3万吨/年NaA型分子筛膜乙醇脱水工业示范

在自行设计并搭建的分子筛膜脱水中试装置上对微波加热技术合成的工业级Na A型分子筛膜管进行乙醇脱水蒸汽渗透的性能研究,为Na A型分子筛膜管的工业应用提供重要的设计依据。根据中试结果,完成了江苏索普集团醋酸加氢制乙醇项目中分子筛膜蒸汽渗透脱水的工艺包设计,并建设完成了3万吨/年的分子筛膜乙醇脱水装置。该装置一次性开车成功,目前已连续运行超过1000小时,运行结果良好。     

费托合成水相副产物混合醇渗透蒸发分离工艺

对以钴基催化剂、浆态床工艺为核心的费托合成中试装置产生的水相副产物的分离提纯过程进行了研究,针对目前混合醇多塔精馏回收工艺能耗高的问题,提出了渗透蒸发与精馏耦合的分离提纯工艺。新工艺保留传统多塔精馏回收工艺中的脱水塔和粗分塔,对原工艺中C_1~C_3混合醇-水的分离提纯采用渗透蒸发技术替代传统的精馏技术。研究结果表明:NaA型沸石分子筛渗透膜是混合醇渗透蒸发脱水适宜的膜分离材料,该渗透膜的渗透通量可达2.4 kg/(m~2·h),粗分塔塔顶产品C_1~C_3混合醇-水混合物经过渗透蒸发,混合醇中含水量由17.09%降低到0.5%以下。费托合成水相副产物混合醇经渗透蒸发-精馏耦合工艺可得到含水量低于0.5%的醇产品,与传统多塔精馏回收工艺相比,渗透蒸发-精馏耦合工艺可节能24%,节能效果显著。     

PEA-NaA /α-Al2OPEA-NaA /α-Al2O3复合支撑分子筛膜的微波水热合成

采用微波水热合成法在聚醚酰亚胺(PEI)-NaA分子筛/α-Al2O3复合载体表面合成了具有高选择性的致密NaA型分子筛膜,重点考察了微波辐射时间对成膜的影响。采用X射线衍射图谱(XRD)和扫描电子显微镜(SEM)对NaA型分子筛膜进行了表征。XRD结果表明,复合载体表面生成的膜中只有NaA分子筛的晶相;SEM结果表明,复合载体基膜表面覆盖了一层致密连续的NaA型分子筛膜。合成的NaA型分子筛膜在不同质量分数乙醇中的渗透汽化性能结果表明,渗透通量随乙醇质量分数增大而减小,分离因子则反之,当乙醇质量分数为95%时,渗透通量仅0.05 kg/(m2.h),而分离因子高达13 000。     

PEI-NaA/α-Al_2O_3复合支撑分子筛膜的微波水热合成

采用微波水热合成法在聚醚酰亚胺(PEI)-NaA分子筛/α-Al2O3复合载体表面合成了具有高选择性的致密NaA型分子筛膜,重点考察了微波辐射时间对成膜的影响。采用X射线衍射图谱(XRD)和扫描电子显微镜(SEM)对NaA型分子筛膜进行了表征。XRD结果表明,复合载体表面生成的膜中只有NaA分子筛的晶相;SEM结果表明,复合载体基膜表面覆盖了一层致密连续的NaA型分子筛膜。合成的NaA型分子筛膜在不同质量分数乙醇中的渗透汽化性能结果表明,渗透通量随乙醇质量分数增大而减小,分离因子则反之,当乙醇质量分数为95%时,渗透通量仅0.05 kg/(m2.h),而分离因子高达13 000。     

