甲醇合成反应机理

用CO/H_2混合气合成甲醇不能没有CO_2,而用CO_2/H_2混合气合成甲醇,虽然反应慢,但却很顺利。这样一个事实,早已引起人们深思它的合成机理。不久前,英帝国化学公司ICI的Chinchen和他的同事们,曾多次对甲醇合成中有关到底是CO进行合成,还是CO_2进行合成的问题及转化过程铜催化剂处于什么状态及ZnO和Al_2O_3到底起什么作用,进行了研究。     

煤制甲醇项目原料气深度净化精脱硫工艺方案和催化剂选型研究

介绍了煤制甲醇项目合成气深度净化脱硫催化剂和CO_2原料气脱硫催化剂的应用情况,以神华宁煤100万t/a煤制甲醇装置为例,研究将合成气和CO_2原料气中硫脱除的工艺设计和催化剂选型。结果表明,CO_2原料气设置COS水解反应器,选用K、Na金属负载催化剂将CO_2中的COS转化为H_2S,合成气和CO_2原料气混合后再设置深度净化精脱硫反应器,选用ZnO型催化剂将硫脱除至5μg/m~3以下,满足甲醇合成催化剂要求的入口总硫控制在30μg/m~3以下的要求。     

甲醇合成催化剂的工艺参数优化及反应机理探讨

对自主研制的甲醇合成催化剂进行工艺参数优化,同时根据实验结果对合成气条件下甲醇合成的反应机理进行探讨。实验采用16通道反应器,考察反应温度和接触时间对合成甲醇反应速率的影响,确定适宜的催化剂工艺条件。结果表明,在较长接触时间下,随着温度的升高,CO转化率、H_2转化率和甲醇相对含量先升高后降低,CO_2转化率降低。在较低温度下,CO_2转化率随接触时间延长基本不变,表明甲醇中碳元素主要来自于CO,而CO_2浓度处于水汽变换反应与加氢形成甲醇反应之间的平衡状态。     

MODELING OF ELEMENTARY PROCESS KINETICS FOR METHANOL SYNTHESIS (Ⅱ )A TRANSIENT KINETIC MODEL OF METHANOL SYNTHESIS FROM CO/CO_2/H_2

在基元过程序列结构判识的基础上,以傅立叶变换红外光谱仪(FTIR)气体池作为检测器,采用动态响应技术,进行了合成甲醇过程瞬态动力学的实验研究,得到了微型反应器尾气中各主要物种的浓度对反应器进料浓度阶跃变化的动态响应数据。基于瞬态速率模型对实验数据的拟合,得到了由H_2/CO/CO_2合成甲醇初步的瞬态动力学关系。     

原位还原Cu/ZnO催化剂上CO_2加氢合成甲醇反应研究

采用室温固相研磨法制备原位还原Cu/ZnO催化剂,并将其用于CO_2加氢合成甲醇反应。利用XRD、BET、TG-DTG等手段对催化剂性能进行了表征,利用高压固定床反应装置对催化剂活性进行了评价,考察了甲酸用量、焙烧温度及升温速率等条件对催化剂性能的影响。结果表明,室温固相研磨得到的前驱体在N_2中焙烧,前驱体氧化分解和还原活化一步完成,无需外加H_2还原,直接制得了原位还原Cu/ZnO催化剂。随甲酸用量、焙烧温度、升温速率增加,催化活性呈现先增加后减小趋势。Cu/Zn摩尔比为1∶1和HCOOH/(Cu+Zn)摩尔比11∶1,前驱体于N_2中焙烧温度573 K和升温速率3 K/min时,制得的原位还原Cu/ZnO催化剂在CO_2加氢合成甲醇反应中呈现最佳活性,CO_2转化率和甲醇产率分别达到了33.44%和28.17%。与空气中焙烧再外加5%H_2还原的Cu/ZnO催化剂相比,原位还原Cu/ZnO催化剂比表面积较高,Cu~0粒径较小,催化活性较高。     

