不同原料制甲醇的能值分析与比较

采用能值分析方法对天然气制甲醇、水煤浆制甲醇、焦炉气制甲醇、黄磷尾气制甲醇和乙炔尾气制甲醇进行了分析与比较。结果表明：水煤浆制甲醇工艺环境负荷率低,能值产出率适中,能值投资率高,可持续发展指数适中,而且所产甲醇能值置换比也较低,因此该工艺优于另外4种工艺。阐述了在石油、天然气供需矛盾日益紧张的今天,我国应充分利用储量丰富的煤炭资源,大力发展水煤浆制甲醇工艺,以满足经济社会高速发展对甲醇的需求。     

金属改性甲醇芳构化催化剂的制备及性能研究

甲醇制芳烃是中国煤基甲醇深加工技术的重点发展方向之一,目前甲醇芳构化催化剂存在芳烃选择性低、收率低等问题。鉴于此,采用等体积浸渍法制备了一系列氧化锌、氧化镍复合改性催化剂,通过X射线荧光光谱（XRF）、氮气物理吸-脱附以及氨的程序升温脱附（NH₃-TPD）等方法对催化剂进行表征分析,通过固定床小试评价装置对催化剂的甲醇芳构化反应性能进行考察,并通过300 t/a固定床中试评价装置对优选催化剂的反应稳定性进行考察。小试实验结果表明,当氧化锌与氧化镍负载比例为2.0（质量比）、负载总量为6.2%（质量分数）时,催化剂具有最佳的甲醇芳构化性能,芳烃选择性为62.98%、收率为19.46%。中试实验结果表明,180 h内甲醇转化率保持100%、芳烃选择性不低于73%、芳烃收率不低于32%。以中国丰富的甲醇资源为原料,生产中国短缺的芳烃产品,一方面可以完善煤化工产业链、优化产品结构,另一方面可以缓解中国石油基芳烃供应不足的局势。     

大型合成氨装置联产甲醇初探：I.天然气与石脑油原料合成氨联产甲醇

针对以天然气与石脑油为原料的大型合成氨装置，提出４种联产甲醇的可行性方案，可使氨厂开发新产品，提高装置经济效益。     

基于熵权-层次分析法的中国现代煤化工行业可持续发展综合评价

中国现代煤化工行业规模扩张迅速,但其可持续发展也面临高资源消耗、环境污染严重等挑战。本研究建立了基于环境、经济、社会和技术这4个方面的中国现代煤化工行业可持续发展综合评价指标体系。采用熵权法和层次分析法相结合的权重模型,量化了煤直接液化、煤间接液化、甲醇制汽油、中低温煤焦油加氢、煤制甲醇燃料、煤制天然气、煤制烯烃、煤制芳烃和煤制乙二醇这9种现代煤化工技术路线在4个方面的可持续性表现以及综合可持续发展指数,为行业的科学发展提供决策支持。研究结果表明,每种技术路线在环境、经济、社会和技术这4个方面的可持续性表现差异较为明显。煤间接液化的综合可持续性表现最优,其次为中低温煤焦油加氢、煤直接液化和煤制天然气;而甲醇制汽油和煤制芳烃的综合可持续性表现较差。除了煤炭资源丰富的地区之外,在水资源较丰富、环境容量较大的地区布局示范项目理论上也支持现代煤化工行业的可持续发展。最后,基于结论提出建议,为现代煤化工行业制定可持续发展战略、科学布局与合理规划提供重要参考。     

Production of benzene,toluene, and xylenes from natural gas via methanol: Process synthesis and global optimization

A systematic global optimization‐based process synthesis framework is presented to determine the most profitable processes to produce aromatics from natural gas. Several novel, commercial, and/or competing technologies are modeled within the framework, including methanol‐to‐aromatics, toluene alkylation with methanol, selective toluene disproportionation, and toluene disproportionation and transalkylation with heavy aromatics, among others. We propose a stand‐alone chemicals facility: the main products are aromatics with allowable by‐products of gasoline, liquefied petroleum gas, and electricity. Several case studies are discussed that produce varying ratios of para‐, ortho‐, and meta‐xylene across multiple refinery capacities. The results indicate that utilizing natural gas for the production of aromatics is profitable with net present values as high as $3800 MM dollars and payback periods as low as 6 years. The required investment for these refineries represents as much as a 65% decrease compared to published estimates of similar coal‐based capacity plants. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1531–1556, 2016     