分子筛膜-精馏耦合用于费托合成水相副产物混合醇回收的工艺流程模拟

费托合成油水相副产物混合醇的回收多采用萃取精馏的分离方法,此方法需要配置7个精馏塔和5路循环回路。通过分析发现,流程冗长的关键因素在于混合醇中除甲醇外各个组分均与水产生共沸,而分子筛膜渗透汽化技术不受汽液平衡的限制,因此可以利用分子筛膜渗透汽化技术将混合醇中的水分先脱除,然后再利用精馏技术对混合醇各组分进行分离。本文完成了精馏-膜分离耦合工艺分离混合醇的全流程模拟,并与传统的萃取精馏工艺流程进行对比。精馏-膜分离耦合工艺大幅简化了原有萃取精馏工艺流程,整体能耗降低30%。并根据此流程在陕西延长石油（集团）有限公司建成了国内第一套膜分离-精馏耦合工艺的1000t/a低碳混合醇回收和分离的工业示范装置。     

T型分子筛膜的制备及其对含酸乙腈-水的分离性能

石化医药行业会产生大量乙腈废液,通过无机分子筛膜分离技术进行回收可以创造可观的经济价值。然而,乙腈废液水含量较高,并且具有一定的酸性,目前应用比较广泛的NaA型分子筛膜不能在该体系下长期使用。使用自制的平均粒径为600 nm的T型分子筛作为晶种,采用真空涂敷法将晶种负载在α-Al₂O₃载体管表面,在150 ℃下水热晶化16 h制备出T型分子筛膜,并对其做膜性能评价实验。结果表明,自制的T型分子筛膜在进料流量为3.5 L/h、温度为100 ℃条件下对含有1%（质量分数）乙酸和10%水（质量分数）的乙腈混合溶液进行膜分离脱水实验,渗透通量为2.51 kg/（m ²·h）;在120 h长时间运行过程中,分离系数保持在2 250以上,T型分子筛膜性能基本保持不变。     

PEA-NaA /α-Al2OPEA-NaA /α-Al2O3复合支撑分子筛膜的微波水热合成

采用微波水热合成法在聚醚酰亚胺(PEA)-NaA分子筛/α-Al2O3复合载体表面合成了具有高选择性的致密NaA 型分子筛膜,重点考察了微波辐射时间对成膜的影响。采用X射线衍射图谱（XRD）和扫描电子显微镜（SEM）对NaA型分子筛膜进行了表征。XRD 结果表明,复合载体表面生成的膜中只有NaA 分子筛的晶相;SEM 结果表明,复合载体基膜表面覆盖了一层致密连续的NaA型分子筛膜。合成NaA型分子筛膜的渗透汽化性能和不同乙醇水溶液浓度对渗透汽化性能的影响的结果表明,渗透通量随乙醇溶液的浓度增大而减小,分离因子则反之,当乙醇溶液浓度为95%时,渗透通量仅0.05 kg/ (m2?h),而分离因子高达13000。     

NaA分子筛膜的合成及在渗透蒸发中的应用

介绍了近几年来国内外在NaA分子筛膜的合成及应用方面的研究进展,重点介绍了NaA分子筛膜渗透蒸发的机理和在有机物脱水中的应用.提供了分子筛膜渗透蒸发与蒸馏过程在有机物脱水中的经济比较,发现渗透蒸发过程能降低一半成本.最后对NaA分子筛膜的制备和渗透蒸发进行了展望.     

透水型分子筛膜在生物燃料乙醇生产中应用的经济性分析

针对生物燃料乙醇生产过程,提出精馏-分子筛膜耦合工艺(膜工艺)进行脱水,并与精馏-分子筛变压吸附工艺进行了比较,结果表明,采用膜工艺可节约蒸汽0. 3 t/t。以年产20万t生物燃料乙醇项目为例,分析了膜通量、膜单价和蒸汽价格对膜工艺综合运行成本的影响,为膜工艺在生物燃料乙醇生产过程中的应用提供了指导。     

酒精脱水渗透汽化中试过程设计与运行

介绍了酒精脱水渗透汽化膜中试装置的设计与运行，并对操作条件进行了优化。结果表明，与传统的精馏过程相比，渗透汽化膜过程用于酒精脱水具有更好的经济效益。     

管式支撑体内表面NaA分子筛膜的合成与表征

采用转动合成方式通过二次生长法在管式α-Al₂O₃支撑体内表面合成了NaA分子筛膜,采用X射线衍射仪（XRD）、场发射扫描式电子显微镜（FE-SEM）和渗透汽化分离技术对所合成的膜进行了系统表征。考察了合成釜转速对分子筛膜合成的影响,结果表明合成釜转速的提高有利于分子筛膜合成。在转速为4 r·min^-1时所合成NaA分子筛膜分离因子高达2370,渗透通量1.86 kg·h^-1·m^-2左右（乙醇/相似文献   

Maxwell-Stefan理论模拟NaA沸石膜分离一氯甲烷中微量水的渗透特性

通过热浸渍晶种法制备了高质量的NaA沸石膜,并将其应用于蒸汽渗透脱除一氯甲烷中的微量水. 实验结果表明,NaA膜对该体系显示了优异的分离性能,水对一氯甲烷的分离系数高达74831,产品中的水含量从0.2582%(w)降低到0.005%(w). 将基于Maxwell-Stenfan理论和Langmuir理想吸附理论推导的吸附-扩散模型用于模拟水渗透流速与渗透侧真空度和进料温度的关系,预测趋势与实验值吻合很好,且拟合得到的参数与文献报道较接近,表明水蒸汽在NaA沸石膜中的传递为表面扩散机制,水蒸汽的吸附对渗透速率的贡献很大. 水蒸汽的吸附热为-34.15 kJ/mol.     

Enhancement of NaA zeolite membrane properties through organic cation addition

Thin NaA zeolite membranes, with uniform and small crystals, were prepared on the tubular -Al₂O₃ support by adding a small amount of tetramethylammonium hydroxide (TMAOH) in the clear synthesis solution. The as-synthesized NaA zeolite membranes were characterized by XRD and SEM. The permeation properties of the membranes were evaluated by pervaporation and gas permeation. The effects of TMAOH amount on membrane formation and permeation properties were investigated. By addition of suitable amount of TMAOH in the clear synthesis solution, the crystals size of NaA zeolite could be remarkably reduced from about 10 μm to 3–4 μm, and the membrane thickness correspondingly reduced from about 16 μm to 5 μm. The thinner membrane prepared by adding TMAOH in the clear synthesis solution, with uniform and small crystal, displayed higher perm-selective properties than that without adding TMAOH. For the as-synthesized NaA zeolite membrane prepared with adding suitable amount of TMAOH (x = 1), the separation factor (water/isopropanol) was 4700 and the flux was 1.67 kg/(m² h), which were higher than that without adding TMAOH of 339 and 1.08 kg/(m² h), respectively. The ideal separation factor of H₂/N₂ was 6.60, higher than that without adding TMAOH of 3.41.     

Scale-up of NaA zeolite membranes onα-Al2O3 hollow fibers by a secondary growth method with vacuum seeding

NaA zeolite membranes were prepared by secondary growth method on the outer surface ofα-Al2O3 hollow fiber supports. Vacuum seeding method was used for planting zeolite seeds on the support surfaces. Hydrother-mal crystallization was then carried out in a synthesis solution with molar ratio of Al2O3:SiO2:Na2O:H2O=1:2:2:120 at 100 °C for 4 h. Effects of seeding conditions on preparation of hollow fiber NaA zeolite membranes were extensively investigated. Moreover, hollow fiber membrane modules with packing membrane areas of ca. 0.1 and 0.2 m2 were fabricated to separate ethanol/water mixture. It is found that the thickness of seed layer is obviously affected by seed suspension concentration, coating time and vacuum degree. Close-packing seed layer is required to obtain high-quality membranes. The optimized seeding conditions (seed suspension mass concentration of 0.5%–0.7%, coating time of 5 s and vacuum degree of 10 kPa) lead to dense NaA zeolite layer with a thickness of 6–8μm. Typically, an as-synthesized hollow fiber NaA zeolite membrane exhibits good pervaporation performance with a permeation flux of 7.02 kg·m?2·h?1 and separation factor N 10000 for sepa-ration of 90%(by mass) ethanol/water mixture at 75 °C. High reproducibility has been achieved for batch-scale production of hollow fiber NaA zeolite membranes by the hydrothermal synthesis approach.     

含甲基纤维素的NaA沸石膜的制备和表征

NaA沸石膜具有规则的孔道结构,利于分子传输,在有机物脱水领域有一定的应用。为使沸石膜生长更连续均匀,提高渗透汽化性能,本文以甲基纤维素作为空间限制剂加入合成液,探究碱度、晶化温度以及晶化时间对膜的影响,按最优条件制备合成液,并依据质量比m(MC)∶m(H₂O)=1∶100添加甲基纤维素,制备NaA沸石膜。表征方法采用XRD、SEM和渗透汽化3种方式,结果表明添加甲基纤维素的沸石膜表面结构完整,生长致密且性能优良,在75℃下对0.6mol/L的NaCl水溶液做渗透汽化测试时,通量达8.33kg/(m²·h),盐离子截留率为99.95%。在0.6mol/L的NaCl的水溶液中测试72h,结果表明添加甲基纤维素的NaA沸石膜时间依存性更好,通量保持在8.30kg/(m²·h)左右,离子截留率稳定在99.90%。渗透汽化分离ω(C₂H₆O)=90%乙醇的水溶液,随着温度从60℃升高到75℃,沸石膜的通量由1.55kg/(m²·h)升高到2.56kg/(m²·h),渗透侧水含量保持在99.90%左右。     

分子筛膜晶种涂敷机的研制

研制了基于800~1000 mm长工业规格不锈钢或陶瓷管状支撑体的晶种涂敷设备。采用先喷涂后摩擦工艺,结合自动化控制技术,实现了分子筛膜大规模制备中晶种的快速涂敷。详细介绍了涂敷机工作原理和主要结构,分析研究了影响设备涂敷性能的主要因素。对不锈钢支撑体进行晶种涂敷制备NaA透水膜实验,在温度为75℃、原料液中乙醇质量分数为90%的条件下,膜渗透通量为4.2~5.8 kg·m^-2·h^-1;渗透液中水质量分数为99.2%~99.8%;生产率为30根/小时,成品率大于98%。     

Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1: Dehydration of solvents

The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m² h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m² h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation.     

On a rapid method to characterize intercrystalline defects in zeolite membranes using pervaporation data

This work presents a mass-balance-based model devoted to the characterization of intercrystalline defects active to permeation in film-like zeolite membranes using pervaporation data. Relevant structural information concerning such domains can be obtained from the slope and intercept of the line that describes the increase of the flux pervaporated through a membrane with the absolute pressure in the liquid feed. Capillary forces appear to govern mass transfer within intercrystalline pores. The suitability of the model is assessed by using a collection of zeolite NaA membranes prepared on our premises for the separation of ethanol/water mixtures. The results show that, although a membrane displays high selectivity, a reduced number of defects in the zeolite layers cannot be ruled out. The model offers the advantage of enabling the characterization of large defects in pervaporation membranes at experimental conditions similar to those in which they are likely to be used.     

Pervaporation dehydration of ethylene glycol by NaA zeolite membranes

Home-made NaA zeolite membranes were used for pervaporation dehydration of ethylene glycol (EG)/water mixtures. Hydrothermal stability of the membranes in pervaporation was investigated for industrial application purpose. The membranes exhibited good stability for water content of less than 20 wt.% at 100 °C. The reduction of operating temperature was effective to improve membrane stability for operating at high feed water content (e.g. 30 wt.%). The influence of feed water content and operating temperature on dehydration of EG was extensively investigated. A permeation flux of 4.03 kg m⁻² h⁻¹ with separation factor of >5000 was achieved at 120 °C for the separation of the solution with 20 wt.% water content. A pilot-scale pervaporation facility with membrane area of 3 m² was built up for dehydration of EG with the water content of 20 wt.%, which showed technical feasibility for industrial application.