CO_2在13x分子筛上的吸附分离——总传质系数及数学模型

以CO_2在分子筛和活性炭上的吸附平衡理论为基础,用微分床层测定CO_2在13x分子筛上的吸附与解吸总传质系数K_0,对描述吸附柱操作的偏微分方程组,分别用Laplace变换和有限差分法直接求解,计算所得透过曲线与实验结果相近似。     

分子筛脱除偏二甲肼微量水静态吸附研究

分别测定了偏二甲肼中微量水在3A、4A、5A分子筛上的吸附等温线,并用Langmuir方程和Freundlich方程进行拟合。同时考察了吸附过程对偏二甲肼、偏腙、二甲胺等组分的影响。结果显示,水在3种分子筛上的吸附实验数据基本都适用2个吸附方程。相对而言,在3A、4A上的吸附等温线用Langmuir方程拟合最为吻合,在5A分子筛上的吸附等温线则显示Freundlich方程更适用些。吸附过程对偏二甲肼、偏腙、二甲胺等组分无影响。     

水汽共存下NH3在13X分子筛上吸附等温线的测定研究

关于纯 NH_3在分子筛上的吸附等温线已有报道。但水汽共存下,NH_3在分子筛上的吸附等温线,尚未见报道。本文采用连续流动装置,进行了水汽共存下,NH_3在13X 分子筛上吸附性能的研究。测定了不同浓度氨水,于不同温度、不同分压下,在13X分子筛上的吸附量,得到各种条件下 NH_3在13X 分子筛上的吸附等温线,对 NH_3吸附量与吸附时间的关系,亦作了考察。     

吸附热预测吸附等温线

实验测定了N2 在沸石分子筛、C2 H6 在活性炭、CO2 在硅胶上的吸附等温线 ,研究用Clausius Clapeyron方程求得等量吸附热、再利用所得的吸附热预测其它温度的吸附等温线数据的方法。将吸附热预测的等温线与实验值及插值法内插得到的吸附等温线数据进行了比较 ,结果表明吸附热预测值与实验值吻合较好。此外还对文献数据利用等量吸附热预测较高压力 ( 65 0kPa)下的等温线 ,均与文献中的实验值一致。为吸附工业操作需要不同温度下的等温线数据和吸附过程的模拟与设计提供了简便、准确的计算方法     

CH4/CO2混合组分在13X分子筛上的吸附平衡及分离性能

采用高精度智能重量分析仪IGA-100对13X分子筛进行CH4、CO2的吸附分离实验。于298、310、326 K温度下,分别测定了CH4、CO2纯组分及混合组分的吸附等温线。纯组分吸附等温线用DL(Double-Langmuir)模型拟合,并通过DL-IAST(Ideal Adsorbed Solution Theory,IAST)模型与实验测定值进行比较。利用该模型计算出不同温度下混合气中各组分的吸附量,得到了CO2的吸附选择性。结果表明,DL-IAST模型可以准确地描述CH4、CO2在13X分子筛上的吸附行为。在298 K时,随着压力的增加,CO2的吸附选择性增加,最后稳定在80左右;当温度一定时,CO2吸附选择性随着混合物中CO2浓度增加而减小。     

正戊烷和正己烷在5A分子筛上的液相吸附性能研究

测定了373~453K温度条件下正戊烷和正己烷在5A分子筛上的液相吸附平衡数据,用Langmuir方程和Freundlich方程对实验吸附等温线数据进行了拟合计算。结果表明,在453K温度下,正戊烷和正己烷在5A分子筛上仍可以达到7%左右的吸附容量,其吸附等温线符合Langmuir吸附等温类型,Langmuir吸附方程能够很好的拟合实验结果。Clapeyron-Clausius方程计算得到的正戊烷和正己烷在5A分子筛上吸附热、吸附熵等热力学数据表明,正戊烷、正己烷均易吸附于5A分子筛上,其吸附热为-24kJ/mol左右。     

