甲醇水蒸气重整制氢研究进展

氢气需求的持续增长,带动制氢技术的不断进步。煤制氢技术投资较高,天然气制氢原料来源受到限制,电解水制氢成本较高。甲醇制氢投资适中,适合各种规模的制氢装置,铜基催化剂反应温度低,低温活性和氢气选择性好,价格低廉,因而甲醇制氢技术得到广泛应用。催化剂载体和助剂的改进研究,对工业催化剂的改进具有重要的指导意义。综述甲醇水蒸气重整制氢工艺、反应机理和催化剂,介绍了催化剂载体和助剂等方面的研究进展情况。     

生物甲烷膜分离提纯系统的设计与优化

以厌氧发酵生物气为原料生产压缩天然气是大规模利用生物质资源的重要途径。首先,在过程模拟软件UniSim Design中基于有限元方法建立了中空纤维膜的离散数值计算模型,适合于模拟渗透切割比非常高的生物甲烷膜分离过程。以单级聚酰亚胺膜分离系统为例研究了关键操作条件--膜的进料压力对处理能力、甲烷收率及压缩天然气生产单耗的影响。目前的评估体系下,提高进料压力有利于提高处理能力和甲烷回收率,而压缩天然气生产单耗在2.70 MPa时最低,为0.46 kW·h·m^-3压缩天然气。通过分析渗透气的甲烷浓度变化趋势,开发了一级二段气体膜分离系统,兼具流程简单、设备投资低、甲烷收率高、产值高的优点。以处理1000 m³·h^-1生物气为例,甲烷收率达95.0%,压缩天然气产量500 m³·h^-1。对应地,装置总投资为3.8×10⁶ CNY,年运行费用及设备折旧为1.5×10⁶ CNY,年经济效益（毛利）超过2.50×10⁶ CNY。     

A new gas to liquids (GTL) or gas to ethylene (GTE) technology

Natural gas is a clean-burning and abundant energy resource, but much of it resides in locations remote from an economic means of transporting it to market. A logical solution for the problem would be to liquefy the natural gas, but this option requires very low temperatures and involves considerable costs. Another solution is to convert the natural gas into hydrocarbon liquids using chemical processing. Fischer-Tropsch technology converts the natural gas into “syngas” (a mixture of carbon monoxide and hydrogen) followed by reaction to liquid fuels. Unfortunately, Fischer-Tropsch technology is expensive.

At Texas A&M University, a research team has conceived a radically new process for converting natural gas into hydrocarbon liquids. It is a “direct” conversion method that does not require producing syngas. The process is essentially three reaction steps and two separation steps to produce hydrocarbon liquids. The process consists of two reaction steps and one separation step to produce ethylene. The process can operate economically with natural gas flows of as low as 300 kSCMD up to any desired capacity.

It is possible to use the GTL technology essentially anywhere natural gas exists from offshore platforms to relatively uninhabited onshore sites. This technology offers an alternative to flaring natural gas when pipelines do not exist. The liquids can be transported in liquid pipelines or in trucks or in tankers. Thus, it offers the opportunity to monetize a resource as well as to reduce undesirable emissions into the atmosphere. The GTE technology is more nearly suited to a location near an existing chemical industry that requires ethylene and/or hydrogen.

SynFuels International Inc. has licensed the technology to commercialize it, and the company has constructed a pilot plant capable of processing 3 kMCMD. The cost of a commercial 300 kSCMD plant should be in the US$ 50–75 million range. The cost of the liquids should be about US$ 25–28 per barrel. Of course, larger capacity plants would require a larger investment but produce a less expensive product.     

气煤联供实现资源高效利用和碳减排技术进展

为解决煤化工过程资源利用率低和碳排放高的问题,有研究者提出以天然气、焦炉气、页岩气等富氢资源和煤炭资源联供方案,旨在实现源头碳减排。文章指出依据联供过程技术的差异,较有代表性的方案可分为集成甲烷部分氧化和集成甲烷干/水蒸气重整的气煤联供过程。文章以生产甲醇为例,从资源利用和经济效益等方面对集成甲烷部分氧化和集成甲烷干/水蒸气重整的气煤联供过程进行分析和比较。集成甲烷部分氧化的工艺碳元素利用率达到57.9%,每吨甲醇排放CO₂为1.50t,较传统煤制甲醇工艺排放减少37.5%。甲醇产品成本稍低于传统工艺。集成甲烷干/水蒸气重整工艺的碳元素利用率最高,达到83.7%。减排效果最明显,每吨甲醇排放CO₂为0.90t,较传统工艺排放减少62.5%,但是由于CO₂转化增加能耗,甲醇产品成本有所提升。由于气煤联供过程有利于CO₂减排,当碳税高于65CNY/tCO₂时,两个气煤联供工艺的生产成本低于传统的煤制甲醇工艺。     

