树脂吸附法从发酵液中提取红霉素的工艺研究

针对传统红霉素生产工艺中存在的问题,提出了膜过滤、吸附、杂质洗涤、红霉素洗脱、洗脱液成盐及树脂再生等步骤组成的红霉素提取新工艺过程。以红霉素发酵液为原料,研究和优化了各单元操作的工艺条件和实际效果。采用孔径为50 nm的无机陶瓷膜对红霉素发酵液进行预处理,过程的平均脱色率为54.0%,平均脱蛋白率为67.5%,红霉素平均收率为92.5%。采用大孔树脂吸附技术对滤液中的有效成分进行浓缩、富集,过程收率为92.6%,结晶后所得红霉素硫氰酸盐的纯度相比原有工艺提高2.31%。筛选出体积分数50%丙酮和50%0.40mol/L NaOH溶液组成的混合溶液对使用后的树脂进行再生,再生后树脂的饱和吸附量不低于新鲜树脂饱和吸附量的80%。     

大孔吸附树脂HZ816对红霉素的固定床吸附过程研究

在上柱质量浓度为2.31—6.56 mg/mL、流量为14.33—42.80 mL/h的范围内研究了固定床吸附柱中大孔吸附树脂HZ816对红霉素的动态吸附过程,考察了原料液质量浓度和进口流量等操作参数对穿透曲线的影响。并采用基于液膜及孔内扩散模型的动力学模型,同时考虑吸附树脂颗粒内外扩散阻力及轴向扩散的影响,研究了固定床上红霉素在大孔吸附树脂中的吸附动力学,并从穿透曲线回归得到液膜传质系数孔内扩散系数。结果表明,在实验范围内,该模型能较好地描述红霉素在HZ816树脂上的吸附过程,由模型拟合得到的液膜传质系数随着原料液质量浓度减小而增大,随着流量升高而增大;孔内扩散系数随着原料液质量浓度增大而减小,随着流量升高而减小。为采用大孔吸附树脂HZ816吸附技术分离纯化红霉素工艺提供了实验和理论基础。     

红霉素在大孔树脂上的吸附动力学研究

采用液膜及孔内扩散模型,模拟不同温度和不同红霉素(EM)初始浓度条件下,大孔吸附树脂HZ816及XAD16吸附红霉素的动态吸附曲线,并获得液膜传质及孔内扩散系数;考察了温度及溶质浓度对红霉素在两种树脂中吸附动力学的影响.结果表明,在实验范围内,红霉素在HZ816和XAD16两种树脂上的吸附平衡数据满足Langmuir吸附等温线方程,液膜及孔内扩散模型能较好地描述红霉素在两种树脂上的吸附动力学,同时,模型拟合得到的液膜传质系数随着温度的升高而增大,随着初始浓度的增大而增大,孔内扩散系数随着温度的升高而增大,随着初始浓度的增大而减小.     

红霉素分子印迹聚合物纳米微球的制备及其吸附特性

以红霉素为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了粒径均一的红霉素纳米分子印迹聚合物微球,优化了分子印迹聚合物的合成条件,确定了模板分子与功能单体的最佳摩尔比为1:3,对其进行了表征. 结果表明,所制聚合物对红霉素的实际最大吸附量可达202.12 mg/g,吸附约200 min达到平衡,对红霉素具有良好的选择性吸附能力.     

蛋黄-壳介孔磁性炭微球的制备及其对红霉素的高效吸附

以溶剂热法制得的Fe₃O₄纳米颗粒为磁核，正硅酸四乙酯(TEOS)为造孔前体，间苯二酚-甲醛树脂(RF)为碳源，一步法制备蛋黄-壳介孔磁性炭微球(Fe₃O₄@C)，并将其作为吸附剂用于去除水中的红霉素。采用TEM、XRD、FTIR、BET和VSM对Fe₃O₄@C进行表征。结果表明，Fe₃O₄@C核壳之间具有大空腔，比表面积为444m²/g，平均孔径为7.7nm，具有超顺磁性。通过静态吸附实验研究了Fe₃O₄@C对红霉素的吸附平衡和速率，并确定了优化的操作条件。结果表明，在吸附剂投加量为1.0g/L、初始红霉素浓度为300mg/L、pH为10的优化条件下，Fe₃O₄@C对红霉素的吸附量为210mg/g。Fe₃O₄@C对红霉素的吸附过程是自发的、吸热的和不可逆的，遵...     