高比表面积活性炭吸附存储天然气性能研究

天然气中少量乙烷和丙烷的存在会直接影响活性炭对天然气的吸附存储容量。为此,体积法测定了高比表面积活性炭对甲烷、乙烷和丙烷的吸附等温线,吸附温度分别为283,293,303和313K;采用Langmuir-Freundlich(LF)方程拟合吸附等温线,得到各气体的方程参数,进而采用LRC关联式预测多组分吸附平衡数据,并计算活性炭对模拟天然气的存储能力。结果表明:活性炭对3种气体的吸附等温线都属于I型等温线,采用L-F方程可以很好地描述各气体的吸附等温线;高比表面积活性炭对模拟天然气的存储量随吸附温度的升高而显著降低,在吸附存储压力为3.5 MPa,吸附温度从283 K上升到313 K,相应的存储量(体积比)由139降低为103;与纯甲烷的吸附存储相比,模拟天然气的吸附储量(体积比)提高约20。     

表面改性活性炭对CO_2的吸附性能

研究了用 H2 O2 ,HNO3加醋酸铜溶液进行表面改性后的活性炭对 CO2 的吸附性能 ,分析了改性前后活性炭的表面化学性质 ,测定了 2 73K下的吸附等温线 ,用 D- A方程对吸附等温线进行了很好的拟合 ,探讨了表面改性对活性炭表面化学性质的影响及其表面化学性质与吸附性能之间的关系。     

改进13X 型分子筛合成条件提高吸附二氧化碳的能力

本文根据国内空分装置的用户反映,提出目前吸附净化所用吸附剂存在的问题。分析了孔结构对吸附质扩散速率的影响。对13X分子筛吸附CO_2的性能开展了试验研究,得到了13X分子筛的合成条件(硅铝比与碱度)与CO_2吸附量的关系,试验结果硅铝比的最佳值为3.5～3.7;碱度的推荐值为0.9～1.0。     

改性分子筛吸附2,2-二甲基丁烷的运行参数研究

M-13X分子筛是13X分子筛经过改性后得到的,具有更好的吸附效果,基于静态吸附试验装置,通过单因素实验得到M-13X吸附2,2-二甲基丁烷时的最佳运行参数为70℃、60%填充率、0.2 MPa、吸附30 min;通过动态吸附,得到了M-13X分子筛的吸附穿透曲线和饱和吸附量;研究通过改变环境温度,得到了M-13X分子筛的吸附等温线。这些研究结果为吸附法处理有机废气的工艺设计提供了参考。     

13X微孔沸石和MCM-41介孔材料的合成及用于处理含Cd2+废水

以天津蓟县钾长石矿粉为主要原料,经选矿、煅烧、水热处理等工艺成功合成了13X微孔沸石. 以气相氧化硅、氢氧化钠、十六烷基三甲基溴化铵等为主要原料,在水热条件下合成了MCM-41有序介孔材料. 采用XRD和N2吸附-脱附等手段对合成的13X沸石和MCM-41介孔材料的物相、比表面积、孔径、孔体积等进行了分析对比. 在此基础上,对13X沸石和MCM-41介孔材料处理含Cd2+废水的效果和机理进行了对比研究,确定了不同分子筛用量、不同初始pH值、不同混合时间下13X沸石和MCM-41介孔分子筛对水中Cd2+的吸附率和吸附量. 研究发现,尽管MCM-41的比表面积和孔径远大于13X沸石,但其对水中Cd2+的处理效果却低于13X沸石,这与13X沸石和MCM-41的孔道结构类型、化学组成、表面荷电性质等有关.     

Adsorption of CO2 on Zeolite 13X and Activated Carbon with Higher Surface Area

In this work, adsorption isotherms and adsorption kinetics of CO₂ on zeolite 13X and activated carbon with high surface area (AC-h) were studied. The adsorption isotherms and kinetic curves of CO₂ on the adsorbents were separately measured at 328 K, 318 K, 308 K, and 298 K and with a pressure range of 0–30 bar by means of the gravimetric adsorption method. The mass transfer constants and adsorption activation energy E_a of CO₂ on the adsorbents were estimated separately. Results showed that at very low pressure the amounts adsorbed of CO₂ on the zeolite 13X was higher than that on the AC-h, while at higher pressure, the amounts adsorbed of CO₂ on the AC-h was higher than that on the zeolite 13X since the AC-h has a larger surface area and a larger total pore volume compared to the zeolite 13X. The adsorption kinetics of CO₂ can be well described by the linear driving force (LDF) model. With the increase of temperature, the mass transfer constants of CO₂ adsorption on both samples increased. The adsorption activation energy E_a for CO₂ on the two adsorbents decreased with the increase of pressure. Furthermore, at low pressure the E_a for CO₂ adsorption on the zeolite 13X was slightly lower than that on the AC-h, while at higher pressure the E_a for CO₂ adsorption on the zeolite 13X was higher than that on the AC-h.     