铜基催化剂还原过程研究综述

铜基催化剂广泛应用于工业生产中,催化剂还原是催化剂生产的最后一道工序,也是工业使用前的第一个步骤,对几种铜基催化剂的还原过程进行综述。铜基催化剂主要应用于CO与H_2合成甲醇和CO低温变换,也可用于CO_2与H_2合成甲醇以及脂肪酯加氢制脂肪醇。铜基催化剂的还原方法主要有液相还原法和气相还原法,其中,气相还原法用途较广。对影响还原的条件(H_2浓度、温度、压力和空速等)及杂质(H_2O、O_2和CO_2等)进行总结,并以甲醇合成催化剂为例对低氢还原法和高氢还原法作了介绍。     

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%。     

气煤联产甲醇天然气转化工艺方案选择

介绍了气煤联产甲醇氢碳互补和天然气转化工艺原理,分析了不同转化工艺的过剩氢,对一段与二段转化的天然气消耗、煤气变换率、CO2排放、动力消耗、投资进行了比较,指出了一段蒸汽转化能起到很好的补氢作用,可使水煤气的变换率为最低,一段蒸汽转化无论是在天然气消耗、动力消耗、CO2排放,还是投资上均优于二段转化,是气煤联产甲醇的最佳转化方案。     

Herstellung von Fahrbenzin aus Kohle oder Erdgas

Production of petrol from coal and natural gas . This article assumes an adequate knowledge of the Fischer-Tropsch process in its original form and as its modern variant, the Synthol process, and adopts the view that coal hydrogenation will only become implementable on an industrial scale in the early 1990. In detail, it considers the integration of the Mobil MTG process in the proven area of methanol production; operation of pilot plant has shown that this process is indeed suitable for industrial scale operation. The production of methanol from natural gas and coal is discussed, as is the subsequent conversion of methanol to petrol; emphasis is placed on the best possible integration of all process plant. Apart from the conventional steam reforming route for methanol production from natural gas, the alternative approach of combing a steam reforming plant with an autothermal cleavage step is also considered; the latter leads to a significant increase in efficiency and a reduction in investment costs. It is also shown for coal as raw material that simultaneous generation of petrol and SNG has considerable advantages of a thermal and financial nature. The principal process steps are described after the manner of keywords and the product costs are presented as functions of the various raw material costs.     

Analysis and modeling of synthesis gas conversion to methanol: New trends toward increasing methanol production profitability

Technologies for methanol production from synthesis gas are analyzed. Their main advantages and disadvantages are determined, and a new methanol synthesis technology without feed circulation is proposed, which, in particular, is also applicable at a significant nitrogen content of the synthesis gas feed. On the basis of the results of laboratory and bench tests of the new process, mathematical models of a catalyst grain and a catalytic reactor and a kinetic model of methanol synthesis are constructed and their parameters are estimated. It is shown that the models fit experimental data. A three-reactor methanol synthesis unit providing 75–80% conversion of the synthesis gas feed is calculated. The crude methanol obtained has a high content of the desired product of 94–99 wt %. It is demonstrated that this process is characterized by much lower feed and energy consumption.     

化学链空分联合化学链制氢的煤制甲醇过程参数优化与分析

我国能源结构决定了以煤为主的甲醇生产路线。传统煤制甲醇过程主要存在过程能量效率低、CO₂捕集能耗高等问题。本文提出了一种化学链空分联合化学链制氢的煤制甲醇新过程,以降低能耗、二氧化碳排放及提高能源效率。化学链空分技术的集成可以替代传统煤制甲醇过程的空气分离单元,并在一定程度上降低能耗。化学链制氢技术的集成,一方面可以替代水煤气变换装置,并且可以极大程度降低二氧化碳捕集能耗;另一方面,化学链制氢技术还可生产用于调整合成气氢与碳比的氢。本文对新过程的核心单元进行了参数优化以及全流程的模拟,基于模拟对新过程的性能进行了分析,结果表明新过程与传统的煤制甲醇过程相比,空分和二氧化碳捕集能耗分别降低了41%和89%。同时,新过程的能量效率提高了18%,二氧化碳排放量降低了45%。     

低温甲醇洗碳捕集改进与优化

减少CO₂排放对环境保护尤为重要。传统低温甲醇洗工艺中大量被贫甲醇吸收的CO₂由于被N₂稀释而直接作为尾气排放进大气中。为探究工艺改进空间,本研究基于Aspen Plus对一传统低温甲醇洗工艺进行模拟,物性方法选用CPA (Cubic-Plus-Association)模型并对该模型的二元交互系数进行回归修正,后与实际数据进行对比确保模型的准确性。对于工艺改进,首先在传统低温甲醇洗工艺的基础上采用四级增压热闪蒸和降压闪蒸相结合的方式进行一次改进以用于CO₂捕集,并对相关参数进行优化以进一步降低系统公用工程消耗。结果显示,虽然一次改进工艺的CO₂产量是传统工艺的3.3倍,但系统能量消耗增加了2.12%,系统(火用)消耗增加了17.81%。接着,在一次改进工艺的基础上采用“半贫液+透平回收”相结合技术进一步进行节能改进,二次改进工艺的CO₂产量不仅与一次改进工艺相当,系统能量消耗和系统(火用)消耗相比于传统低温甲醇洗工艺也分别降低了17.16%和5.85%。     