硅胶表面罗红霉素分子印迹聚合物的制备及选择性吸附性能

以γ-氨丙基三甲氧基硅烷(AMPS)为硅胶表面改性剂,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,罗红霉素(ROX)为模板分子,制备得到罗红霉素分子印迹硅胶材料(ROX-MIP-PMAA/SiO₂),采用红外、扫描电镜和粒径测定等方法对其进行了表征.通过静态和动态吸附实验研究了ROX-MIP-PMAA/SiO₂对罗红霉素的吸附性能,并以红霉素为竞争底物,研究其选择吸附性能.结果显示,ROX-MIP-PMAA/SiO₂对罗红霉素的吸附能力明显大于非印迹硅胶(NIP-PMAA/SiO₂),其对罗红霉素和红霉素的分离因子为1.21,说明其对罗红霉素具有较好的选择吸附性能.     

缓冲盐溶液反萃分离红霉素A、C的研究

用NaH2PO4-Na2HPO4缓冲盐溶液反萃醋酸丁酯相中的红霉素,以纯化酯相中的红霉素A。分别考察了缓冲盐pH值、相比(体积比)、温度对红霉素A、C反萃取的影响。实验结果表明:随着pH值的增加,红霉素A的反萃率大大减少,红霉素C的反萃率先增加后减小,当pH=8时,酯相中红霉素A纯度最高且损失最低;随着相比(A/O)的增加,红霉素A、C的反萃率及酯相中的红霉素A纯化效果都略有提高,但综合考虑反萃剂用量和红霉素A损失,可知相比(A/O)为2∶1时较优;随着温度的增加,红霉素A、C的反萃率都大大减小,且酯相中的红霉素A纯度略有下降,但因红霉素A反萃损失较少,可考虑在328 K时,反萃2次,除去大量红霉素C的同时损失较少的红霉素A。     

桥红霉素亚胺的合成

以红霉素肟为起始原料,经三乙酰化、桥化、还原、乙酰化四个步骤合成桥红霉素亚胺,总收率28%。桥红霉素亚胺用于生产新型抗生素类药物——桥红霉素,它是在红霉素内酯环结构上脱掉cladinosesugar,并将红霉素内酯环上6,11位相连,成为全新的红霉素衍生物。此药不但克服了该类抗生素药物的耐药性,而且具有较好的抗菌活性。     

红霉素溶析结晶过程的介稳特性

在工业生产中,红霉素采用溶析结晶的方法制备,红霉素溶析结晶过程的介稳特性直接影响红霉素晶体的粒径和粒度分布.本研究采用差重法测定丙酮水溶液中红霉素的溶解度,采用激光散射法测定红霉素的超溶解度,由此获得红霉素-丙酮-水结晶体系的介稳区宽度.红霉素在丙酮水溶液中的溶解度随着丙酮浓度的降低而减小,32℃以下的各溶解度曲线有逐渐趋于一点的趋势.50℃时,介稳区的宽度随着丙酮浓度的降低而变窄,并于质量比Mwater/MAcetone约为1.7时趋于最小值;红霉素的超溶解度随着反溶剂水导入速率的增大而减小,导致介稳区宽度变窄;搅拌速率的增加使红霉素的超溶解度先减小再增大,介稳区宽度于转速约为340r·min-1时达最小值.基于以上研究结果形成的变温、变搅拌强度的红霉素动态溶析结晶方法制备的红霉素晶体的粒度增大且分布集中,其生物效价也有明显提高.     

