Dalian Institute of Chemical Physics, Chinese Academy of Science 甲醇制烯烃技术发展及其商业化应用 Recent development of methanol-to-olefin technology and its commercialization 刘中民 Zhongmin Liu 中国科学院大连化学物理研究所 Dalian Institute of Chemical Physics, Chinese Academy of Science www.dicp.ac.cn；zml@dicp.ac.cn 2011.09.19 DICP

内容 Contents DICP DICP 背景 Background 第一代甲醇制烯烃技术 DMTO technology DMTO的基本特征 Some basic aspects on DMTO DMTO技术工业性试验 Demonstration tests of DMTO technology 经济性 Economics 商业化 Commercialization 第一套装置开车 Start-up of the world first methanol to olefin plant 新一代甲醇制烯烃技术 DMTO-II technology DMTO-II的原理和技术特征 DMTO-II Principle Features DMTO-II 工业性试验 DMTO-II demonstration tests 结论 Conclusion remarks DICP DICP

烯烃生产技术路线和MTO Technical Routes for Olefin Production & MTO Naphtha Feedstock China US Japan 67% 39% 93% >800oC, H2O, C2=＋C3= Yield～45% 石脑油Naphtha 乙烯 丙烯 C2H4 C3H6 >800oC，+H2O 乙烷Ethane 煤、天然气 Coal, Natural Gas 合成气Syngas 甲醇Methanol DMTO (MTO) Well developed technology DICP

MTO反应特点 Characteristic of Methanol to Olefin reaction 酸性催化特征 Acid catalyzed reaction 高转化率：100% High conversion 低压反应 Low pressure is favorable to light olefin selectivity 强放热 Exothermic reaction 400-500oC，100% conversion H = -22.4～-22.1 KJ/mol methanol 快速反应 Fast reaction 100% conversion at 0.04s contact time 分子筛催化的形状选择性效应：高选择性 Shape selective effect should be applied for high olefin selectivity First generation of catalyst: Modified ZSM-5 Small pore SAPO molecular sieve could be good candidate for developing new catalyst DICP

DMTO Demonstration DICP 目标 Objective 合作三方 Partner To develop DMTO technology for the design of large scale commercial units 合作三方 Partner 中国科学院大连化学物理研究所 Dalian Institute of Chemical Physics 提供中试工艺技术和催化剂 Providing pilot technology for design and the catalyst 中国石化集团洛阳石油化工工程公司 Luoyang Petrochemical Engineering Company, Sinopec 工程放大和试验装置设计 Engineering design 陕西新兴煤化工科技发展有限责任公司 Shanxi Xinxing Coal Chemical Technology Ltd 投资建设、管理运行试验装置 Investment, construction, management, operation 股东：陕西省投资集团公司，正大煤化有限公司，陕西煤业集团公司 Joint venture company: Shanxi Investment Group, Zhengda Coal Chemical Ltd, Shanxi Coal and Chemical Group DICP

工业性试验结果总结 DMTO Demonstration tests 原料 Feedstock CH3OH 规模 Scale 50t/d 反应器类型 Reactor type Fluidized bed 单程转化率 Single pass conversion % >99％ 收率 Yield of ethylene and propylene, wt％ 33.73 选择性 Selectivity of ethylene and propylene, wt％ >79.1 原料单耗 Feedstock consumption for each ton of ethylene and propylene, t/t 2.96 催化剂 Catalyst D803C-II-01 DICP DICP

Commercialization of DMTO 神华包头煤制烯烃项目 Baotou Coal-to-Olefin Project of China Shenhua Group 规模：180万吨甲醇 60万吨聚烯烃 Scale： 1,800 KTA Methanol  600 KTA polyolefin 2006年12月由国家发改委批准 Approved by NDRC（Dec, 2006） 世界上第一套煤制烯烃商业化工厂 First coal to olefin plant in the world 2010年8月8日甲醇制烯烃装置开车 Have been started operation from 8th, August, 2010 其他国内项目 Other projects in China DMTO技术已经许可了超过700万吨/年烯烃产量 ~7,000KTA olefin has been licensed to construct MTO units for production olefin with DMTO technology 在海外将建设商业化装置 The construction of commercially unit will be licensed outside China 许多国际烯烃公司已经与我们联系 Many international olefin companies have contacted us for the technology licensing 和CBI-Lummus 合作，联合烯烃分离进行技术推广 Cooperating with CBI-Lummus DICP DICP

新一代甲醇制烯烃技术 New generation of DMTO technology (DMTO-II) 目的 Objective 进一步提高烯烃选择性，降低甲醇原料消耗 Further improve olefin selectivity and reduce methanol consumption based on DMTO technology 合作伙伴 Partner 大连化学物理研究所 Dalian Institute of Chemical Physics (DICP) 陕西煤化工工程中心 Shaanxi Coal Chemical Technology Center 洛阳石油化工工程公司 Luoyang Petrochemical Engineering Co. (LEPC), Sinopec 对外技术实施许可 Authorized licensing agent 新兴能源科技公式 SYN Energy Technology Co., Ltd DICP DICP

DMTO-II的技术特征 Technical Features of DMTO-II DMTO-II是DMTO基础上的再发展，兼有DMTO的技术特征 DMTO-II was developed on the basis of DMTO technology, DMTO-II possesses all features of DMTO technology DMTO-II还具有如下新的特征 New Features of DMTO-II Technology 甲醇转化反应与C4+转化反应采用同一种催化剂 One Catalyst with two functions: catalyze both methanol and C4+reactions 甲醇转化和C4+转化均采用流化反应方式，分别在不同的反应区进行，可以耦合构成相互联系的完整系统 Fluidized reaction technology was used for both methanol conversion reaction and C4+reaction, and by using one fluidized regenerator to buildup a coupling system and to realize a coupling effect of the two reactions. 利用C4+转化反应强吸热的特点，在高温区进行C4+转化反应，既符合该反应的转化要求，也能实现热量的耦合Keeping methanol conversion same effect as DMTO, and converting C4+ with high olefin selectivity at the same time, so that to increase olefin selectivity for the whole process 甲醇转化和C4+转化目的产物一致，产物分布类似，可以共用一套分离系统 Same target product and similar product distributions for both reactions allow using one separation system DICP DICP