焦炉煤气-甲醇产业链延伸技术方案的经济分析

与煤制甲醇和天然气制甲醇工艺相比,焦炉煤气制甲醇不仅可以有效利用焦炉煤气中的氢,而且具有低成本的优势。在焦炉煤气制甲醇工艺基础上,文中提出了3种具有发展潜力的焦炉煤气综合利用方案:①气化煤气-焦炉煤气制甲醇生产方案;②焦炉煤气-乙炔-甲醇下游产品方案;③气化煤气-焦炉煤气-乙炔-甲醇下游产品方案。以200×104 t焦炭的生产规模分析了3种方案经济性,其毛利润分别为24.21亿元,18.92亿元和28.74亿元;内部收益率分别为28.29%、24.34%和27.11%。气化煤气-焦炉煤气-乙炔-甲醇下游产品方案充分发挥了规模效应和产品高附加值的特点,具有明显的经济优势;系统灵活性高,抵御市场风险能力强。     

各种甲醇生产路线对比

<正>目前甲醇生产主要有:煤气化制甲醇、天然气制甲醇、焦炉煤气制甲醇、焦炉煤气+天然气制甲醇、焦炉煤气+转炉煤气制甲醇5种方法,其对比如下表:从表中可以看出:焦炉煤气+转炉煤气制甲醇路线的生产成本最有优势,仅为2 169元/t,比煤气化制甲醇低697元/t,比天然气制甲醇低528元/t;焦炉煤气+转炉煤气制甲醇和焦炉煤气+天然气制甲醇路线的能耗比较低。焦炉煤气+转炉煤气制甲醇的能耗比煤气化制甲醇低0.62tce/t;除煤气化制甲醇外,其余甲     

双气源耦合,优化工艺提高焦化园区整体效益的探索

龙源焦化园区焦炉煤气供应不足,甲醇装置产能浪费严重,提出了新建一套气化装置,气化煤气一部分用于焦炉燃烧,置换出约15%的回炉煤气;另一部分与变压吸附制取天然气后的焦炉煤气耦合,进行甲醇合成,以达到增产达效的目的。经计算,年气化20万t焦粒,与焦炉煤气耦合后,可以提取压缩天然气1亿m3、增产甲醇7.80万t。通过进行投资与效益分析,该项目具有很高的经济和社会效益,年可创造经济效益9 654万元。     

焦炉煤气制甲醇3种流程的比较

3种焦炉煤气制甲醇的流程比较见下表，从中可以看出，焦炉煤气提氢配转炉煤气生产甲醇工艺路线最优。     

黄陵矿业年产30万吨焦炉煤气制甲醇项目投产

陕西煤化集团黄陵矿业煤化工公司年产30万吨焦炉煤气制甲醇项目2013年5月18日顺利开车．产出合格的精甲醇,这是迄今为止国内最大规模的焦炉煤气制甲醇生产装置。该项目于2011年6月开工建设,利用焦炉煤气为原料,采用先进的空分、循环水等辅助系统,分为净化、压缩、合成、精馏4个生产单元,年产甲醇30万吨,年产值可达7-35亿元。利用焦炉煤气制甲醇不仅属于循环经济和节能减排项目．而且具有成本优势,从根本上解决了焦炉煤气放空所造成的环境污染,并可带动相关产业发展,符合陕西省产业结构调整的发展方向。     

山西焦煤集团100万t/a甲醇项目核心工艺包已通过审查

<正>近日,山西焦煤集团飞虹化工股份有限公司100万t/a焦炉煤气制甲醇综合改造项目召开了甲醇合成装置工艺包审查会。据悉,甲醇合成装置主要是将由气化生产的粗煤气、焦炉煤气经脱硫、脱碳等过程净化为合成气,进行提压、升温、催化反应等过程生产出MTO级甲醇产品,与会人员对专利商提交的工艺包进行了系统、严格的审查,对审查出的问题和意见,要求在终版工艺包文件中进行修改和落实,确保终版工艺包的交付。     