油页岩综合利用系统的能值分析

为了综合评价油页岩综合利用系统的环境可持续性,以吉林桦甸处理量为300×10⁴t/a油页岩综合利用项目为例,应用能值分析理论,构建该系统的能值评价指标体系。研究结果表明:虽然页岩油的能值转化率(Tr)要高于传统原油,但油页岩综合利用系统环境负载率(ELR)低,对环境影响小,系统可持续发展指数(ESI)较高,系统富有活力和发展潜力;与桦甸式干馏工艺相比,将锅炉灰渣用于建材,不仅能增加系统副产物,提高能值产率(EYR),还能有效地改善其他各项能值指标。     

Separation of fatty acid methyl esters from tall oil by selective adsorption

Fatty acid methyl esters (FAME) and resin acids (RA) were separated from tall oil by selective adsorption. Commercial nonmodified molecular sieve 13X was used as adsorbent. The adsorption isotherms of fatty acids (FA), FAME, and RA on molecular sieve 13X at 25°C were determined using various solvents. The solvents were methanol, ethanol, isopropanol, acetone, benzene, hexane, isooctane, petroleum ether (40–60°C), and petroleum naphtha (80–180°C). With each solvent, FA and RA were adsorbed to a greater extent than FAME. Adsorption isotherms for RA and FAME in binary adsorption systems were also determined using petroleum ether, petroleum naphtha, benzene, and isopropanol. For each component in the binary adsorption, the equilibrium amounts are lower than the values for pure component adsorption. The adsorption of FAME decreased in the presence of RA markedly in petroleum ether and petroleum naphtha. This fact may be the indication of the phenomenon of selective adsorption. Separation was accomplished by adding a solution of esterified tall oil in solvents used in the binary adsorption systems, through a column packed with molecular sieve 13X. With petroleum naphtha, FAME and RA were recovered in yields of 93 and 94%, respectively, from esterified tall oil. Petroleum naphtha gave the best results. The effects of particle size of adsorbent and flow rate of solvent on the efficiency of the separation were also investigated in fixed-bed column studies. The particle size of adsorbent did not apparently alter the results. Changes in the particle size should not significantly change the number of available adsorption sites in a microporous molecular sieve.     

从蒽醌法生产过氧化氢尾气中回收重芳烃

采用活性炭纤维吸附回收装置回收蒽醌法过氧化氢生产工艺中尾气夹带的重芳烃 ,回收率可达98%以上 ,不仅减轻了环境污染 ,而且回收了资源 ,具有明显的经济和环保效益     

石脑油萃取脱芳烃技术研究进展

现有的萃取脱芳烃工艺技术成熟,种类多,工业应用广,但在处理低芳烃含量的石脑油(质量分数小于15%)时普遍存在能耗高、经济效益低等问题。本文回顾了萃取脱芳烃的多种工艺,重点讨论了常规溶剂和离子液体对石脑油中芳烃的萃取效果,认为常规溶剂中的环丁砜、N-甲基吡咯烷酮以及复合溶剂环丁砜(水)-三甘醇、环丁砜(水)-N-甲基吡咯烷酮、环丁砜-2-丙醇、RAH-1脱芳烃效果优异,能为改进目前的石脑油萃取脱芳烃工艺提供基础数据;离子液体中咪唑类离子液体如1-丁基-3-甲基咪唑六氟磷酸盐、1-丁基-3-甲基咪唑双(三氟甲基磺酰)亚胺盐、1-丁基-3-甲基咪唑四氯化铁等,有潜力用于低芳烃的石脑油萃取脱芳中,指出开发能够对复杂原料中低含量芳烃萃取的新型离子液体将会是以后的研究方向。     

甲醇制芳烃催化剂及相关工艺研究进展

当前我国芳烃生产面临石油资源短缺等困难,而我国丰富的煤炭资源和当前过剩的甲醇产能为煤基甲醇制芳烃提供了价格低廉的原料,对于我国的能源安全具有重要意义。本文综述了近年来国内外甲醇制芳烃（MTA）技术的相关研究进展,分别介绍了MTA固定床、流化床技术;针对传统MTA过程产物复杂,分离能耗大,经济效益差等不足,归纳总结了更具经济性的甲醇一步法制对二甲苯（MTPX）以及甲醇一步法制对二甲苯联产低碳烯烃（MTO&PX）技术;针对传统MTA催化剂稳定性差等不足,对比介绍了甲醇直接制芳烃以及低碳烯烃制芳烃路线,结果表明甲醇经低碳烯烃制芳烃工艺路线具有催化剂寿命长、产品组成易调节等优势。最后,本文认为分子筛限域效应、分子筛表面修饰新技术、金属-酸双活性中心协同效应是未来MTA研究的重要方向。     

