CO2

Quy trình sản xuất metanol từ CO2 đang trở thành một giải pháp tiềm năng trong việc giảm thiểu phát thải carbon. Đánh giá technoeconomic của quy trình này không chỉ xem xét hiệu suất sản xuất mà còn phân tích chi phí và lợi ích kinh tế. Việc sử dụng CO2 làm nguyên liệu để sản xuất metanol không chỉ giúp giảm lượng khí thải mà còn tạo ra sản phẩm có giá trị. Nghiên cứu này tập trung vào việc so sánh các quy trình khác nhau như hydrogenation, bi-reforming và tri-reforming để xác định quy trình tối ưu nhất về mặt kinh tế và môi trường.

1.1. Quy trình hydrogenation

Quy trình hydrogenation CO2 thành metanol là một trong những phương pháp phổ biến nhất. Nghiên cứu cho thấy rằng quy trình này có thể đạt được hiệu suất cao với điều kiện tối ưu. Tuy nhiên, chi phí sản xuất vẫn là một yếu tố quan trọng cần xem xét. Việc sử dụng các chất xúc tác hiệu quả có thể giảm thiểu chi phí và tăng cường hiệu suất. Theo nghiên cứu, chi phí sản xuất metanol từ CO2 thông qua hydrogenation có thể cạnh tranh với các nguồn năng lượng truyền thống nếu được tối ưu hóa đúng cách.

1.2. Quy trình bi reforming

Quy trình bi-reforming kết hợp CO2 và metan để sản xuất metanol. Phương pháp này không chỉ giúp giảm thiểu lượng CO2 mà còn tận dụng nguồn năng lượng từ khí tự nhiên. Nghiên cứu cho thấy rằng quy trình này có thể đạt được hiệu suất cao và giảm thiểu phát thải carbon. Tuy nhiên, chi phí đầu tư ban đầu cho thiết bị và công nghệ vẫn là một thách thức lớn. Việc phân tích chi phí và lợi ích cho thấy rằng quy trình bi-reforming có tiềm năng lớn trong việc sản xuất metanol bền vững.

1.3. Quy trình tri reforming

Quy trình tri-reforming là một phương pháp tiên tiến hơn, kết hợp CO2, metan và hơi nước để sản xuất metanol. Phương pháp này không chỉ giúp tối ưu hóa hiệu suất sản xuất mà còn giảm thiểu phát thải khí nhà kính. Nghiên cứu cho thấy rằng quy trình tri-reforming có thể đạt được hiệu suất cao hơn so với hai quy trình trước đó. Tuy nhiên, chi phí vận hành và bảo trì vẫn cần được xem xét kỹ lưỡng. Việc đánh giá kinh tế kỹ thuật cho thấy rằng tri-reforming có thể là một lựa chọn khả thi cho tương lai.

II. Tác động môi trường và kinh tế

Việc sử dụng CO2 để sản xuất metanol không chỉ mang lại lợi ích kinh tế mà còn có tác động tích cực đến môi trường. Tái chế CO2 giúp giảm thiểu lượng khí thải carbon, góp phần vào việc chống biến đổi khí hậu. Nghiên cứu cho thấy rằng quy trình sản xuất metanol từ CO2 có thể giảm thiểu phát thải carbon đáng kể so với các quy trình truyền thống. Hơn nữa, việc sản xuất metanol từ CO2 có thể tạo ra nguồn năng lượng tái tạo, giúp giảm phụ thuộc vào nhiên liệu hóa thạch.

2.1. Phân tích chi phí

Phân tích chi phí là một phần quan trọng trong đánh giá technoeconomic. Chi phí sản xuất metanol từ CO2 phụ thuộc vào nhiều yếu tố như giá nguyên liệu, chi phí năng lượng và chi phí vận hành. Nghiên cứu cho thấy rằng việc tối ưu hóa quy trình sản xuất có thể giảm thiểu chi phí và tăng cường lợi nhuận. Việc sử dụng các công nghệ tiên tiến và chất xúc tác hiệu quả có thể giúp giảm chi phí sản xuất và tăng cường tính cạnh tranh của sản phẩm trên thị trường.

