利用海外甲醇资源发展我国烯烃产业的可行性分析

根据当前全球的甲醇供需形势,特别是我国甲醇引进的现状和发展趋势,针对利用海外甲醇资源采用甲醇制烯烃技术发展我国烯烃产业的发展思路,分析了海外采购甲醇资源的可行性以及外采甲醇通过甲醇制烯烃（MTO）工艺生产烯烃与以石脑油为原料采用蒸汽裂解工艺生产烯烃的经济性对比,指出了我国利用海外甲醇资源发展烯烃产业的优势和风险。     

甲醇制烯烃工业装置用能分析及建议

甲醇制烯烃作为重要制取低碳烯烃的工艺路线,现阶段装置能耗鲜有提及。本文简要介绍甲醇制烯烃工艺技术特点并结合某公司1.8Mt/a甲醇制烯烃工业装置实际生产运行情况,依据能量转换和传输、工艺利用和能量回收"三环节"理论分析装置用能情况。结果表明,装置的工艺利用和能量回收环节节能潜力较大,应提高低温位热能和再生烟气利用效率,进一步挖掘甲醇制烯烃装置节能降耗潜力。     

甲醇制低碳烯烃工艺及催化剂的研究进展

以煤或天然气经甲醇制低碳烯烃工艺是缓解石油资源紧张的有效方法,已引起世界各国的高度重视。综述了国内外具有代表性的以甲醇为原料生产乙烯、丙烯等低碳烯烃工艺技术的研究进展及工业化应用情况,对甲醇制烯烃、甲醇制丙烯这两种工艺技术进行了比较。介绍了ZSM-5,SAPO-34等相关催化剂的改性研究和应用情况,并对我国发展以煤或天然气为原料经甲醇生产低碳烯烃的项目提出了建议。     

中国正积极推进煤化工产业技术

<正>国内具有自主知识产权的煤制油、煤气化、煤(甲醇)制烯烃、煤制芳烃、煤制乙醇和煤制乙二醇等技术不断研发成功并逐步完善。目前,我国甲醇制烯烃工业化技术已有中国科学院大连化学物理研究所的甲醇制低碳烯烃(DMTO)及其二代技术DMTO-Ⅱ、中国石油化工股份有限公司的甲醇制烯烃(SMTO)等工艺,低碳烯烃总产能合计约为16.47Mt/a。     

甲醇转化制烯烃技术的新进展

从分子筛催化剂和工艺(包括UOP公司的甲醇制烯烃(MTO)技术、Lurg i公司的甲醇制丙烯(MTP)技术、ExxonM ob il公司提出的含氧化合物制烯烃(OTO)技术)两方面综述了近年来国外一些大公司在甲醇转化制烯烃方面的研究进展,分析了未来可能的发展动向。     

天然气甲醇法制烯烃工艺进展

介绍了国内外天然气甲醇法制烯烃工艺中SAPO-34分子筛催化剂研究进展和改进的MTO新工艺,指出由于甲醇装置规模、催化剂性能和天然气价格等因素的影响,天然气制烯烃技术的发展任重道远。只有研究出高效的催化剂和先进的MTO工艺流程,才能使天然气制烯烃工艺在我国尽快工业化。     

天然气制烯烃技术进展

介绍了国内外天然气制烯烃技术发展概况,论述了以天然气为原料经合成甲醇进一步生产烯烃（乙烯,丙烯及丁烯）的ＭＴＯ工艺,并对我国今后天然气制烯烃技术的开发提出了建议。     

天然气制烯烃及GSMTO工艺进展

介绍了天然气制烯烃的３ 种研究方向, 天然气直接制 烯烃; 天 然气经合成气制烯烃; 天然气经甲醇制烯烃 （ Ｇ Ｓ Ｍ Ｔ Ｏ） 。简介了 Ｇ Ｓ Ｍ Ｔ Ｏ 工艺技术, 比较了天然气制烯烃与石脑油制烯烃的经济性, 并介绍了 Ｇ Ｓ Ｍ Ｔ Ｏ 工艺实现工业化的难点。     

甲醇制烯烃副产C_5~+回炼对工艺的优化

为了提高甲醇制烯烃工艺中乙烯和丙烯的收率,更大程度地转化甲醇制烯烃的副产物,在甲醇制烯烃工艺过程中增加C_5~+裂解工艺。概述了C_5~+在SAPO-34催化剂上进行裂解的反应机理,提出了用再生后的高温催化剂对混合C_5~+进行裂解,裂解的同时在催化剂活性中心产生积碳,分析了C_5~+积碳后再生催化剂对甲醇制烯烃的反应性能,从C_5~+裂解生成低碳烯烃和未反应完的C_5~+吸附在催化剂上可以抑制甲醇生成C_5~+两方面来降低单位烯烃的甲醇消耗量。C_5~+积碳可能产生低甲基苯类烃池物种,使催化剂对乙烯选择性增加,产生的低甲基苯类烃池物种对附着在水洗塔塔盘的蜡状物质具有较好的溶解作用,优化了水洗塔的运行。     