沼气变压吸附剂吸附性能比较

研究了工程上常用的3种吸附剂CO2吸附剂硅胶、13X分子筛和碳分子筛在高压(0.1~1 MPa)下对CO2和CH4的吸附容量、稳定性和选择性,以确定其在沼气变压吸附分离中应用的可行性. 结果表明,硅胶的吸附稳定性非常好,0.1 MPa时吸附选择性系数为8~10,能有效分离CH4?CO2;13X分子筛对CH4和CO2吸附容量最高、吸附选择性最好,重复使用5次CO2的吸附容量略有下降;以CH4的损失率作为评价标准时,13X分子筛吸附CH4的损失率最低. 降压不能使被碳分子筛吸附的CH4完全解吸,吸附位不能充分释放,不适用于CH4与CO2的分离.     

低湿CO2/H2O混合气体吸附特性实验

CO₂捕集、封存及利用是实现“双碳”目标的重要途径,为将碳捕集后的低湿CO₂/H₂O进行CO₂提纯和资源化利用,采用动态吸附实验研究了不同温度（303K、313K）、H₂O含量（0.7%~3.0%）的CO₂/H₂O在活性炭、活性氧化铝、分子筛3A和13X四种吸附剂上的动态吸附穿透曲线、吸附床温度分布、吸附量,分析了CO₂/H₂O分离系数和吸附热。结果表明,在CO₂/H₂O动态吸附过程中,吸附床温度与各组分浓度随时间变化趋势相同。H₂O饱和时间随进气温度升高而缩短;H₂O含量增加,抑制CO₂吸附;活性炭和氧化铝中H₂O的饱和时间随H₂O含量增加而增长,但分子筛3A和13X饱和时间缩短。H₂O吸附量随H₂O含量增加而增加,吸附热随吸附量增加而减小,CO₂则相反。分子筛3A对CO₂吸附量最小且CO₂/H₂O分离系数最大。H₂O含量小于1%时,CO₂吸附量最大的分子筛13X分离系数大于活性氧化铝,分子筛3A和13X适合分离低湿CO₂/H₂O。     

Competitive adsorption of N2O and CO on CuZSM-5, FeZSM-5, CoZSM-5 and bimetallic forms of ZSM-5 zeolite

The behavior of copper-, iron- and cobalt-exchanged ZSM-5 (Si/Al = 20) and bimetallic forms of the same zeolite was investigated with reference to the adsorption of N₂O and CO at 303 K. The interactions of both gases with investigated zeolites have been studied using microcalorimetry and infrared spectroscopy. The values of differential heats of adsorption and the amounts of adsorbed gases were determined. Both gases react with the charge-balancing cations as active sites for adsorption. CuZSM-5 shows significantly better performances than FeZSM-5 and CoZSM-5, toward both gases; additionally, nitrous oxide can be chemisorbed on CuZSM-5. Adsorption capabilities of FeZSM-5 and CoZSM-5 are increased with the addition of copper ions. The heats of CO interaction with copper-containing samples have been found to be higher then the heats of N₂O interaction, while for FeZSM-5 and CoZSM-5 samples similar heats were detected for both gases. In the case of CuZSM-5, as a result of competitive adsorption between previously adsorbed N₂O and incoming CO from the gas phase, a surface reaction is found.     