2.2. Tác động môi trường

Tác động môi trường của quy trình sản xuất metanol từ CO2 là một yếu tố quan trọng cần xem xét. Việc giảm thiểu phát thải carbon và sử dụng năng lượng tái tạo có thể giúp bảo vệ môi trường. Nghiên cứu cho thấy rằng quy trình sản xuất metanol từ CO2 có thể giảm thiểu lượng khí thải carbon so với các quy trình truyền thống. Hơn nữa, việc sử dụng metanol như một nguồn năng lượng có thể giúp giảm ô nhiễm không khí và bảo vệ sức khỏe cộng đồng.

III. Kết luận và khuyến nghị

Nghiên cứu về đánh giá technoeconomic quy trình sản xuất metanol từ CO2 cho thấy rằng đây là một giải pháp khả thi cho việc giảm thiểu phát thải carbon và tạo ra sản phẩm có giá trị. Các quy trình như hydrogenation, bi-reforming và tri-reforming đều có tiềm năng riêng, tuy nhiên, cần có sự tối ưu hóa để đạt được hiệu suất và chi phí tốt nhất. Khuyến nghị cho các nghiên cứu tiếp theo là cần tập trung vào việc phát triển công nghệ và cải tiến quy trình để tăng cường tính bền vững và hiệu quả kinh tế.

3.1. Đề xuất nghiên cứu tiếp theo

Cần có thêm các nghiên cứu về việc phát triển công nghệ mới và cải tiến quy trình sản xuất metanol từ CO2. Việc nghiên cứu các chất xúc tác mới và tối ưu hóa điều kiện phản ứng có thể giúp tăng cường hiệu suất và giảm chi phí sản xuất. Hơn nữa, cần có các nghiên cứu về tác động môi trường của quy trình sản xuất để đảm bảo rằng quy trình này thực sự bền vững.

3.2. Tăng cường hợp tác giữa các bên

Tăng cường hợp tác giữa các nhà nghiên cứu, doanh nghiệp và chính phủ là cần thiết để phát triển quy trình sản xuất metanol từ CO2. Việc chia sẻ kiến thức và công nghệ có thể giúp tăng cường hiệu quả và tính bền vững của quy trình. Hơn nữa, cần có các chính sách hỗ trợ từ chính phủ để khuyến khích việc đầu tư vào công nghệ sản xuất metanol từ CO2.

Trích đoạn nội dung tài liệu

TECHNO-ECONOMIC EVALUATION OF CO2 UTILIZATION PROCESSES: HYDROGENATION, BI- AND TRI-REFORMING OF CO2 INTO METHANOL PRODUCTION Nguyen Bui Huu Tuan A Thesis Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science The Petroleum and Petrochemical College, Chulalongkorn University in Academic Partnership with The University of Michigan, The University of Oklahoma, Case Western Reserve University, and Institut Français du Pétrole 2015 Thesis Title: Techno-Economic Evaluation of CO2 Utilization Processes: Hydrogenation, Bi- and Tri-Reforming of CO2 into Methanol Production By: Nguyen Bui Huu Tuan Program: Petroleum Technology Thesis Advisors: Dr. Uthaiporn Suriyapraphadilok Prof. Rafiqul Gani Accepted by The Petroleum and Petrochemical College, Chulalongkorn University, in partial fulfillment of the requirements for the Degree of Master of Science. College Dean (Asst.

Pomthong Malakul) Thesis Committee:. Bunyaphat Suphanit) iii ABSTRACT 5673038063: Petroleum Technology Program Nguyen Bui Huu Tuan: Techno-Economic Evaluation of CO2 Utilization Processes: Hydrogenation, Bi- and Tri-Reforming of CO2 into Methanol Production Thesis Advisors: Dr. Uthaiporn Suriyapraphadilok, and Prof. Rafiqul Gani 244 pp.

Keywords: CO2 mitigation / Methanol synthesis / Aspen Plus / CO2 hydrogenation More efforts to capture CO2 are being encouraged in order to minimize its concentration in air. However, the CO2 capture cost is still quite high and is a major problem in advancing more sustainable processes. One viable solution is using cap- tured CO2 as raw material to convert to valuable products so that CO2 capture and utilization can become economically feasible. Thus, utilizing CO2 as feedstock to produce higher value products shows the potential for economy and environment.