合成甲醇基元过程瞬态动力学的模型化(Ⅱ)——合成甲醇瞬态动力学

在基元过程序列结构判识的基础上,以傅立叶变换红外光谱仪(FTIR)气体池作为检测器,采用动态响应技术,进行了合成甲醇过程瞬态动力学的实验研究,得到了微型反应器尾气中各主要物种的浓度对反应器进料浓度阶跃变化的动态响应数据。基于瞬态速率模型对实验数据的拟合,得到了由H_2/CO/CO_2合成甲醇初步的瞬态动力学关系。     

甲醇合成催化剂Cu/CeO_2活性位的形成机制与初始催化机理探索

结合甲醇合成催化剂在制备过程中和反应初期得到的表征信息(XRF、XRD、HRTEM、H_2-TPR等),对催化剂Cu/CeO_2活性位的形成机制与初始催化机理进行了探索。结果表明,催化剂Cu/CeO_2制备过程中,除了CuO被完全还原外,载体CeO_2的表面也有部分被还原;CO/H_2在Cu/CeO_2上合成甲醇之前,会有短暂的CO_2生成,当CO_2生成达到峰值时,甲醇合成活性开始出现。     

降低甲醇装置转化气中CO_2含量技术研究

金牛旭阳20万t/年甲醇项目,在甲醇合成反应中CO和CO_2都能合成甲醇,但在正常情况下CO的转化率要高于CO_2转化率约10%,因此,在不增加原料气和动力消耗的情况下,通过调整工艺参数,来降低转化气中CO_2含量,提高CO含量,能提高甲醇产量,可以给企业带来可观的经济效益。     

原位还原Cu/ZnO催化剂上CO_2加氢合成甲醇反应研究

采用室温固相研磨法制备原位还原Cu/ZnO催化剂,并将其用于CO_2加氢合成甲醇反应。利用XRD、BET、TG-DTG等手段对催化剂性能进行了表征,利用高压固定床反应装置对催化剂活性进行了评价,考察了甲酸用量、焙烧温度及升温速率等条件对催化剂性能的影响。结果表明,室温固相研磨得到的前驱体在N_2中焙烧,前驱体氧化分解和还原活化一步完成,无需外加H_2还原,直接制得了原位还原Cu/ZnO催化剂。随甲酸用量、焙烧温度、升温速率增加,催化活性呈现先增加后减小趋势。Cu/Zn摩尔比为1∶1和HCOOH/(Cu+Zn)摩尔比11∶1,前驱体于N_2中焙烧温度573 K和升温速率3 K/min时,制得的原位还原Cu/ZnO催化剂在CO_2加氢合成甲醇反应中呈现最佳活性,CO_2转化率和甲醇产率分别达到了33.44%和28.17%。与空气中焙烧再外加5%H_2还原的Cu/ZnO催化剂相比,原位还原Cu/ZnO催化剂比表面积较高,Cu⁰粒径较小,催化活性较高。     

气液固相催化合成甲醇本征动力学

研究了以液体石蜡为液相介质在铜基催化剂上由CO、CO_2与氢气合成甲醇的本征动力学,按CO和CO_2加氢生成甲醇的反应途径,提出了反应机理,建立了6种动力学模型,经参数估值及模型筛选,得出了最终模型,该模型的计算值与实验值吻合很好,对CO及CO_2转化速率的平均偏差分别为3.69%和3.92%。     

Cu/Zn/Al/Zr纳米纤维催化剂上的CO2加氢合成甲醇过程

A highly active Cu/Zn/Al/Zr fibrous catalyst was developed for methanol synthesis from CO₂ hydrogenation.Various factors that affect the activity of the catalyst,including the reaction temperature,pressure and space velocity,were investigated.The kinetic parameters in Graaf’s kinetic model for methanol synthesis were obtained.A quasistable economical process for CO₂ hydrogenation through CO circulation was simulated and higher methanol yield was obtained.     

Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2

The effect of zirconia promotion on Cu/SiO₂ for the hydrogenation of CO and CO₂ at 0.65 MPa has been investigated at temperatures between 473 and 573 K. With increasing zirconia loading, the rate of methanol synthesis is greatly enhanced for both CO and CO₂ hydrogenation, but more significantly for CO hydrogenation. For example, at 533 K the methanol synthesis activity of 30.5 wt% zirconia-promoted Cu/SiO₂ is 84 and 25 times that of unpromoted Cu/SiO₂ for CO and CO₂ hydrogenation, respectively. For all catalysts, the rate of methanol synthesis from CO₂/H₂ is higher than that from CO/H₂. The apparent activation energy for methanol synthesis from CO decreases from 22.5 to 17.5 kcal/mol with zirconia addition, suggesting that zirconia alters the reaction pathway. For CO₂ hydrogenation, the apparent activation energies (~12 kcal/mol) for methanol synthesis and the reverse water-gas shift (RWGS) reaction are not significantly affected by zirconia addition. While zirconia addition greatly increases the methanol synthesis rate for CO₂ hydrogenation, the effect on the RWGS reaction activity is comparatively small. The observed effects of zirconia are interpreted in terms of a mechanism which zirconia serves to adsorb either CO or CO₂, whereas Cu serves to adsorb H₂. It is proposed that methanol is formed by the hydrogenation of the species adsorbed on zirconia.     

Influence of titania on zirconia promoted Cu/SiO2 catalysts for methanol synthesis from CO/H2 and CO2/H2

The effects of adding mixtures of titania and zirconia on the methanol synthesis activity and selectivity of Cu/SiO₂ were investigated. The synthesis of methanol from both CO/H₂ and CO₂/H₂ mixtures was examined at 0.65 MPa and temperatures between 448 and 573 K. For CO hydrogenation, the addition of ZrO₂ alone increased the methanol synthesis activity of Cu/SiO₂ by up to three-fold. Substitution of a portion of the ZrO₂ by TiO₂ decreased the methanol synthesis activity of the catalyst relative to that observed when only ZrO₂ is added. ZrO₂ addition also enhanced the methane synthesis activity by as much as seven fold. In the case of CO₂ hydrogenation, the maximum methanol synthesis activity is achieved when a 50/50 wt% mixture of ZrO₂ and TiO₂ is added to Cu/SiO₂. Neither the presence of the oxide additive nor its composition had any effect on the activity of the reverse water–gas-shift reaction, which suggests that this reaction proceeds only on Cu. The observed effects of ZrO₂ and TiO₂ on the catalytic activity of methanol synthesis from CO and CO₂, and methane synthesis from CO, are interpreted in terms of the strength and concentration of acidic and basic groups on the surface of the dispersed oxide.     

净化气补CO_2提高甲醇合成转化率的技术改造

针对解化化工公司因低温甲醇洗出口净化气中的CO2含量偏低,影响甲醇合成转化率及粗甲醇产量的问题,进行了技术改造。通过将合成氨厂低温甲醇洗装置出CO2再生塔的CO2送入甲醇合成工段低温甲醇洗净化气管,达到提高入甲醇合成塔合成气中CO2含量的目的。运行结果表明,净化气补入CO2后,甲醇合成塔合成气中CO2体积分数提高至3%,甲醇合成转化率提高了4%,粗甲醇耗净化气量明显下降。     

Effects of space velocity on methanol synthesis from Co2/Co/H2 over Cu/ZnO/Al2O3 catalyst

The space velocity had profound and complicated effects on methanol synthesis from CO₂/CO/H₂ over Cu/ZnO/Al₂O₃ at 523 K and 3.0MPa. At high space velocities, methanol yields as well as the rate of methanol production increased continuously with increasing CO₂ concentration in the feed. Below a certain space velocity, methanol yields and reaction rates showed a maximum at CO₂ concentration of 5–10%. Different coverages of surface reaction intermediates on copper appeared to be responsible for this phenomenon. The space velocity that gave the maximal rate of methanol production also depended on the feed composition. Higher space velocity yielded higher rates for CO₂/ H₂ and the opposite effect was observed for the CO/H₂ feed. For CO₂/CO/H₂ feed, an optimal space velocity existed for obtaining the maximal rate.     