Modular methanol manufacturing from shale gas: Techno‐economic and environmental analyses of conventional large‐scale production versus small‐scale distributed,modular processing

This article presents comparative techno‐economic and environmental analyses of four representative shale gas monetization options, namely, conventional shale gas processing, large‐scale methanol manufacturing, modular methanol manufacturing with shale gas supplied by pipelines, and modular methanol manufacturing with consideration of plant relocation. We first present shale gas supply models for the four gas monetization options. Next, the process designs for shale gas processing and methanol manufacturing from shale gas are described. We develop detailed process simulation models for shale gas processing and methanol manufacturing with different scales using raw shale gas extracted from the Marcellus, Eagle Ford, and Bakken shale plays. On this basis, techno‐economic analyses and environmental impact analyses are conducted for the four shale gas monetization options to systematically compare their economic and environmental performances based on the same conditions. The results show that modular methanol manufacturing is more economically competitive than conventional shale gas processing, although it leads to higher environmental impacts. Besides, modular methanol manufacturing is better than large‐scale methanol manufacturing for raw shale gas produced from distributed, remote wells from both economic and environmental perspectives. © 2017 American Institute of Chemical Engineers AIChE J, 64: 495–510, 2018     

苯与合成气烷基化催化剂的研究进展

对二甲苯（PX）是制备聚酯材料的重要原料,随着我国经济快速发展,对二甲苯的需求日益增长。目前PX主要通过石化路线生产,由于我国石油资源短缺,迫切需要开发基于煤化工路线的PX生产技术。通过苯与合成气烷基化制备PX是一条新的煤化工路线,近年来受到关注。本文综述了苯与合成气烷基化的最新进展,讨论了贵金属（Pt）、铜基氧化物、锌基氧化物（ZnZr、ZnCr）与沸石的复合以及负载和机械混合两类复合方式对催化效果的影响,分析了甲醇合成与烷基化反应的耦合机制以及反应条件的匹配关系;并与其他三种煤制芳烃技术,即合成气制芳烃、甲醇制芳烃以及苯与甲醇烷基化制烷基苯做了对比分析,表明该技术路线具有成本较低和工艺路线短的优势。     

催化裂化装置回炼加氢石脑油对产品的影响

加氢石脑油作为催化裂化装置急冷油进入提升管进行回炼,对回炼加氢石脑油期间产品分布和产品性质有较为明显的影响。干气、液化气和柴油收率明显下降,汽油收率明显升高,汽油辛烷值和芳烃含量也呈下降趋势,稳定汽油有效烯烃含量明显降低,对醚化反应操作有较大的影响。通过分析催化裂化装置回炼加氢石脑油对产品分布和产品性质的影响,为未来生产调整提供数据参考。     

东北亚石油工业面临的新挑战及应对措施

当前,东北亚石油工业面临着油气供需缺口不断增大、国际油价高企影响炼油业效益、环保政策日趋严格、石油进口来源和进口渠道存在诸多风险等新挑战,为此,东北亚石油工业界应携手建立地区性对话机制和石油安全应急体系,加强油气勘探开发、油气进口及储运、炼油化工、提高资源利用效率、发展循环经济、开发应用替代能源等方面的合作。     

Coproduction of liquid transportation fuels and C6_C8 aromatics from biomass and natural gas

The coproduction of liquid transportation fuels and C₆?C₈ aromatics from the thermochemical conversion of biomass and natural gas (BGTL+C₆_C₈) is investigated in this article. An optimization‐based process synthesis framework incorporating multiple synthesis gas conversion technologies, such as Fischer–Tropsch synthesis or methanol conversion, is described. Production of aromatics can proceed through several technologies, such as naphtha reforming and aromatization of hydrocarbons via a metal‐promoted H‐ZSM‐5 catalyst. This is the first article in the literature to incorporate an aromatics complex for the coproduction of liquid fuels and C₆?C₈ petrochemicals within a rigorous process synthesis and deterministic global optimization framework. The optimal process topologies across several case studies are discussed and the results indicate that the coproduction of aromatics with liquid fuels can significantly increase the profitability of these refineries. © 2015 American Institute of Chemical Engineers AIChE J, 2015 2014 American Institute of Chemical Engineers AIChE J, 61: 831–856, 2015     

多产品工业系统的能值分析

介绍了起源于生态领域的能值分析方法. 为了扩展能值分析方法的应用范围,根据能值分析的基本思想,并以能量守恒和能值守恒为依据,建立了多产品工业系统能值分析模型. 将能量分率作为分配系数,提出了评价多产品工业系统的评价指标：共生指数. 为了获得对比结果,还对相应的单产物系统提出了数均指数. 若共生指数优于数均指数,则多产品联产系统优于单产系统. 通过垃圾焚烧热电联产方案的能值分析,验证了多产品的能值分析模型. 并与常规燃煤热电联产系统进行了比较,以说明能值分析方法的优势.     