Methanol that can be synthesized through CO2 with the support of catalysts has been broadly aimed as a potential product. Methanol is largely employed in the chemical industry, especially in manufacturing formaldehyde, MTBE and acetic ac- id. Furthermore, owing notable combustion characteristics as well as emitting fewer pollutants than conventional fuels permits methanol be employed as fuel in vehicles. The aim of this research is to model and design feasible processes as a CO2 treatment approach through the production of methanol as well as to evaluate and compare the methanol production between the different options, which are hydro- genation, bi-reforming and tri-reforming processes, in terms of an established set of performance criteria.

ราฟิ ก กานี่ 244 หน้า ในปั จจุบนั ได้มีความพยายามในการลดปริ มาณของก๊าซคาร์ บอนไดออกไซด์ในบรรยากาศ แต่ เ นื่ อ งจากการดัก จับ ก๊ า ซคาร์ บ อนไดออกไซด์ มี ค่ า ใช้จ่ า ยค่ อ นข้า งสู ง วิธี ก ารหนึ่ งที่ จ ะท าให้ กระบวนการลดก๊าซคาร์ บอนไดออกไซด์มีความคุม้ ค่าและยัง่ ยืน คือการนาก๊าซคาร์ บอนไดออกไซด์ที่ ดักจับได้มาเป็ นวัตถุดิบในการเปลี่ ยนเป็ นสารเคมีหรื อสารอื่น ๆ ที่ สร้ างมู ลค่าได้และมี ความคุ ม้ ค่า ในทางเศรษฐศาสตร์ และในขณะเดียวกันสามารถช่วยลดภาวะโลกร้อน ก๊าซคาร์ บอนไดออกไซด์สามารถนามาเป็ นวัตถุดิบในการสังเคราะห์เมทานอลโดยใช้ตวั เร่ ง ปฏิ กิริยา เมทานอลเป็ นสารเคมี และตัวท าละลายที่ มีการใช้อย่างแพร่ หลายและมี อตั ราการใช้เป็ น จานวนมาก เมทานอลเป็ นวัตถุดิบในกระบวนการผลิตฟอร์ ม ัลดี ไฮด์ สารเร่ งค่าออกเทน ตลอดจน กรดอะซิ ติก นอกจากนี้ เมทานอลยังมีสมบัติเป็ นเชื้ อเพลิงที่ดี และปลดปล่อยก๊าซมลพิษในปริ มาณที่ น้อยกว่าเชื้อเพลิงฟอสซิ ล ซึ่ งมีความเป็ นไปได้ในการนาเมทานอลมาใช้เป็ นเชื้อเพลิงในเครื่ องยนต์ จุดมุ่งหมายของงานวิจยั นี้ เพื่อออกแบบและสร้ างแบบจาลองกระบวนการผลิ ตเมทานอล ตลอดจนการวิเคราะห์ ประเมินผล และเปรี ยบเทียบกระบวนการผลิตเมทานอลด้วยกระบวนการต่างๆ ได้แก่กระบวนการไฮโดรจีเนชัน กระบวนไบ-รี ฟอร์ มมิง และ ไทร-รี ฟอร์ มมิง ทั้งในเชิ งเทคนิ คและ เศรษฐศาสตร์ v ACKNOWLEDGEMENTS This thesis was successfully completed not only due to my dedication but also with the extended support by a number of people and organizations. I am proud to appreciate all who support me to let this work done. First and foremost, I sincerely appreciate Dr. Uthaiporn Suriyapraphadilok and Prof.

Rafiqul Gani, my advisors for providing invaluable knowledge, creative comments, untouchable experience in classroom, giving me the best opportunity of visiting Computer Aided Process-Product Engineering Center (CAPEC), Technical University of Denmark, and kind support throughout this research work. I would like to thank Assoc. Thirasak Rirksomboon and Dr. Bunyaphat Suphanit for being my thesis committee.

Their suggestions and comments are very beneficial for me and this work. I would like to acknowledge to Mr. Kosan Roh, Mr. Emmanouil Papadakis and Ms.

Maria-Ona Bertran for the excellent supporting regarding Aspen Plus with patience and total availability to help. I am grateful for the scholarship and funding of the thesis work provided by The Petroleum and Petrochemical College, Chulalongkorn University and by the Computer Aided Process Engineering Center, Technical University of Denmark, Denmark. This research work was partially supported by the Ratchadapisek Sompoch Endowment Fund (2013), Chulalongkorn University (CU-56-900-FC) and Thailand Research Fund (IRG5780012). I presented my gratitude to all faculty members, research staff and other staff of the Petroleum and Petrochemical College, for the support and guidance given for better completion of the work.