低温甲醇洗净化工艺技术进展及应用概况

低温甲醇洗是一种节能型的酸性气体净化工艺,目前已在国内外百余套氨合成、甲醇合成、羟基合成、工业制氢、城市煤气、天然气脱硫等生产装置中得到了广泛的应用.介绍了该工艺近期的技术进展,与其它净化工艺在能耗、投资费用方面的比较及工艺技术特点,并简述了在酸性气体净化装置中的实际应用情况.     

加压固定床粗煤气再转化工艺研究

通过理论分析,综合加压固定床煤气化工艺和烃类转化工艺的技术特点,提出加压固定床粗煤气再转化工艺。加压固定床粗煤气再转化工艺取消了现有加压固定床煤气化工艺中煤气水分离、酚氨回收、废气焚烧、变换工艺洗涤塔、低温甲醇洗工艺萃取系统和石脑油分离系统等装置,降低固定资产投资46.9亿元（现用煤气化工艺化工固定资产投资117.25亿元）;每年减少使用原料煤96.84万～118.18万t,约合1.29亿元（以褐煤120元/t计）;取消使用二异丙基醚0.21万t/a、减少甲醇用量0.96万t/a和质量分数32%的NaOH用量0.36万t/a;取消含尘煤气水和含油煤气水排放量1585.71 t/h（原排放污水1761.9 t/h）;减少废水处理装置土地使用面积17790 m2以上。提高CO2利用率,提高硫回收率。加压固定床粗煤气再转化工艺具有工艺、设备和工程建设投资少,工艺运行成本低,环境保护好等显著特点。     

Neues Verfahren zur Methanol- und Ammoniak-Synthese. Der Gas/Feststoff/Feststoff-Rieselströmungsreaktor – ein neuer Reaktortyp zur Führung chemischer Gleichgewichtsprozesse

New process for the production of methanol and ammonia. The gas/solids/solids thrickle flow reactor – a new kind of reactor for chemical equilibrium processes . A new process for the production of ammonia or methanol has been developed in the high pressure laboratory of Twente Technical University. The reactants can be made to react completely in a single reactor pass, thus avoiding expensive recirculation. Complete reaction without recirculation is accomplished by a combination of two reversible processes: a chemical reaction and a selective adsorption of the reaction product on a solid in constant flow. On introduction of an inert-gas free stoichiometric mixture of reactants into the reactor, the exhaust gas outlet can be closed. If there is an excess of one of the reactants or of inert gas, it can leave from the top of the reactor. Such a process has been accomplished in a new gas/solids/solids trickle flow reactor in which a granulated adsorbent ?rains”? through a fixed bed of catalyst. The present article describes the use of this kind of reactor for methanol synthesis. Considerable savings in production costs are expected relative to the modern Lurgi low pressure process. A pilot plant is to be built to characterize and evaluate the new process. Royal Dutch Shell has registered a patent application.     

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。     

An efficient technique for improving methanol yield using dual CO2 feeds and dry methane reforming

Steam methane reforming (SMR)-based methanol synthesis plants utilizing a single CO₂ feed represent one of the predominant technologies for improving methanol yield and CO₂ utilization. However, SMR alone cannot achieve full CO₂ utilization, and a high water content accumulates if CO₂ is only fed into the methanol reactor. In this study, a process integrating SMR with dry methane reforming to improve the conversion of both methane and CO₂ is proposed. We also propose an innovative methanol production approach in which captured CO₂ is introduced into both the SMR process and the recycle gas of the methanol synthesis loop. This dual CO₂ feed approach aims to optimize the stoichiometric ratio of the reactants. Comparative evaluations are carried out from a techno-economic point of view, and the proposed process is demonstrated to be more efficient in terms of both methanol productivity and CO₂ utilization than the existing stand-alone natural gas-based methanol process.     