A review on research and development of green composites from plant protein‐based polymers

Depletion of petroleum resources, together with increasing environmental concerns, calls for new solutions for many of our needs such as fuels, heating, materials, technical oils, and so on. Because of the ubiquitous use of petroleum‐based products in their persistence in the environment and their fossil‐fuel derived, alternatives to these traditional plastics are being explored. Totally, “green” biomaterials are of extra interest. Thus, strong composites containing both “green fibers” from plants and “green/biopolymers” from plants would be an ideal solution and they represent an emerging area in polymer science. Introduction and production of these composites into the material market would be important for environmental sustainability as their use can decrease the volume of petroleum‐derived plastic waste dumps. This article reviews the current research efforts, techniques of production, trends, challenges, and prospects in the field of green composites from protein‐based polymers. Green composites are comparatively cheap and abundant, but further research and development is needed for a broader utilization. POLYM. COMPOS., 38:1504–1518, 2017. © 2015 Society of Plastics Engineers     

A sustainability root cause analysis methodology and its application

In the design of chemical/energy production systems, a major challenge is to identify the bottleneck issues and improve its sustainability effectively. Due to the multi-dimensional feature of sustainability, how to account for the impacts of various design factors and the cause-and-effect relationships can be very difficult. This paper will present a sustainability root cause analysis method based on the combination of Pareto Analysis and Fishbone diagram. The sustainability of the process is assessed incorporating economic, environmental, societal and efficiency concerns.This methodology is able to help the designers focus the attention on the most important fundamental causes, discover opportunities for sustainability improvement and provide critical guidance to design for sustainability. The efficacy of this methodology will be demonstrated through a case study on a biodiesel production technology.     

神府煤液化油石脑油馏分重整生产芳烃的研究

由于煤液化油石脑油馏分(200℃)中芳烃潜含量较高,利用煤液化油石脑油馏分为原料,进行加氢精制,将原料中的硫氮含量降至1 mg/kg左右,满足重整进料要求,然后在小型固定床连续反应器上进行加氢重整生产芳烃试验。着重考察重整反应前、后族组成的变化及主要芳烃化合物的产率。结果表明,加氢重整过程中发生正构烷烃异构化反应;环烷烃主要发生脱氢芳构化反应转化为芳香烃;煤液化油石脑油馏分适宜进行催化重整,C_1~C_4烃气产率6.03%,氢气产率3.60%;重整后,芳烃含量达83.20%,其中C_6~C_8芳烃含量61.03%,是提取BTX的良好原料。石脑油的馏程对芳烃的组成和产率有一定影响,适宜的馏程为60~160℃。     

The status of exploitation techniques of natural gas hydrate

Natural gas hydrate (NGH) has been widely considered as an alternative form of energy with huge potential, due to its tremendous reserves, cleanness and high energy density. Several countries involving Japan, Canada, India and China have launched national projects on the exploration and exploitation of gas hydrate resources. At the beginning of this century, an early trial production of hydrate resources was carried out in Mallik permafrost region, Canada. Japan has conducted the first field test from marine hydrates in 2013, followed by another trial in 2017. China also made its first trial production from marine hydrate sediments in 2017. Yet the low production efficiency, ice/hydrate regeneration, and sand problems are still commonly encountered; the worldwide progress is far before commercialization. Up to now, many gas production techniques have been proposed, and a few of them have been adopted in the field production tests. Nevertheless, hardly any method appears really promising; each of them shows limitations at certain conditions. Therefore, further efforts should be made on the economic efficiency as well as sustainability and environmental impacts. In this paper, the investigations on NGH exploitation techniques are comprehensively reviewed, involving depressurization, thermal stimulation, chemical inhibitor injection, CO₂–CH₄ exchange, their combinations, and some novel techniques. The behavior of each method and its further potential in the field test are discussed. The advantages and limitations of laboratory studies are also analyzed. The work could give some guidance in the future formulation of exploitation scheme and evaluation of gas production behavior from hydrate reservoirs.