天然气经甲醇制烯烃技术进展

介绍了天然气经甲醇制烯烃的意义,重点论述了天然气经甲醇制烯烃的技术进展,并对天然气经甲醇制烯烃几种新技术的经济性进行了比较分析。结果表明,天然气经甲醇制烯烃不仅在技术上是可行的,而且在经济上也比石脑油制烯烃更有竞争能力。     

靶向生产低碳烯烃的催化裂化技术开发背景、开发思路和概念设计

低碳烯烃是重要的石油化工原料,现有的低碳烯烃生产技术主要有蒸汽裂解、催化裂解、烯烃裂解和甲醇制烯烃。对这些技术特征进行分析,发现蒸汽裂解和催化裂解工艺存在着乙烯/甲烷比过低,且甲烷产率过高,而烯烃裂解工艺原料来源不足,甲醇制烯烃工艺原料主要来自煤制甲醇,造成高碳排放。现有的低碳烯烃生产技术仍有系列科学问题需要完善,为此提出靶向生产低碳烯烃的催化裂化工艺,从原料结构、催化剂活性组元和催化反应工程3个方面进行创新,深度集成现有技术,形成多产乙烯+丙烯+丁烯、乙烯+丙烯、丙烯、丙烯+丁烯4个不同的生产方案,且生产方案之间可灵活切换。     

催化裂化条件下甲醇与石脑油交互作用研究

为进一步研究甲醇作为催化裂化部分进料反应过程的特征,对催化裂化条件下甲醇与石脑油的交互作用规律进行了考察。利用小型固定流化床装置对甲醇与石脑油共同进料的反应过程进行研究。实验结果表明:随着石脑油中甲醇比例的增加,产物中气体烃产率、焦炭产率、二甲醚产率及低碳烯烃选择性增加;裂化汽油中烷烃含量、芳烃含量先增加后降低,烯烃含量增加;甲醇与石脑油的交互作用使得甲醇转化为低碳烯烃的反应程度加深,同时促进了石脑油的裂化反应。该研究初步探究了甲醇与石脑油的交互作用规律,为更深入的研究甲醇作为催化裂化部分进料的反应过程提供基础数据。     

Feeding Methanol in an FCC Unit

The feasibility analysis of integrating methanol to olefins (MTO) with fluidized catalytic cracking (FCC) process is based on their similarities and compatibility. Feeding methanol in FCC is proposed to produce more light olefins. According to the characters of FCC, the effects of reaction temperature, water co-feed, and the coke content of catalyst in methanol conversion were studied systematically. It is concluded that high light olefins yields from methanol conversion were obtained on the FCC condition. Feeding methanol in FCC at the bottom of riser as the proper position was suggested on the ground of comparison with MGD process of FCC. The research proved the feasibility of feeding methanol in FCC and provided important reference for its commercial application in a certain degree.     

几种催化剂对甲醇转化制低碳烯烃催化反应的影响

本实验利用脉冲微型反应器-色谱装置，考察了甲醇在四种FCC工业平衡剂，LOSA-1助剂及SAPO-34上的转化反应过程。结果表明：在GOR-Ⅱ上纯甲醇的烃和低碳烯烃收率为19.91%和11.41%，在SAPO-34上为21.90%和16.52%，在LOSA-1助剂上为26.73%和12.01%，当GOR-Ⅱ中的LOSA-1比例为5.00%时，烃和低碳烯烃收率有最大值为27.52%和15.72%；在GOR-Ⅱ上40%甲醇水溶液的烃和低碳烯烃收率为9.09%和6.20%，在SAPO-34上为24.71%和20.08%；而甲醇在CHZ-4、DACS-GQ1及RAG-10上的烃和低碳烯烃收率均较低，RAG-10用量提高后烃和低碳烯烃收率可达到11.12%和6.04%。由实验结果可知:四种FCC工业平衡剂中，甲醇在GOR-Ⅱ上的烃和低碳烯烃收率较好，在GOR-Ⅱ中添加LOSA-1后烃和低碳烯烃收率有所提高，这为研究甲醇在FCC催化剂上制低碳烯烃的反应规律提供了初步的参考。     

Feeding Methanol in an FCC Unit

Abstract

The feasibility analysis of integrating methanol to olefins (MTO) with fluidized catalytic cracking (FCC) process is based on their similarities and compatibility. Feeding methanol in FCC is proposed to produce more light olefins. According to the characters of FCC, the effects of reaction temperature, water co-feed, and the coke content of catalyst in methanol conversion were studied systematically. It is concluded that high light olefins yields from methanol conversion were obtained on the FCC condition. Feeding methanol in FCC at the bottom of riser as the proper position was suggested on the ground of comparison with MGD process of FCC. The research proved the feasibility of feeding methanol in FCC and provided important reference for its commercial application in a certain degree.     

