微通道内乙醇胺吸收CO2的过程特征（英文）

Process characteristics of CO2 absorption using aqueous monoethanolamine(MEA) in a microchannel reactor were investigated experimentally in this work.A T-type rectangular microchannel with a hydraulic diameter of 408 μm was used.Operating parameters,i.e.temperature,pressure and molar ratio of MEA to CO2 were studied.Under 3 MPa pressure,the mole fraction of CO2 in gas phase could decrease from 32.3% to 300×10?6 at least when gas hourly space velocity ranged from 14400 to 68600 h?1 and molar ratio of MEA to CO2 was kept at 2.2.In particular,the effects of temperature on CO2 absorption flux,mass transfer driving force,gas-liquid contact time and en-hancement factor were analyzed in detail and found that mass transfer enhancement by chemical reaction was a crucial factor for the process of CO2 absorption.     

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.     

Simultaneous desulfurization and denitrification of flue gas by pre-ozonation combined with ammonia absorption

A process of simultaneous desulfurization and denitrification of flue gas was conducted in this study. The flue gas containing 200 mg·m^-3 NO, 1000-4000 mg·m^-3 SO₂, 3%-9% O₂, and 10%-20% CO₂ was first oxidized by O₃ and then absorbed by ammonia in a bubbling reactor. Increasing the ammonia concentration or the SO₂ content in flue gas can promote the absorption of NO_X and extend the effective absorption time. On the contrary, both increasing the absorbent temperature or the O₂ content shorten the effective absorption time of NO_X. The change of solution pH had substantial influence on NO_X absorption. In the presence of CO₂, the NO_X removal efficiency reached 89.2% when the absorbent temperature was raised to 60 °C, and the effective absorption time can be maintained for 8 h, which attribute to the buffering effect in the absorbent. Besides, both the addition of Na₂S₂O₃ and urea can promote the NO_X removal efficiency when the absorbent temperature is 25 °C, and the addition of Na₂S₂O₃ had achieved better results. The advantage of adding Na₂S₂O₃ became less evident at higher absorbent temperature and coexistence of CO₂. In all experiments, SO₂ removal efficiency was always above 99%, and it was basically not affected by the above factors.     

超重力强化AMP-PZ复合溶液脱碳技术及表观动力学

为提高工业上火电厂乙醇胺（MEA）吸收塔脱碳工艺中脱碳率和反应速率,提出了超重力技术耦合2-氨基-2-甲基-1-丙醇-对二氮己环（AMP-PZ）混合胺脱碳方法。正交实验表明：不同操作参数对脱碳率的影响显著性大小依次为：超重力因子、气液比、吸收剂质量浓度、主吸收剂含量、温度;最佳操作条件为：超重力因子为60,气液比为15,吸收剂质量分数为25%,主吸收剂质量分数为60%,温度为25℃,CO₂脱除率可达97.16%。相对传统的乙醇胺（MEA）吸收塔法,CO₂脱除率提高了7.16%。相同操作条件下,旋转填料床的脱碳反应速率常数比曝气反应装置高一倍。建立了超重力场中AMP-PZ脱碳表观动力学模型,不同操作参数对反应速率常数的显著性影响大小依次为：超重力因子>气液比>吸收剂质量浓度。     

二段式吸收塔强化水洗技术提纯沼气过程

压力水洗技术已成为提纯沼气的关键技术之一。采用填料吸收塔进行CO₂脱除实验研究,考察了液气比、吸收压力、吸收温度、CO₂初始含量、填料层高度对CO₂脱除率的影响,以及液气比、沼气流量对总体积吸收系数的影响,并运用填料塔与喷雾塔结合的二段式吸收塔进行压力水洗提纯沼气的过程强化实验。实验结果表明,吸收压力和液气比的增大、吸收温度的降低、填料层高度的增加有利于CO₂的脱除,体积总吸收系数随着液气比及沼气流量的增加而增大。二段式吸收塔能够提高CO₂吸收效果,当沼气处理量为10 L·min^-1,填料层高度为100 cm,CO₂含量小于3%时,与填料塔相比二段式吸收塔可以减少约12%的吸收液用量,并且采用110 cm填料的二段式吸收塔获得最佳的提纯效果,CO₂脱除率达到97.4%。     