Finally, I wish to thank my family and friends for their endless love and support of my graduate education, especially to my parents for their ability to bring balance to my life at this challenging time. Their encouragement and support from beginning to the end makes this thesis possible. TABLE OF CONTENTS PAGE Title Page i Abstract (in English) iii Abstract (in Thai) iv Acknowledgements v Table of Contents vi List of Tables x List of Figures xviii Abbreviations xxi List of Symbols xxii CHAPTER I INTRODUCTION 1 II LITERATURE REVIEW 3 2.1 Sources of Carbon Dioxide (CO2) 3 2.1 Fossil Fuel Combustion/Use 4 2.2 Land Use Changes 6 2.2 Carbon Capture and Utilization 8 2.1 CO2 Fixation into Organic Compounds 9 2.2 CO2 Reduction to C1 or Cn Molecules 26 2.1 Direct CO2 Hydrogenation into Methanol 37 2.2 Bi-reforming of CO2 into Methanol 42 2.3 Tri-reforming of CO2 into Methanol 45 vii CHAPTER PAGE III EXPERIMENTAL 48 3.1 Materials and Equipment 48 3.1 Literature Survey Study 48 3.4 Economic Evaluation 49 IV CASE STUDY 1: HYDROGENATION OF CO2 INTO METHANOL 50 4.1 Base Case Design 50 4.1 Inlet Methanol Reactor Temperature 66 4.2 Inlet Methanol Reactor Pressure 68 4.4 Optimal Design Factors and Performance Results 69 4.3 Alternative Design Ideas 70 4.1 Performance Results 71 V CASE STUDY 2: BI-REFORMING OF CO2 INTO METHANOL 75 5.1 Base Case Design 75 5.2 Sustainability Analysis 80 viii CHAPTER PAGE 5.1 Bi-reforming-related Variables 90 5.2 Methanol synthesis-related Variables 94 5.3 Optimal Design Factors and Performance Results 96 5.3 Alternative Design Ideas 97 5.1 Performance Results 97 VI CASE STUDY 3: TRI-REFORMING OF CO2 INTO METHANOL 102 6.1 Base Case Design 102 6.1 Tri-reforming-related Variables 116 6.2 Methanol synthesis-related Variables 120 6.3 Optimal Design Factors and Performance Results 122 6.3 Alternative Design Ideas 123 6.1 Performance Results 124 VII COMPARISION AMONG DIFFERENT PROCESSES 128 7.1 Net CO2 Emission Evaluation 128 7.2 Economic Evaluation 128 VIII CONCLUSIONS AND RECOMMENDATION 130 REFERENCES 132 ix CHAPTER PAGE APPENDICES 149 Appendix A CO2 Conversion Process Flowsheet and Steam Tables Implemented by Aspen Plus 8.6 149 Appendix B Economic Evaluation for Each Process 187 Appendix C Calculation of Indirect CO2 Emission 243 CURRICULUM VITAE 244 x LIST OF TABLES TABLE PAGE 2.1 Sources of CO2 emissions 3 2.2 The physical and chemical properties of CO2 9 2.3 Use of CO2 in the chemical industry for the synthesis of organic compounds 9 2.4 Applications and market of different carboxylates 21 2.5 Current processes of carboxylate production 22 2.6 Different catalytic systems for the hydrogenation of CO2 to formic acid 24 2.7 Free energy of formation of various C1 molecules 27 2.8 Summary of catalytic reforming of CO2/CH4 in the literature 28 2.9 Properties of methanol 29 2.10 Overview of nickel-based catalysts in steam reforming 33 2.11 Overview of catalysts in partial oxidation 34 4.1 Tabulated information of the relevant results from CO2 capture simulations 51 4.2 Cost to produce hydrogen with different scenarios 52 4.3 Input data of the methanol synthesis 55 4.6 Net CO2 emission for only methanol synthesis 57 4.7 Net CO2 emission for the total process 58 4.8 Profitability of the base case 65 4.9 Relationship between the inlet methanol reactor temperature and net CO2 emission 67 xi TABLE PAGE 4.10 Relationship between the inlet methanol reactor temperature and production cost 67 4.11 Relationship between the inlet methanol reactor pressure and net CO2 emission 68 4.12 Relationship between the inlet methanol reactor pressure and production cost 68 4.13 Comparison of operating conditions between the optimized and base case 69 4.14 Comparison of environmental and economic aspects between the optimized and base case 69 5.1 Input data of the methanol production 79 5.4 Net CO2 emission for methanol production 81 5.5 Profitability of the base case 88 5.6 Relationship between the inlet bi-reforming reactor temperature and net CO2 emission 90 5.7 Relationship between the inlet