充分利用焦炉转炉煤气资源发展甲醇产品

简要分析了我公司发展甲醇产品的区位优势。对几种甲醇原料路线进行了比较，并对以焦炉煤气和转炉煤气为原料生产甲醇进行了物料衡算和经济效益分析，说明以焦炉煤气和转炉煤气为原料生产甲醇在技术经济方面的优势。     

20亿m~3/a煤制天然气项目气化工艺方案的选择

以新疆伊犁新天煤化工有限责任公司20亿m3/a煤制天然气项目气化工艺方案的选择为例,介绍了流化床气化工艺、气化床(喷流床)气化工艺和移动床(固定床)气化工艺的技术特点;对比分析了Lurgi碎煤加压气化工艺、GSP气化工艺和Shell粉煤气化工艺的消耗指标。结果表明:①由于当地煤种成浆性较差,不宜采用Texaco水煤浆气化工艺;②从投资、运行、管理等方面综合考虑,在Lurgi,GSP,Shell 3种工艺方案中,Lurgi碎煤加压气化工艺具有一定的优势。     

安全仪表系统(SIS)在焦炉煤气制甲醇行业的应用

世界范围内,我国的焦化规模属于最大的,大量的焦化生产带来了焦炉煤气难以全部有效利用的难题,假若直接排入到大气中,空气污染将不可避免,势必造成煤气资源的浪费。以焦炉煤气为原料生产甲醇时目前较为普遍的一种煤气利用方式,且具有环保和经济可行的特点。为了保证焦炉煤气制甲醇生产的安全性,必须设置独立的SIS系统。     

山西省焦炉煤气综合利用的设想

山西2004年焦炭产量8000万t左右,占全国30%以上,富裕焦炉煤气约70亿m3/a。根据山西省焦炉煤气资源浪费、环境污染的实际情况,提出了在山西综合利用焦炉煤气的设想,并重点介绍了由焦炉煤气生产甲醇及其下游产品如甲醛、醋酸、醋酐等的设想。通过经济性分析,上述项目全部实施,可创造利润51.2亿元。在充分利用有限资源的同时,也创造了经济效益。     

一种低能耗捕集CO2煤基甲醇和电力联产过程设计

传统的煤制甲醇过程所需合成气的氢碳比为2.1左右,而煤气化粗合成气氢碳比仅为0.7左右,因此需要将部分合成气进行变换来调节氢碳比。然而,变换气与未变换气混合后使得CO₂浓度降低,从而导致CO₂捕集能耗增加。提出了一种低能耗捕集CO₂煤基甲醇和电力联产过程。新联产过程中部分粗合成气首先经过变换,将CO转变为H₂和CO₂,CO₂浓度提高,在此时进行CO₂捕集可实现捕集能耗的降低。经CO₂捕集后,得到富H₂气体,富H₂气体分流后与另一部分煤气化粗合成气混合调节甲醇合成的氢碳比。对新的过程进行了建模、模拟与分析。结果表明相比传统的带CO₂捕集的煤制甲醇和IGCC发电过程,新的联产过程的能量节约率可达到16.5%,CO₂捕集能耗下降30.3%。     

煤和焦炉气联供制烯烃过程的建模模拟与分析

由于煤富碳少氢,煤制烯烃过程生产1 t产品将排放约5.8 t CO₂.与此同时,中国焦炭工业每年产生约7×10¹⁰ m³的副产物焦炉气,这些富氢的焦炉气大多被燃烧或直接排放进入大气,对环境造成严重影响的同时还浪费了巨大的经济价值.本文对焦炉气辅助煤制烯烃的新过程进行了建模模拟与系统分析.焦炉气与煤元素互补,焦炉气中的H₂可用来调节合成气的氢碳比;CH₄可通过甲烷水蒸气重整和甲烷干重整两个过程,提高合成气的氢碳比的同时降低煤制烯烃过程排放的CO₂,提高碳元素利用率,实现节能减排.这个新的联供过程的能效比煤制烯烃过程提高了约10个百分点,而CO₂排放量则减少了约95%.     