合成氨工艺脱碳方法评述

介绍了4种脱碳方法的发展现状,并对其性能优劣进行评述:碳酸丙烯酯(PC)法不仅溶剂损失大,净化气中CO2含量高,而且碳丙溶液对碳钢有腐蚀,生产效率低,能耗高;N-甲基二乙醇胺(MDEA)法溶液损耗小,净化度高,且对设备无腐蚀;聚乙二醇二甲醚(NHD)法不仅溶剂损耗低,净化度高,而且对设备腐蚀极小,能耗低,工艺流程简单,投资低。低温甲醇洗法工艺流程复杂,设备较多,投资高,但运行成本较低,而且溶液具有较好的热稳定性和化学稳定性,吸收选择性好,净化度高。脱碳方法的评述将会对合成氨工业生产中脱碳方法的选取起到一定的参考启示作用。     

不同CO2捕集技术的CO2耦合绿氢制甲醇工艺研究

大量的化石燃料燃烧导致温室气体排放增加,全球气候变暖。世界各国以全球协约的方式减排CO₂,我国也由此提出“碳达峰·碳中和”目标。CO₂捕集以及转化制液体燃料和化学品是双碳目标下行之有效的碳减排措施之一,不仅可以实现CO₂的资源化利用,同时也缓解了国家能源安全问题。本文以燃煤电厂烟气CO₂捕集和CO₂合成甲醇为研究对象,分析了基于四种不同CO₂捕集技术的CO₂耦合绿氢制甲醇工艺。对四种不同CO₂捕集技术的CO₂制甲醇工艺进行了严格的稳态建模和模拟,分析和比较了不同CO₂捕集技术情景下的CO₂制甲醇工艺的技术和经济性能。结果表明,MEA、PCS、DMC和GMS情景的单位甲醇能耗分别是7.81、5.48、5.91和4.66 GJ/ t CH₃OH,GMS情景的单位能耗最低,其次是PCS情景,但随着更高效相变吸收剂的开发,PCS情景的单位甲醇产品的能耗将降低至2.29~2.58 GJ/t CH₃OH。四种情景的总生产成本分别是4314、4204、4279和4367 CNY/ t CH₃OH,PCS情景的成本最低,更具有经济优势。综合分析表明PCS情景的性能表现最好,为可用于燃煤电厂最佳的碳捕集技术,为CO₂高效合成燃料化学品提供方向,缓解化石燃料短缺和环境污染问题。     

不同CO2捕集技术的CO2耦合绿氢制甲醇工艺研究

大量的化石燃料燃烧导致温室气体排放增加,全球气候变暖。世界各国以全球协约的方式减排CO₂,我国也由此提出“碳达峰·碳中和”目标。CO₂捕集以及转化制液体燃料和化学品是双碳目标下行之有效的碳减排措施之一,不仅可以实现CO₂的资源化利用,同时也缓解了国家能源安全问题。本文以燃煤电厂烟气CO₂捕集和CO₂合成甲醇为研究对象,分析了基于四种不同CO₂捕集技术的CO₂耦合绿氢制甲醇工艺。对四种不同CO₂捕集技术的CO₂制甲醇工艺进行了严格的稳态建模和模拟,分析和比较了不同CO₂捕集技术情景下的CO₂制甲醇工艺的技术和经济性能。结果表明,MEA、PCS、DMC和GMS情景的单位甲醇能耗分别是7.81、5.48、5.91和4.66 GJ/ t CH₃OH,GMS情景的单位能耗最低,其次是PCS情景,但随着更高效相变吸收剂的开发,PCS情景的单位甲醇产品的能耗将降低至2.29~2.58 GJ/t CH₃OH。四种情景的总生产成本分别是4314、4204、4279和4367 CNY/ t CH₃OH,PCS情景的成本最低,更具有经济优势。综合分析表明PCS情景的性能表现最好,为可用于燃煤电厂最佳的碳捕集技术,为CO₂高效合成燃料化学品提供方向,缓解化石燃料短缺和环境污染问题。     

Energy efficiency analysis of natural gas hydrates production method

The decomposition of natural gas hydrates is a phase change process, which involves the consumption and conversion of various forms of energy, such as electrical energy, chemical energy, and thermal energy. In order to evaluate the economy capacity of natural gas hydrates exploitation, an exergy model was established to calculate the energy efficiency ratio (EER) of hydrate production method. The CO₂ replacement method is taken as a case study to introduce the calculation equation and flow chart of energy efficiency ratio in any production period. The amount of CO₂ injection, gas production and mole fraction of methane in produced gas are three key parameters in the process of CO₂ replacement. The ratio between the amount of gas production and CO₂ injection is defined as production injection ratio to eliminate the influence of deposit size. This work studied the influence of production injection ratio and the mole fraction of methane in produced gas on EER. The results show that the EER of gas hydrates production by CO₂ replacement is between 0.31 and 6.4 under the set conditions, and it increases with the increase of production injection ratio. In addition, increasing the mole fraction of methane in produced gas can reduce the energy consumption for gas separation and increase EER. Therefore, there are two effective ways to increase EER of CO₂ replacement through controlling the amount of gas production and the mole fraction of methane in produced gas. The EER model is established to provide guidance for the optimization of gas hydrate mining process.