bi-reforming reactor temperature and production cost 90 5.8 Relationship between the inlet bi-reforming reactor pressure and net CO2 emission 91 5.9 Relationship between the inlet bi-reforming reactor pressure and production cost 91 5.10 Relationship between the CO2/CH4 ratio and net CO2 emission 92 5.11 Relationship between the CO2/CH4 ratio and production cost 92 5.12 Relationship between the H2O/CH4 ratio and net CO2 emission 93 xii TABLE PAGE 5.13 Relationship between the H2O/CH4 ratio and production cost 93 5.14 Relationship between the inlet methanol reactor temperature and net CO2 emission 94 5.15 Relationship between the inlet methanol reactor temperature and production cost 94 5.16 Relationship between the inlet methanol reactor pressure and net CO2 emission 95 5.17 Relationship between the inlet methanol reactor pressure and production cost 95 5.18 Comparison of operating conditions between the optimized and base case 96 5.19 Comparison of environmental and economic aspects between the optimized and base case 97 5.20 Comparison of environmental and economic aspects between the base and alternative case 99 5.21 Net CO2 emission for methanol production 100 5.22 Purge gas stream characteristics 100 6.1 Input data of the methanol production 106 6.4 Net CO2 emission for methanol production 108 6.5 Profitability of the base case 114 6.6 Relationship between the inlet tri-reforming reactor temperature and net CO2 emission 116 6.7 Relationship between the inlet tri-reforming reactor temperature and production cost 117 6.8 Relationship between the inlet tri-reforming reactor pressure and net CO2 emission 117 xiii TABLE PAGE 6.9 Relationship between the inlet tri-reforming reactor pressure and production cost 118 6.10 Relationship between the CH4/Flue gas ratio and net CO2 emission 118 6.11 Relationship between the CH4/Flue gas ratio and production cost 119 6.12 Relationship between the H2O/Flue gas ratio and net CO2 emission 119 6.13 Relationship between the H2O/Flue gas ratio and production cost 120 6.14 Relationship between the inlet methanol reactor temperature and net CO2 emission 120 6.15 Relationship between the inlet methanol reactor temperature and production cost 121 6.16 Relationship between the inlet methanol reactor pressure and net CO2 emission 121 6.17 Relationship between the inlet methanol reactor pressure and production cost 122 6.18 Comparison of operating conditions between the optimized and base case 123 6.19 Comparison of environmental and economic aspects between the optimized and base case 123 6.20 Comparison of environmental and economic aspects between the base and alternative case 125 7.1 Net CO2 emission from alternatives of three conversion processes 128 7.2 Comparison of economic aspects among different scenarios 129 xiv TABLE PAGE A1.1 Stream table of the hydrogenation of CO2 into methanol for the base case design 151 A1.2 Stream table of the hydrogenation of CO2 into methanol for the optimized case design 155 A2.1 Stream table of bi-reforming of CO2 into methanol for the base case design 159 A2.2 Stream table of bi-reforming of CO2 into methanol for the optimized case design 164 A2.3 Stream table of bi-reforming of CO2 into methanol for the alternative case design 169 A3.1 Stream table of tri-reforming of CO2 into methanol for the base case design 174 A3.2 Stream table of tri-reforming of CO2 into methanol for the optimized case design 179 A3.3 Stream table of tri-reforming of CO2 into methanol for the alternative case design 184 B1.1 Raw material and product prices 187 B1.3 Raw materials annual price 188 B1.4 Products annual price 188 B1.5 Annual electricity cost 189 B1.6 Annual cooling water cost 189 B1.7 Equipment sizing and purchase cost 190 B1.8 Breakdown of capital cost 191 B1.9 Breakdown of production cost 192 B1.11 Products annual price 194 B1.12 Raw materials annual price 194 B1.13 Annual electricity cost 195 xv TABLE PAGE B1.14 Annual cooling water cost 195 B1.15 Equipment sizing and purchase cost 196 B1.16 Breakdown of capital cost 197 B1.