对发展天然气化工的认识与建议

在分析当前国外天然气化工技术发展动向和国内现状的基础上，提出天然气制合成气新工艺、甲醇制低碳烯烃(MTO工艺)、合成液体燃料以及天然气凝液化工利用等课题是值得重视的技术开发方向；且在工艺开发的同时，必须充分重视新型设备的研制。在甲醇下游产品开发方面则应重视碳酸二甲酯(DMC)、草酸二甲酯(DMO)和二甲醚(DME)。同时，结合国情对加快技术进步提出了若干建议。     

SYNTHESIS OF HYDROCARBONS FROM DIMETHYL ETHER: SELECTIVTTIES TOWARDS LIGHT HYDROCARBONS

The depleting supplies of non-renewable petroleum reserves, as well as their escalating costs, have directed a great deal of research toward the synthesis of hydrocarbons from coal. Synthesis of methanol from coal-derived synthesis gas is a well established technology, and methanol has been used as a feedstock for the synthesis of gasoline range hydrocarbons and olefins commercially. However, an efficient hydrocarbon synthesis process has been developed at the University of Akron using dimethyl ether as the starting feedstock. This UA/ EPRI' s DTH ( Dimethyl Ether to Hydrocarbons) process has significant advantages over its counterpart methanol conversion process in the areas of heat duties, hydrocarbon selectivities, product yield, and reactor size

Lower olefins are the intermediate products in the conversion of dimethyl ether to aromatic hydrocarbons. C2-C4 olefins and paraffins can be selectively produced by varying the operating parameters of the process, viz., temperature, pressure, DME concentration in the feed, space time, catalyst-to-inert packing ratio, etc. The present work focuses on the effect of key process variables on the dimethyl ether conversion to low molecular weight hydrocarbons in a fixed bed microreactor system over ZSM-5 type zeolite catalyst. Experimental results with respect to gaseous hydrocarbon product yields and selectivities have been examined in this study     

甲醇作为催化裂化部分进料反应过程的可行性分析

通过对甲醇制低碳烯烃(MTO)工艺与催化裂化(FCC)工艺的相似性分析,论述了二者结合的可能性。分析了FCC提升管反应器中的温度分布、催化剂活性变化和水存在的状况,以及这些因素对MTO反应的影响。同时对不同的甲醇加入方式进行了分析,并与FCC的多产液化气和柴油工艺(在提升管反应器底部注入汽油)进行比较,提出适宜的甲醇加入位置为FCC提升管反应器底部,先于原料油进料。此过程既可将甲醇转化为低碳烯烃,又有利于重油的催化裂化反应。初步论证了甲醇作为FCC部分进料的可行性,为甲醇作为FCC部分进料以多产低碳烯烃的进一步研究指出了方向。     

SYNTHESIS OF HYDROCARBONS FROM DIMETHYL ETHER: SELECTIVTTIES TOWARDS LIGHT HYDROCARBONS

ABSTRACT

The depleting supplies of non-renewable petroleum reserves, as well as their escalating costs, have directed a great deal of research toward the synthesis of hydrocarbons from coal. Synthesis of methanol from coal-derived synthesis gas is a well established technology, and methanol has been used as a feedstock for the synthesis of gasoline range hydrocarbons and olefins commercially. However, an efficient hydrocarbon synthesis process has been developed at the University of Akron using dimethyl ether as the starting feedstock. This UA/ EPRI' s DTH ( Dimethyl Ether to Hydrocarbons) process has significant advantages over its counterpart methanol conversion process in the areas of heat duties, hydrocarbon selectivities, product yield, and reactor size

Lower olefins are the intermediate products in the conversion of dimethyl ether to aromatic hydrocarbons. C2-C4 olefins and paraffins can be selectively produced by varying the operating parameters of the process, viz., temperature, pressure, DME concentration in the feed, space time, catalyst-to-inert packing ratio, etc. The present work focuses on the effect of key process variables on the dimethyl ether conversion to low molecular weight hydrocarbons in a fixed bed microreactor system over ZSM-5 type zeolite catalyst. Experimental results with respect to gaseous hydrocarbon product yields and selectivities have been examined in this study