In situ IR studies on the mechanism of methanol synthesis from CO/H2 and CO2/H2 over Cu-ZnO-Al2O3 catalyst

Methanol synthesis from CO/H₂ and CO₂/H₂ was carried out at atmospheric pressure over Cu/ZnO/Al₂O₃ catalyst. The formation and variation of surface species were recorded by in situ FT-IR spectroscopy. The result revealed that both CO and CO₂ can serve as the primary carbon source for methanol synthesis. For CO/H₂ feed gas, only HCOO-Zn was detected; however, for CO₂/H₂, both HCOO-Zn and HCOO-Cu were observed, and without CH₃O-Cu. HCOO-Zn was the key intermediate. A scheme of methanol synthesis and reverse water-gas shift (RGWS) reaction was proposed.     

Methanol synthesis over Cu/SiO2 catalysts

The rates of CO and CO/CO₂ hydrogenation at 4.2 MPa and 523 K are reported for a series of Cu/SiO₂ catalysts containing 2 to 88 wt.% Cu. These catalysts were prepared on a variety of silica sources using several different Cu deposition techniques. In CO/CO₂ hydrogenation, the rate of methanol formation is proportional to the exposed Cu surface area of the reduced catalyst precursor, as determined by N₂O frontal chromatography. The observed rate, 4.2×10^–3 mole CH₃OH/Cu site-sec, is within a factor of three of the rates reported by others over Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts under comparable conditions. These results suggest that the ZnO component is only a moderate promoter in methanol synthesis. Hydrogenation of CO over these catalysts also gives methanol with high selectivity, but the synthesis rate is not proportional to the Cu surface area. This implies that another type of site, either alone or in cooperation with Cu, is involved in the synthesis of methanol from CO.     

The promoting effect of alcohols in a new process of low-temperature synthesis of methanol from CO/CO2/H2

The catalytic promoting effects of eleven different alcohols, as reaction medium, on the synthesis of methanol from feed gas of CO/CO₂/H₂ on Cu/ZnO solid catalyst were investigated. Added alcohol altered the reaction route to realize a low-temperature synthesis method where formate was an intermediate. Many alcohols showed catalytic promoting effect for methanol formation at temperature as low as 443 K, remarkably lower than that in the present industrial ICI process.     

CO2对CuO/ZnO/Al2O3催化剂前体老化及催化性能的影响

采用并流共沉淀法制备CuO/ZnO/Al2O3甲醇合成催化剂前体,在通入CO2条件下老化,采用XRD、FT-IR、DTG、H2-TPR、XPS等表征手段对制备的前体及焙烧后的催化剂进行表征,研究不同CO2通入量对前体晶相转变、微观结构及其焙烧后催化性能的影响。研究结果表明,老化阶段通入CO2后,沉淀母液的pH值趋于7,产生CO32?离子,进而影响Zn2+的沉淀,促进Cu2+进入Zn5(CO3)2(OH)6晶格中取代Zn2+形成绿铜锌矿(Zn,Cu)5(CO3)2(OH)6物相,有助于增强焙烧后催化剂的Cu-Zn之间协同作用,增加活性组分Cu分散度。CO2通入量为40 mL/min时,制备的催化剂在浆态床合成甲醇过程中表现出良好的催化活性和稳定性,甲醇时空收率（STY）达到301.78 g/(kg?h),失活率仅为0.15%/d,与未通入CO2辅助老化制备的催化剂相比,时空收率提高了9.72%,平均失活率降低了33.33%。     

Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst

ZrO₂-doped CuZnO catalyst prepared by successive-precipitation method was investigated by ICP-AES, BET, TEM, XRD, EXAFS, H₂-TPR and CO/CO₂ hydrogenation. The active phase of copper in CuZnO catalyst prepared by co-precipitation method was well-crystallized. The presence of ZrO₂ led to a high copper dispersion, which was distinctive from CuZnO. Though the activity for carbon monoxide hydrogenation was little lower than that of CuZnO catalyst, ZrO₂-doped CuZnO catalyst showed much higher activity and selectivity towards methanol synthesis from carbon dioxide hydrogenation. Moreover, ZrO₂-doped CuZnO catalyst showed high performance for methanol synthesis from CO₂-rich syngas.