Performance characteristics of fluidized bed syngas methanation over Ni-Mg/Al2O3 catalyst

The performance characteristics of isothermal fluidized bed syngas methanation for substitute natural gas are investigated over a self-made Ni–Mg/Al2O3 catalyst. Via atmospheric methanation in a laboratory fluidized bed reactor it was clarified that the CO conversion varied in 5% when changing the space velocity in 40–120 L·g?1·h?1 but the conversion increased obviously by raising the superficial gas velocity from 4 to 12.4 cm·s?1. The temperature at 823 K is suitable for syngas methanation while obvious deposition of uneasy-oxidizing Cγoccurs on the catalyst at temperatures around 873 K. From a kinetic aspect, the lowest reaction temperature is suggested to be 750 K when the space velocity is 60 L·g?1·h?1. Raising the H2/CO ratio of the syngas increased proportionally the CO conversion and CH4 selectivity, showing that at enough high H2/CO ratios the active sites on the catalyst are sufficient for CO adsorption and in turn the reaction with H2 for forming CH4. Introducing CO2 into the syngas feed suppresses the water gas shift and Boudouard reactions and thus increased H2 consumption. The ratio of CO2/CO in syngas should be better below 0.52 because varying the ratio from 0.52 to 0.92 resulted in negligible increases in the H2 conversion and CH4 selectivity but decreased the CH4 yield. Introducing steam into the feed gas affected little the CO conversion but decreased the selectivity to CH4. The tested Ni–Mg/Al2O3 catalyst manifested good stability in structure and activity even in syngas containing water vapor.     

Study on a multifunctional energy system producing coking heat, methanol and electricity

A multifunctional energy system (MES) capable of consuming coke oven gas (COG) and coal, and simultaneously producing coking heat, methanol and electricity, was subject to an exergy analyses based on Energy Utilization Diagrams (EUDs). In this system a coal-fired coke oven is adopted to produce coke and COG, where non-coking coal is burned to supply thermal energy to the coking process. The COG and coal gas gasified from coal in a gasifier, were mixed to produce syngas for methanol synthesis. Since COG rich in hydrogen and coal gas rich in CO, the mixture of COG and coal gas can easily adjust the mole ratio of CO to H₂ of syngas instead of the conversional reforming and shift processes. The active component of syngas is firstly converted into methanol and then the rest is introduced to a gas turbine for power generation. As a result, the overall efficiency of the MES system is about 62.3%, and its energy savings ratio is about 15% comparing with individual systems. The paper provides a new approach to use coal more efficiently and cleanly.     

煤和焦炉气联供制合成天然气过程的建模、模拟与分析

近年来中国的煤制天然气项目快速发展。然而煤制天然气项目的CO₂排放量大、污水产量高难处理,生产过程能效低。与此同时,中国焦炭工业每年产生约700亿立方米的副产物焦炉气,这些富氢的焦炉气大多被燃烧或直接排放进入大气,对环境造成严重影响,同时还浪费了巨大的经济价值。煤和焦炉气联供制天然气新工艺可有效解决这些问题。焦炉气与煤元素互补,焦炉气中的氢气可用来调节合成气的氢碳比;甲烷可通过甲烷干重整过程降低煤制烯烃过程排放的CO₂,提高碳元素利用率,实现节能减排。本文针对煤和焦炉气联供制天然气这个新的工艺过程进行建模、模拟与分析,发现新过程的能效比煤天然气烃过程提高了约8个百分点,而CO₂排放量则减少了约60%。     

Fuel processor based on syngas production via short contact time catalytic partial oxidation reactors

Short contact time catalytic partial oxidation (SCT-CPO) of natural gas is a promising technology for syngas production, representing an appealing alternative to existing processes. The high conversion and selectivity observed since the earlier works in this field can make this process attractive. Moreover, the SCT-CPO reactors can be autothermally operated and the possibility to use air as oxidant appears a feasible route to reduce syngas production costs: these two issues make possible the use of a SCT-CPO reactor as the reformer of a fuel processor for H₂ production for fuel cells.