纳米锑掺杂氧化锡制备中超临界CO_2干燥的工艺优化及动力学

纳米锑掺杂氧化锡(ATO)具有优越的光电性能,在制备过程中前驱体干燥处理至关重要。为掌握ATO前驱体的超临界CO2干燥工艺特性,研究了超临界干燥的时间、温度、压力和CO2流量等工艺参数对纳米ATO粒径、比表面积等的影响,进一步探讨了超临界CO2流量对干燥动力学的影响规律,并拟合了干燥曲线方程。结果表明:温度35~40℃、压力10~14 MPa、CO2流量1.2~1.8 L·h-1、干燥5~6 h,最终能够获得平均粒径20~30 nm、高比表面积的纳米ATO材料;流量对干燥速率有明显影响,醇分比0.4为干燥速率由恒速转为降速的临界点,醇凝胶干燥动力学方程能够很好地描述ATO醇凝胶干燥工艺过程。研究结果可为湿法制备纳米材料的湿凝胶干燥工业化生产和控制提供参考。     

离子液体水溶液吸收模拟烟气中SO2

建立了一套放大脱硫装置, 利用该装置研究了乙醇胺乳酸盐([MEA]L)水溶液在不同条件下吸收SO₂的性能, 确定出了较优的实验条件, 并在该条件下进行吸收-解吸SO₂循环实验。研究结果表明:烟气中SO₂的去除率随[MEA]L中水分的增加而增加;SO₂的去除率随着气液比的减少而增加, 在气液比为420, SO₂浓度为2850～14280 mg·m^-3范围内时, 出口烟气中SO₂浓度均小于285 mg·m^-3, 满足排放标准;烟气中的CO₂对[MEA]L水溶液吸收SO₂没有影响;利用蒸汽对富液进行解吸再生, 解吸后的贫液可以继续使用, 并且仍具有很高的SO₂去除率。     

A large-scale experimental study on CO2 capture utilizing slurry-based ab-adsorption approach

The increasing concentration of CO_2 in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_2 from various sources with energy conservation is of great significance.Herein,a series of experiments were carried out to successfully test the slurry-based ab-adsorption method for continuously capturing CO_2 in the large-scale cycled separation unit with cost-effect taking into account the scale-up criteria.A bubble column(with height 4900 mm and inner diameter 376 mm) and a desorption tank(with volume 310 L) are the essential components of the separation unit.The novel slurry used in this study was formed with zeolitic imidazolate framework-8 and 2-methylimidazole-water solution.The influence of operation conditions was investigated systematically.The results show that increasing sorption pressure and slurry height level,decreasing gas volume flow and sorption temperature are beneficial for separation processes.The volume fraction of CO_2 in the feed gas was also studied.Although the scale-up effect had been observed and it was found that it exerted a negative effect on CO_2 capture,depending on experimental conditions,CO_2 removal efficiency could still reach 85%-95% and the maximum CO_2 loading in the recycled slurry could be up to0.007 mol·L~(-1)·kPa~(-1).Furthermore,the slurry-based method could be operated well even under very moderate regeneration conditions(333 K and 0.05 MPa),which means that the novel approach shows greater energy conservation than traditional amine absorption methods.     

水力喷射-空气旋流器用于湿法烟气脱硫及其传质机理

在一种新型高效的气液传质设备--水力喷射-空气旋流器(WSA)中,以Ca(OH)₂料浆为吸收剂进行了模拟烟气湿法脱硫的实验研究。结果表明:脱硫率随进口气速增加而增加;随液体喷射速度增加先增加,增加到一定程度后几乎不变;随烟气中SO₂的进口浓度增加而减小,存在一适宜的Ca(OH)₂浓度和回流比。在气体流量24～72 m³·h^-1、循环液体量0.4～0.8 m³·h^-1、料浆中Ca(OH)₂浓度7500 g·m^-3时,对SO₂浓度为1891～6373 mg·m^-3的烟气进行湿法脱硫,脱硫率达88.9%～97.7%,且WSA的旋流气体和喷射液体在湿法脱硫中具有自清洁能力,未发现内部结垢和喷孔堵塞现象。总体积传质系数K_Ga、有效相界面积a均随进口气速u_G增大而增大,而总传质系数K_G随u_G增加变化较小;当液体喷射速度 u_L≤0.26 m·s^-1时,K_Ga和K_G随u_L增加快速增大,之后增加缓慢,而a随u_L几乎线性增加,K_Ga和K_G随吸收剂中Ca(OH)₂浓度c_L增加有一最大值。结合实验数据拟合得到了相关的经验公式,这些关联式能较好地预测WSA的湿法脱硫传质性能。气体旋流场强度对总体积传质系数K_Ga和有效相界面积a起支配作用,脱硫传质过程同时受气膜和液膜阻力控制,但以液膜控制为主。     

Ni-CeO2-K/γ-Al2O3催化剂上沼气联合重整制合成气

采用超声波辅助等体积浸渍法制备Ni-CeO₂-K/γ-Al₂O₃催化剂用于沼气联合重整反应,采用 BET、XRD、TG/DTG等技术对催化剂性质进行了表征,在微型固定床反应装置中研究了反应温度、体积空速、原料气组成等对沼气联合重整反应特性的影响,并对催化剂的稳定性进行了研究。结果表明,助剂CeO₂的加入,提高了催化剂中Ni的分散度,降低了催化剂还原温度。升高反应温度和减小体积空速,能够提高沼气中CH₄和CO₂的转化率;原料气中加入水蒸气,能够明显提高H₂/CO体积比;加入的O₂容易与H₂、CO发生反应,CH₄转化率稍有提高。在常压、反应温度850℃、体积空速为100000h^-1、摩尔比CH₄∶CO₂∶H₂O∶O₂∶Ar=1∶0.5∶0.5∶0.1∶0.01的优化条件下,沼气中CH₄转化率超过95%,CO₂转化率超过75%,生成合成气H₂/CO体积比约为1.6,反应48h后,催化剂未见积炭,保持稳定的活性。与沼气干重整相比,沼气联合重整不利于沼气中CO₂的转化。     

Performance of CO2 absorption in a diameter-varying spray tower

The application of spray towers for CO₂ capture is a development trend in recent years. However, most of the previous jobs were conducted in a cylindrical tower by using a single spray nozzle, whose configuration and performance is not good enough for industrial application. To solve this problem, the present work proposed a diameter-varying spray tower and a new spray mode of dual-nozzle opposed impinging spray to enhance the heat and mass transfer of CO₂ absorption process. Experiments were performed to investigate the mass transfer performance (in terms of the CO₂ removal rate (η) and the overall mass transfer coefficient (K_Ga_e2 are major factors, which affect the absorption performance and the maximums of η and K_Ga_e that are 94.0% and 0.574 kmol·m^-3·h^-1·kPa^-1, respectively, under the experimental conditions. Furthermore, new correlations to predict the mass transfer coefficient of the proposed spray tower are developed in various CO₂ concentrations with a Pearson Correlation Coefficient over 90%.     

CO2 absorption performance in a rotating disk reactor using DBU-glycerol as solvent

Gas–liquid mass transfer of rotating disk reactor was studied in CO_2 absorption using 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU)-glycerol solution as solvent. Effects of the rotating disk structure and various operation parameters on the CO_2 absorption rate and CO_2 removal efficiency were investigated. The rotating disk with optimal holes is conducive to mass transfer of CO_2 and the formation of thin liquid film at the opening increases the gas–liquid contact area. With the increase of rotating speed, the liquid flow pattern on the rotating disk surface changes from thin film flow to separated streams and creates extra liquid lines attached to the rim of the disk,which leads to a very complicated change on the CO_2 absorption rate and CO_2 removal efficiency. The overall gas-phase mass transfer coefficient increases 138% as the rotating speed increasing from 250 to 1400 r·min~(-1).Increasing temperature from 298 to 338 K can enhance the CO_2 absorption rate due to lowering the viscosity of the solvent. The rate-determined step for the absorption is focused on the gas side. The rotating disk reactor can effectively enhance the absorption of CO_2 with viscous DBU-glycerol solvents.     

磁场对氨水吸收烟气中CO2的促进作用

开发了一种新型磁场辅助氨法烟气脱碳技术。含碳烟气通入混有磁性颗粒的氨水溶液,在外加磁场的作用下发生脱碳反应。对该技术的运行特性开展了实验研究。结果表明,外加8 mT恒稳磁场,2 g·L^-1纳米级Fe₃O₄颗粒,氨水的CO₂脱除效率比不添加磁场和颗粒时最多可提高8.8%。外加磁场可以有效提高低浓度氨水的CO₂脱除效率。在模拟烟气流量增加时,外加磁场能有效减缓CO₂脱除效率下降的趋势。同时,外加磁场使得CO₂脱除效率曲线向低温方向移动5℃,有助于提高低温条件下的CO₂脱除效率。磁场可提高气液接触效率、降低相间传质阻力、增强氨水反应活性,从而提高氨水吸收CO₂性能。     

2-甲基咪唑/乙二醇体系常温脱除天然气中的二氧化碳

将2-甲基咪唑溶于乙二醇中形成混合溶液体系,利用该体系常温下实现对天然气中二氧化碳的脱除。首先分别测定单组分甲烷和二氧化碳在体系中的吸收容量,在0.1 MPa下,CO₂在2-甲基咪唑/乙二醇混合溶液中溶解度约为0.87 mol·L^-1,高于同等条件下CO₂在大部分离子液体中的溶解度,二氧化碳的吸收容量远大于甲烷的;然后对混合气CH₄/CO₂进行分离,发现该体系能较好吸收分离CH₄/CO₂。最后考察了体系的再生性和重复利用性,得出2-甲基咪唑/乙二醇溶液体系能完全再生并且能重复使用。     

富氧燃烧烟气压缩净化及高浓度CO2制备工艺研究

富氧燃烧技术是目前最有可能大规模推广和商业应用的碳捕集与封存技术之一,其中,烟气压缩净化及CO₂提纯对于整个富氧燃烧系统至关重要。然而,目前研究多聚焦于富氧燃烧后烟气压缩净化的工艺验证,而对烟气压缩纯化各单元运行特性的研究仍不深入,特别是烟气压缩净化过程杂质污染组分的迁移转化、系统运行参数与污染物脱除效率的关联仍不明确。且现有研究对净化后烟气的深度提纯及高浓度CO₂制备的关注也相对较少,直接关系到富氧燃烧系统运行经济性。因此,针对富氧燃烧烟气净化及CO₂提纯需求,系统探究了富氧燃烧烟气压缩纯化过程SO₂、NO_x吸收脱除以及CO₂深度提纯等各子系统的运行特性,其中SO₂与NO_x脱除采用压缩-酸液吸收,CO₂深度提纯采用低温精馏。结果表明:通过烟气净化可实现SO₂脱除效率达100%,NO脱除效率达99%,同时实现纯度为99.99%的食品级液态CO₂制备。烟气净化过程中,气相反应占据主导,提高压力可缩短反应时间;当SO₂吸收塔运行压力超过0.8 MPa时,SO₂脱除效率可达100%;当NO吸收塔运行压力超过3.0 MPa时,NO排放浓度可达超低排放标准。CO₂提纯过程中,提高压力会降低液体CO₂纯度。SO₂吸收塔运行压力为1.6 MPa、NO吸收塔运行压力为3.0 MPa、CO₂提纯塔运行压力为3.8 MPa时,系统整体功耗最低,为0.37 MJ/kg。     

热解温度和反应气氛对输送床煤快速热解的影响

在连续进料量为1.2 kg·h^-1的输送床反应器中考察了热解温度和反应气氛对不连沟次烟煤快速热解的影响。N₂气氛下,随着煤热解温度升高,焦油产率先增加后减小,600℃时达到最大值10.3%;对应的半焦产率下降,气体产率以及气油比增加。高温促进了煤挥发分的释放以及挥发分在气相中的二次反应,部分产物从固相和液相产品转化为气相产品,氢气、甲烷和乙烯等气体组分的产率明显增加。700℃下,H₂气氛能够抑制挥发分二次反应的发生,起到稳定自由基和加氢的作用,显著提高焦油产率和油品品质,同时有利于甲烷的生成。CO气氛在一定程度上同时提高了轻质和重质焦油产率。CO₂和水蒸气能够促进焦油的二次反应,特别是重质焦油的裂解,具有一定的提质作用,但会导致焦油产率下降。CH₄气氛促进了重质焦油组分的生成,使得热解焦油产率提高。     

玉米秸秆循环流化床气化中试试验

玉米秸秆是农业生产过程中产生的剩余物,其热解气化是秸秆类生物质处理应用的重要选择方向。为此,采用循环流化床气化中试装置对玉米秸秆进行了气化试验,研究空气当量比ER、原料含水率对反应温度、气化燃气组分与热值、气化效率及燃气中的焦油含量等气化特性影响规律,并通过改变进料量试验得到了在不同负荷运行条件下的优化工作参数。结果表明：①随着ER的增大,循环流化床气化炉内的反应温度升高,气化燃气中的CO₂含量增加,焦油与CO含量及燃气热值降低,气化效率随ER的增大呈现先增大后减小趋势,较理想的ER为0.26,此时的气化效率达到70.2%、燃气热值为5.1MJ/m³;②原料含水率的增大降低了气化炉内的反应温度,当原料含水率在5%～15%之间逐渐增大时,燃气中的H₂含量、燃气热值及气化效率均有提升,当含水率由15%继续增大到25%过程中,燃气热值与气化效率均出现了快速下降;③根据气化炉额定进料量设计值,改变进料负荷在66%～120%范围内,调节ER在0.26～0.3时均可得到较好的运行工况,对应得到的燃气热值为4.8～5.1MJ/m³、气化效率为69%～72%。     

SIMULTANEOUS ABSORPTION OF H2S AND CO2 INTO A SOLUTION OF SODIUM CARBONATE

The simultaneous absorption of H₂S and CO₂ has been studied both experimentally and theoretically. A model has been developed which predicts the absorption rates of H₂S and CO₂ into a sodium carbonate solution. The absorption rates are calculated according to the two-film theory. In the liquid film, the finite rate of the CO₂ reaction was considered. Otherwise, in the liquid film as well as in the liquid bulk, equilibrium conditions for all reactions were assumed. Absorption experiments were performed on a packed column using a counter-flow strategy. In the experiments the influence of the initial carbonate concentration, the gas flow rate and the temperature on the removal efficiencies of H₂S and CO₂ and the selectivity of H₂S were investigated. It is desirable to absorb the H₂S but not the CO₂. The agreement between the absorption model and the experimental results from the absorber tower was satisfactory. The mass transfer coefficients were determined by fitting the experimental data to the model with respect to the H₂S and CO₂ content in the outgoing gas. The H₂S content was used to determine the gas side mass transfer coefficient and the CO₂ content was used to determine the liquid side mass transfer coefficient, The effective contact area of mass transfer was taken from published data. With a constant packing height, both the experiments and the model indicated that high carbonate concentration benefits the removal efficiency of H₂S. Higher gas flow rate also benefits the selectivity for H₂S. However, the removal efficiency will decrease. At higher temperatures the selectivity and the removal efficiency of H₂S decreased. Under the conditions investigated, the absorption of H₂S was essentially controlled by gas-side mass transfer and the absorption of CO₂ was controlled by liquid-side mass transfer     

超亲水SiO2修饰膜的构建及其油水乳液分离性能

采用硅溶胶和多巴胺作为修饰剂,通过一步反应在微孔聚丙烯膜(MPPM)表面构建了SiO₂修饰层。利用FTIR、ESEM和EDX对膜进行了表征,发现膜表面SiO₂颗粒分布非常均匀。水/油接触角及纯水通量实验结果表明,修饰膜具有超亲水性及水下超疏油性,透水能力强,水通量大[在0.1 MPa时,水通量高达(5100±500)L·m^-2·h^-1]。油水乳液分离结果表明,修饰膜能有效分离油水乳液,在0.05 MPa时,油水乳液水通量达2830 L·m^-2·h^-1,油截留率达99.8%以上,即使过膜压力增大到0.15 MPa,油截留率也能保持在99%以上,且膜表面的油污可用水清洗除去,展现出很好的应用前景。     

旋流气液两相强化吸收CO2的传质性能

为强化二氧化碳的吸收过程,采用一类旋流逆向气液多级接触的方式,以NaOH溶液为吸收剂,研究其与大跨度浓度CO₂(2.5%～15%)接触反应的传质性能。分别探讨了吸收剂浓度、吸收剂流量、烟气CO₂浓度、烟气流量及反应温度对气相总体积传质系数(K_ga)的定量影响。结果表明,在实验条件下,其K_ga可达(4.53×10^-5)～(9.22×10^-5)kmol·m^-3·s^-1·kPa^-1。与双级直流喷雾和单级旋流喷雾相比,旋流逆向气液多级接触能够有效强化大跨度浓度CO₂的吸收过程。K_ga随吸收剂浓度、流量和反应温度的增加而增加,随CO₂浓度增加呈现先增加后减小(CO₂浓度大于5%)的非线性关系,随气体流量增加先增加后趋于稳定。