Carbon monoxide electrooxidation on Pt and PtRu modified zeolite X

Zeolite NaX was modified by Pt and Pt/Ru nanodispersed metallic clusters. This modification was achieved by zeolite impregnation with acetylacetonate salt/acetone solution, followed by acetone evaporation and thermal decomposition of organometallic complex. Samples characterization was performed by X-ray diffraction analysis, nitrogen adsorption?Cdesorption measurements and Raman spectroscopy. The incorporation of metal into zeolite cavities induced the amorphisation of the zeolite framework on the local level. The mixture of modified zeolite and 10?wt% of carbon black, in a form of thin layer, was pasted to a glassy carbon surface by Nafion. Electrocatalytic properties of metal-modified zeolites were tested in CO electrooxidation reaction. The mutual influence between Pt and Ru atoms enhanced electroactivity of Pt/Ru-modified zeolite toward carbon monoxide electrooxidation. The behavior of untreated 13X zeolite was investigated under the same condition in order to asses the influence of the support. Gradual deactivation of 13X electrode occurred.     

分子筛负载CuCl制备CO吸附剂的研究

利用机械混合法将CuCl直接负载于分子筛13X、NaY和NH4X表面上制备高效CO吸附剂.实验结果表明,样品在320℃真空活化后,13X和NaY载体制备的吸附剂表现出较好的CO吸附性,CuCl的最佳分散质量分数分别为0.40 g CuCl/g 13X及0.45 g CuCl/g NaY,CO吸附量分别高达76 mL/g及84 mL/g,脱附质量分数分别为40％和60％,且CO/CO2分离比分别可达1.4和1.9.XRD表明,吸附剂经真空活化后CuCl晶相消失,表明CuCl在载体表面均匀分散,并且可能部分阳离子发生交换,进而提高了CO的吸附量.     

C2H4/CO2混合体系在活性炭上吸附的实验与模型

通过重量法测定吸附等温线,研究了C2H4/CO2混合体系在活性炭上的吸附分离。采用高精度的智能重量分析仪,测定了C2H4和CO2纯组分以及混合组分在活性炭上的吸附等温线,将测量值与DL-IAST模型计算值进行比较,并计算出了C2H4的吸附选择性。结果表明,DL-IAST模型可以准确地描述C2H4和CO2纯组分在活性炭上的吸附;不同摩尔分数下,C2H4/CO2混合体系的DL-IAST模型计算值与实验值吻合得较好,C2H4摩尔分数越大,模型的相对偏差就越小;随着压力的增加,C2H4的吸附选择性减小,C2H4摩尔分数越大,C2H4的吸附选择性也减小。DL-IAST可以准确地描述C2H4/CO2混合体系的吸附等温线以及推算出C2H4的吸附选择性。     

Ethylene recovery from low grade gas stream by adsorption on zeolites and controlled desorption

Carbon dioxide was partially removed from a nitrogen stream, which also contained some ethylene, by adsorption on a 4A (Na-A) zeolite. The treated nitrogen stream was then passed over a 13X (Na-X) zeolite bed upon which ethylene and any remaining carbon dioxide were adsorbed. Ethylene was recovered by desorption at 68 Pa pressure into a slow flow of nitrogen as stripping gas. The ethylene concentration in the extracted gas was extremely dependent on the nitrogen flow-rate, whereas the concentration of carbon dioxide remained practically constant. Thus, it was possible to obtain a gas mixture greatly enriched in ethylene with a reasonably low content of carbon dioxide.     

CuCI负载型吸附剂吸附CO的研究

利用Cu＋能与C0结合形成羰基络合物,将Cu＋盐负载到分子筛表面,经过热处理能达到自发单层分散状态,有效提高了C0的吸附量。利用直接混合法将CuCl负载于13X分子筛表面上制备高效的CO专用吸附剂。实验结果表明,将样品置于管式炉内,流动N2氛围保护下,在350℃焙烧4h后,CuCl／13X质量比0．4：1．0吸附剂表现出较好的吸附性能,C0吸附量可迭45mL／g,对工业分离混合气体有重要的意义。XRD也显示,不同质量比的CuCl／13X样品,在N2氛围中350℃焙烧4h后,CuCl晶相峰从有变无,说明CuCl均匀分散于栽体表面,提供了更多的与C0络合的铜离子活性中心,进而提高了吸附剂对C0的吸附量。