The present work refers to an experimental study of syngas production from CH₄ and O₂ via a SCT-CPO reactor made of a fixed bed of Rh/-Al₂O₃ spheres. The main obtained results are: (i) an increase in GHSV produces an enhancement of transport rates and this in turn determines an improvement in CH₄ conversion, despite the reduction in residence time; (ii) the catalyst pellets get hotter than the gas phase thus favouring the H₂ and CO production; syngas formation is in fact both thermodynamically and kinetically promoted at high temperatures; (iii) a similar improvement of conversion was obtained with a reduction of the catalyst particle size, thanks once again to an increase in the heat transport and a higher geometrical surface area of the catalyst itself. By a slight increase of the O₂ fed to the reactor, H₂ and CO yields can be maximised and a complete CH₄ conversion achieved.     

铁基氧载体化学链CO2重整CH4方法制备合成气

提出一种铁基氧载体（Fe₃O₄/FeO）化学链CO₂重整CH₄方法制备合成气。为评价该系统的性能,采用Aspen Plus软件对其进行过程模拟和热力学分析。以CH₄转化率、CO₂转化率、能源利用效率和产气氢碳比（H₂/CO）为评价指标,得到系统的优化运行条件,并研究各操作参数（包括各反应器的温度和压力、氧载体甲烷比和CO₂甲烷比）对系统性能的影响。结果表明：当系统处于优化工况时,得到CH₄转化率为97.91%、CO₂转化率为32.76%、能源利用效率为93.77%及产气氢碳比为0.93。该系统能有效利用CO₂和CH₄这两种温室气体获得较低氢碳比的合成气,利于二甲醚的高效合成。     

高温烟气中煤焦气化行为

针对高温烟气中煤焦的气化行为,本文采用FactSage 6.1计算了煤焦在高温烟气下的高温反应特性,并利用热重分析仪分析了煤焦气化行为。通过沉降炉实验进一步研究了不同温度、气体配比、粒径条件下气体产物的动态析出特性,同时计算了评价指标α、β、LHV值。结果表明：随着温度的升高,气体产物H₂和CO的含量增加,β、α、LHV值增大,CH₄和CO₂的含量下降。在温度为1200℃时,β、α值分别由CO₂/CO比为10∶70时的10.80%、5.21%增加到CO₂/CO比为50∶30时的24.71%、41.06%。同时,随着CO₂/CO比值的增大,高温烟气对煤焦气化反应抑制减弱。通过对比反应温度和粒径对煤焦气化反应的影响,得出反应温度远大于粒径对煤焦气化反应的影响。通过实验验证了向高温烟气中喷吹煤焦制备高品质可燃气体方法的可行性。     

褐煤热解-气化-制油系统的CO2减排策略

褐煤热解-气化-制油系统是现代煤化工发展的一个重要研究内容。来自系统多个单元产生的CH₄和CO₂如果发生重整反应,将重整得到H₂/CO比值较高的合成气添加到制油流程中,可实现更多的C被固定到产品中而减少CO₂的直接排放量。对CH₄-CO₂和CH₄-H₂O两种重整反应方式、来自煤热解和费托合成两股甲烷气和典型的干粉气化和水煤浆气化两种流程进行了组合研究。分析结果显示,来自热解和费托合成的甲烷重整后不足以提供调节合成气H₂/CO比例所需的氢气,水煤气变换反应对于褐煤制油系统来说是必需的。从C转化成油的角度来看,采用干粉气化和CH₄-H₂O重整的方案是较好的选择。     

Mechanistic study of partial oxidation of methane to synthesis gas over supported rhodium and ruthenium catalysts using in situ time-resolved FTIR spectroscopy

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane to synthesis gas and the interaction of CH₄/O₂/He (2/1/45) gas mixture with adsorbed CO species over SiO₂ and γ-Al₂O₃ supported Rh and Ru catalysts at 500–600°C. It was found that CO is the primary product for the reaction of CH₄/O₂/He (2/1/45) gas mixture over H₂ reduced and working state Rh/SiO₂ catalyst. Direct oxidation of methane is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product for the reaction of CH₄/O₂/He (2/1/45) gas mixture over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway of CO formation over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts is via the reforming reactions of CH₄ with CO₂ and H₂O. The effect of space velocity on the partial oxidation of methane over SiO₂ and γ-Al₂O₃ supported Rh and Ru catalysts is consistent with the above mechanisms. It is also found that consecutive oxidation of surface CO species is an important pathway of CO₂ formation during the partial oxidation of methane to synthesis gas over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts.