乙醇发酵与渗透汽化在硅橡胶膜生物反应器中的耦合强化

用硅橡胶膜生物反应器(SMBR)实验研究了发酵-渗透汽化的耦合性能。发酵微生物采用酿酒活性干酵母,所用的碳源为工业级葡萄糖。间歇发酵过程由于产物抑制作用在乙醇浓度达到90g稬-1时就趋于停滞,而经耦合渗透汽化膜分离后,发酵罐内的乙醇浓度迅速降低并维持在40g稬-1,且发酵在此浓度下可以连续稳定地进行。 在SMBR运行达到稳态后,乙醇的体积产率为1.5gL-1h-1。SMBR中所用的聚二甲基硅氧烷(PDMS)复合膜由实验室自行制备,它能稳定分离含有酵母细胞的发酵液。当发酵液中乙醇浓度为92.7~49.5g稬-1时,PDMS复合膜的总通量为1490~1164g穖-2h-1,分离因子为6.9~7.8,与分离相同进料浓度的清洁模型溶液相比分别平均高出31%和14%。乙醇发酵和渗透汽化在硅橡胶膜生物反应器中能够相互耦合并得到强化。     

硅橡胶膜生物反应器中乙醇发酵与渗透汽化的耦合

用硅橡胶膜生物反应器(SMBR)实验研究连续发酵-渗透汽化的耦合性能。发酵微生物采用酿酒干酵母,所用碳源为工业级葡萄糖。发酵过程由于产物抑制作用,在乙醇质量浓度达到73 g/L时趋于停滞,而耦合渗透汽化膜后,发酵罐内的乙醇质量浓度降低并维持在40 g/L,使发酵可以连续稳定地进行。在SMBR运行达到稳态后,乙醇的体积产率为4.02 g/(L.h)。发酵液中乙醇质量浓度维持在20~63 g/L,聚二甲基硅氧烷(PDMS)膜的总渗透通量为1 220~800 g/(m2.h),分离因子为5~9.2。与传统发酵和分离相同进料质量分数的乙醇溶液相比,乙醇发酵和渗透汽化在硅橡胶膜生物反应器中能相互耦合并得到强化。与较小规模耦合系统(发酵体积1 L和2 L)比较,性能稳定良好。     

发酵-渗透汽化连续耦合合成ABE的动力学

采用PDMS膜生物反应器和丙酮丁醇梭菌进行了生产ABE的封闭循环连续发酵实验,研究了发酵和渗透汽化分离连续耦合条件下的发酵动力学行为。发酵-分离连续耦合实验运行持续时间长达192 h。运行过程中,细胞质量浓度维持在0.84～4.00 g/L,发酵液中ABE的总质量浓度为5.14～17.54 g/L,葡萄糖质量浓度大约为16.08～35.15 g/L,总体积产率为0.36 g/(L.h)。结果表明,膜生物反应器系统运行稳定,发酵-渗透汽化分离连续耦合生产ABE的操作模式具有可行性和优越性。     

发酵-渗透汽化连续耦合生产ABE的动力学研究

采用PDMS膜生物反应器和丙酮丁醇梭菌进行了生产ABE的封闭循环连续发酵实验,研究了发酵和渗透汽化分离连续耦合条件下的发酵动力学行为。发酵-分离连续耦合实验运行持续时间长达 192 h。运行过程中,细胞浓度维持在 0.84~4.00 g/L,发酵液中ABE的总浓度为5.14~17.54 g/L,葡萄糖浓度大约为16.08~35.15 g/L,总体积产率为0.36 g/(L?h)。实验结果表明,膜生物反应器系统运行稳定,发酵-渗透汽化分离连续耦合生产ABE的操作模式具有可行性和优越性。     

硅橡胶膜在渗透汽化分离中的应用及研究进展

综述了硅橡胶膜在渗透汽化分离(有机废水处理、生物发酵分离)中的应用及其制备技术(无机物填充改性、共缩聚或引入侧链基团改性)的最新研究进展.     

操作条件对渗透汽化法分离乙醇/水的影响

生物发酵产生燃料醇类过程中,由于发酵液产物复杂,产物抑制作用十分严重,极大地降低了发酵效率。将渗透汽化引入发酵过程中,采用透醇膜不断地移出发酵产物将十分有利于发酵过程的进行。实验采用聚二甲基硅氧烷(PDMS)/聚偏氟乙烯(PVDF)复合膜,将其应用于模拟醇类发酵液体系的分离。将操作温度、进料液浓度、膜下游侧压力等作为对复合膜渗透汽化性能的影响条件。实验结果表明,随着进料液温度的升高,通量随之升高,分离因子上升到一定值后下降。当温度为59.85℃时,分离因子达到最大,为9.37,通量为3.26kg·m~(-2)·h~(-1)。膜下游侧压力越小,通量越大,分离因子越高;进料液浓度越高,总通量越高,分离因子降低。     

渗透汽化分离精油中挥发性芳香化合物的研究进展

精油及其挥发性组分在化妆品、食品和药品工业、农业及食品保鲜等领域有着广泛的应用潜力。目前挥发性精油的分离主要采用的是分段蒸馏技术,该技术存在成本高、能耗大且容易造成精油组分破坏等缺陷,因此其应用受到了极大的限制。渗透汽化（pervaporation,PV）是一种用于液体混合物分离的新型膜分离技术,具有高效节能、环境友好和容易操作等优点,特别是能够实现热敏性物质的高效单级分离,因此在挥发性精油的分离和挥发性芳香化合物组分精制等方面具有巨大的应用潜力。本文系统总结了渗透汽化技术在挥发性精油分离领域的最新进展,综述了用于分离挥发性精油的渗透汽化膜材料、分离工艺及其应用现状,并对渗透汽化用于大规模分离挥发性精油过程中面临的挑战进行了讨论。     

膜生物反应器 CCCF 过程中酵母细胞生长特性研究

渗透汽化膜生物反应器CCCF过程乙醇发酵中酵母细胞的生长表现出五个不同的阶段,即：快速生长期、乙醇抑制期、二次生长期、平衡期和衰亡期。采用摇瓶实验对发酵副产物（主要为有机酸和甘油）的抑制行为进行检测,结果表明随着副产物浓度的增加,抑制作用越来越强,细胞生长表现出较长的迟滞期和较低的细胞浓度。当副产物浓度达到膜生物反应器中发酵后期的浓度时,细胞的比生长速率和得率仅分别为0．061和0．024。     

PDMS膜在ABE连续发酵中的渗透汽化性能研究

构建了膜生物反应器封闭循环ABE连续发酵系统,研究了系统中PDMS膜的渗透汽化性能.实验共进行2轮,第一轮进行274 h,采用发酵-渗透汽化间歇耦合的方式;第二轮进行312 h,前196 h采用发酵-渗透汽化连续耦合,之后实行间歇耦合.间歇耦合操作模式下,2轮的丁醇分离因子分别为11.00和12.94,总通量分别为711.07和579.98 g/(m2·h);连续耦合操作模式下,第二轮丁醇分离因子为5.54,总通量为555.80g/(m2·h).实验中膜性能稳定,分离性能良好,未出现膜堵塞和膜破损现象.     

模拟的发酵液组分对聚二甲基硅氧烷/陶瓷复合膜渗透汽化性能的影响

对所制备的聚二甲基硅氧烷（PDMS）/陶瓷复合膜进行了渗透汽化性能表征。通过在乙醇-水混合体系中添加不同的模拟发酵液组分;如葡萄糖（多羟基醛）、甘油（多元醇）、丁二酸（有机酸）、KCl（无机盐）;考察了各组分对复合膜渗透汽化性能的影响。研究发现：在333 K下;在乙醇浓度为65 g·L-1的混合物中添加不同浓度的第三组分;有机添加物对膜的渗透汽化性能没有明显影响;而无机盐的加入使膜的分离因子稍有提高。所制备的PDMS/陶瓷复合膜;在上述渗透汽化过程中表现出良好的稳定性和对乙醇的优先选择性;渗透通量和分离因子（醇/水）分别在4.5～4.7 kg·m^-2·h^-1、8.3～10.3之间。     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry     

硅橡胶复合膜用于新型白酒风味成分渗透汽化分离

用自制硅橡胶PDMS平板复合膜,分别在30、35、40℃和1325Pa膜下侧压力的条件下,渗透蒸发分离50°新型白酒中的风味物质。实验结果表明,PDMS复合膜对新型白酒风味物质具有良好的选择分离性能:5种酯类(乳酸乙酯除外)和乙缩醛的分离脱除率达100%,对高级醇也有良好的分离表现,乙醛的脱除率也超过87%。将分离后的酒液进行重组,得到较原酒品质更高的新酒,其感官评价大大好于原酒。膜在高浓度乙醇中能保持良好的稳定性,30、35和40℃时,对新型白酒的平均总渗透通量分别可达2297g/(m2·h)、2753g/(m2·h)和3539g/(m2·h),平均分离因子(均按乙醇-水体系计算)分别为5 22、5 22和5 32。     

Processing of ethanol fermentation broths by Candida krusei to separate bioethanol by pervaporation using silicone rubber‐coated silicalite membranes

BACKGROUND: Pervaporation employing ethanol‐permselective silicalite membranes as an alternative to distillation is a promising approach for refining low‐concentration bioethanol solutions. However, to make the separation process practicable, it is extremely important to avoid the problems caused by the adsorption of succinate on the membrane during the separation process. In this work, the pervaporation of an ethanol fermentation broth without succinate was investigated, as well as the influence of several fermentation broth nutrient components. RESULTS: Candida krusei IA‐1 produces an extremely low level of succinate. The decrease in permeate ethanol concentration through a silicone rubber‐coated silicalite membrane during the separation of low‐succinate C. krusei IA‐1 fermentation broth was significantly improved when compared with that obtained using Saccharomyces cerevisiae broth. By treating the fermentation broth with activated carbon, bioethanol was concentrated as efficiently as with binary mixtures of ethanol/water. The total flux was improved upto 56% of that obtained from the separation of binary mixtures, compared with 43% before the addition of activated carbon. Nutrients such as peptone, yeast extract and corn steep liquor had a negative effect on pervaporation, but this response was distinct from that caused by succinate. CONCLUSION: For consistent separation of bioethanol from C. krusei IA‐1 fermentation broth by pervaporation, it is useful to treat the low nutrient broth with activated carbon. To further improve pervaporation performance, it will be necessary to suppress the accumulation of glycerol. Copyright © 2009 Society of Chemical Industry     

Reliable production of highly concentrated bioethanol by a conjunction of pervaporation using a silicone rubber sheet‐covered silicalite membrane with adsorption process

For the production of highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, pervaporation performance was investigated using a silicalite membrane entirely covered with a silicone rubber sheet to prevent direct contact with acidic compounds. By using a resistance model for membrane permeation, the separation factor of the covered silicalite membrane towards ethanol can be estimated from the individual pervaporation performances of the silicalite membrane and the silicone rubber sheet. No decrease in the ethanol concentration through the silicone rubber sheet‐covered membrane was caused when ethanol solutions containing succinic acid were supplied. By directly passing the permeate‐enriched ethanol vapor mixed with water vapor through a dehydration column packed with a molecular sieve of pore size 0.3 nm, highly concentrated bioethanol up to 97% (w/w), greater than the azeotropic point in the ethanol/water binary systems, can be obtained from 9% (w/w) fermentation broth. Copyright © 2004 Society of Chemical Industry     

Stabilized production of highly concentrated bioethanol from fermentation broths by Zymomonas mobilis by pervaporation using silicone rubber‐coated silicalite membranes

Since pervaporation performance of ethanol‐permselective silicalite membrane, which is an aluminum‐free hydrophobic zeolite, in the separation of fermentation broths by yeast are negatively affected by succinic acid, the potential of pervaporation using silicone rubber‐coated silicalite membranes of ethanol fermentation broths, not containing succinic acid, by Zymomonas mobilis was investigated for the reliable production of concentrated bioethanol. In the separation of fermentation broths, the pervaporation performance was influenced by nutrients used for the preparation of fermentation broths. In the separation of a broth prepared with yeast extract, pervaporation performance was greatly compromised by accumulation of a substance(s) having an ultraviolet absorption maximum at approximately 260 nm not only in total flux, but also in permeate ethanol concentration compared to the separation of binary ethanol/water mixtures. When supplying a prepared broth with corn steep liquor without the accumulation of a substance(s) having an ultraviolet absorption maximum at approximately 260 nm, the permeate ethanol concentration did not decrease. Treating the prepared broth with activated carbon was effective in restraining the decrease in total flux. Pervaporation performance is also deteriorated by the adsorption of lactic acid contained in corn steep liquor onto the silicalite crystals. In the separation of ternary mixtures of ethanol/water/lactic acid, accomplished by adjusting the ternary mixtures to pH > 5, more than 90% of the permeation flux in the separation of binary ethanol/water mixtures was obtained, and the permeate ethanol concentration was comparable to that obtained in the separation of binary mixtures. For stably performing pervaporation, it is important to prepare ethanol fermentation broths by Zymomonas mobilis in which lactic acid concentration is as low as possible. Copyright © 2007 Society of Chemical Industry     

Drastic improvement of bioethanol recovery using a pervaporation separation technique employing a silicone rubber‐coated silicalite membrane

A coupled fermentation/pervaporation process for reliable production of concentrated ethanol was studied using ethanol permselective silicalite membranes coated with two types of silicone rubber, KE‐45 and KE‐108, as a hydrophobic material. Ethanol recovery was greatly improved by using a membrane coated with KE‐45 silicone rubber. The recovered ethanol concentration in the permeate was 67% (w/w), and the amount of recovered ethanol from the broth was more than 10 times higher than that using a non‐coated membrane. Succinic acid and glycerol, by‐products created during fermentation, interfered with the pervaporation performance of the coated membrane when used to separate an ethanol/water solution. Copyright © 2003 Society of Chemical Industry     

碳分子筛填充硅橡胶膜用于渗透蒸发分离稀醋酸-水溶液

From the reference[1] it is known that the addition of silicalite-1 in silicone rubber membranes results in an increase of both flux and selectivity for alcohol in the separation of alcohol/water by pervaporation.In order to enhance performance of pervaporation toward the aqueous solution of acetic acid,incorporation of carbon molecular sieve(CMS)into a PDMS membrane was investigated. CMS is widely used in adsorption processes because of its high selectivity toward certain compounds[2]. It was assumed that the flux and selectivity of pure PDMS membrane could be enhanced owing to the preferential adsorption of CMS to organics.CMS content in the membrane and several important pervaporation operation parameters, including feed concentration of acetic acid, and feed temperature, were investigated.     

丙酮、乙醇对丁醇渗透汽化性能的影响

考察了全硅沸石silicalite-1对丁醇-水、丙酮-水、乙醇-水、丙酮-丁醇-水、乙醇-丁醇-水5种体系中各溶剂的吸附作用。采用自制的silicalite-1/硅橡胶杂化渗透汽化透醇膜,研究了温度对丙酮、丁醇、乙醇分离性能的影响以及不同分离温度下丙酮、乙醇的浓度对丁醇、水渗透汽化性能的影响,结果表明丙酮和乙醇的存在会促进丁醇的透膜性。     

A study on the effect of cross-linkers on pervaporation performance of room temperature vulcanised silicone rubber membranes for butanol recovery

As a rising membrane separation technology, pervaporation (PV) has been regarded as one of the most promising separation technology applied in separation of azeotropic mixtures due to its high selectivity and low energy consumption. In a PV process, separation process mainly occurs in the PV membrane, so it is of significance to develop a membrane with high performance. Room temperature vulcanised (RTV) silicone rubber is a kind of membrane material possessing good hydrophobicity and low glass transition temperature. It is widely used in the recovery of organic compounds from their dilute aqueous solutions. In this paper, RTV silicone rubber membranes were fabricated by a typical one-pot method and characterised by Fourier transform infrared spectroscopy, thermal gravimetric analysis, water contacting angle, differential scanning calorimetry, scanning electron microscopy and swelling experiment. The membranes were used in PV recovery of n-butanol from its dilute aqueous solution (about 1?wt-%). The influences of temperature and cross-linkers on the performance of PV were discussed at the same time. In conclusion, RTV silicone rubber membrane cross-linked by vinyltrimethoxysilane (WD-21), which obtained membrane selectivity of 82.9 with butanol permeability of 1.1_?×_?10⁶ Barrer at 50°C, got the best performance.     

Pervaporation and Dialysis of Water-Ethanol Solutions Using Silicone Rubber Membranes

Abstract

Ethanol-water solutions may be concentrated by pervaporation through silicone rubber and regenerated cellulose film. Using silicone, separation factors (SF) decrease as the ethanol concentration in the feed solution increases (SF = 6.5 using 12.9 w/w% ethanol and 1.4 using 83.2% ethanol at 30°C). The temperature effect on separation factors is negligible, but is appreciable on permeation rates.

Ethanol permeation rates in the dialysis mode are not linear with ethanol chemical potentials in solution; silicone swelling coefficients also increase noticeably with alcohol concentration in aqueous solutions, indicating that preferential ethanol sorption occurs and is responsible for the separation.