用乳酸法从红霉素母液中回收红霉素

红霉素生产的母液中,还存在少量的红霉素,回收其中的红霉素,过去采用缓冲液法。这种方法,体积大,工艺繁杂,回收率低。在伟大领袖毛主席“抓革命、促生产”方针的指引下,西安制药厂红霉素车间职工,坚持党的基本路线,大搞三结合的技术革新、技术革命运动,于一九七六年对从红霉素母液中捞取红霉素的方法,进行了摸索改进,终于找到了一条从母液中回收红霉素的新方法——乳酸成盐法,并已正式用于生产。     

Selective adsorption of oleuropein from olive (Olea europaea) leaf extract using macroporous resin

Extraction, optimization, and adsorption of oleuropein from olive (Olea europaea) leaves were carried out, respectively. Face-centered composite design model was chosen for designing the experimental conditions for extraction of olive leaves through response surface methodology. Olive leaf extract obtained under the optimum conditions was concentrated by several macroporous resins (Amberlites XAD 2, XAD 4, XAD 7HP, and XAD 16). The crude and purified extracts were evaluated according to their total phenolic material (TPM) and oleuropein concentration. XAD 7HP showed the best performance regarding adsorption (91%) and desorption ratio (97%) for oleuropein. Pseudo-first- and second-order and Elovich kinetic models were efficient to represent the experimental data for the adsorption of TPM and oleuropein with high correlation coefficients. Equilibrium data were fitted to Langmuir and Freundlich isotherms at four different temperature values. The antioxidant capacity of the extracts was evaluated with several assays such as Cupric ion reducing antioxidant capacity, 2,2-diphenyl-1-picrylhydrazyl, and 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt.     

ENRICHMENT AND PURIFICATION OF BITESPIRAMYCIN USING MACROPOROUS RESIN

Bitespiramycin was purified by selective adsorption. The adsorption and desorption properties of bitespiramycin on six different macroporous resins (HZ806, HZ816, HZ820, HZ830, XAD16, and SP207) were compared systematically. According to the adsorption capacity and selectivity towards 4″-O-isovalerylspiramycin, HZ820 was chosen as the most suitable resin for bitespiramycin purification. The equilibrium data on HZ820 in a batch system were well described by Langmuir and Freundlich models. The film and pore diffusion model was successfully measured in batch adsorption kinetics. Dynamic adsorption and desorption experiments were also performed using a packed column of HZ820 to optimize the separation process of 4″-O-isovalerylspiramycin from aqueous solution. After being treated with HZ820, the 4″-O-isovalerylspiramycin content increased from 80.4% to 91.7%, and the 4″-O-isovalerylspiramycin III content increased from 41.7% to 64.4%.     

大孔吸附树脂对芦丁的吸附实验探索

以芦丁为吸附质,考察不同种类的大孔吸附树脂对芦丁水溶液的吸附、树脂活化处理方法、吸附实验的实施方法和树脂的最佳用量。结果表明,最佳操作条件如下:树脂活化时间5 d,吸附前用95%乙醇浸泡会明显增加吸附量,吸附实验增重物确定为玻璃珠子,树脂适宜用量约为1.20000 g。并做了6种大孔树脂在芦丁水溶液中的吸附等温线,得出大孔树脂在芦丁中的吸附,会发生毛细下降效应,通过对大孔树脂的物化参数分析,发现大孔树脂的比表面积并不是决定吸附量的最主要因素,而由大孔树脂的物化参数以及溶剂的性质等协同作用决定。     

Importance of Surface Area and Pore Size Distribution of Resin for Organic Toxicants Adsorption

Adsorption of benzoic acid and reactive brilliant blue 4 (RBB4) by hypercrosslinked resins and macroporous resins was examined. Micropore areas were much higher in the hypercrosslinked resins than macroporous resins while the pore volume and average pore diameter of macroporous resins were superior to the hypercrosslinked resins. The investigation showed that the pore size distributions of the resins significantly influenced the adsorption capacity of adsorbents. Adsorption of benzoic acid was dominated by BET surface area and the micropore area while the adsorption of RBB4 shifted to a pore-size-dominant process. The maximum mol adsorption capacities of benzoic acid were all higher than those of RBB4 by the resins, showing the influence of the molecular dimension on adsorption. The adsorption thermodynamic parameters were calculated and it revealed that the adsorption was an exothermic, spontaneous, and more ordered process. Adsorption kinetics and elution processes were also investigated for establishing the appropriate adsorption conditions for purifying wastewater containing benzoic acid or RBB4.     

Equilibria,Kinetics, and Mechanisms for the Adsorption of Four Classes of Phenolic Compounds onto Synthetic Resins

The adsorption of five phenolic compounds of four different classes from aqueous batch solutions onto four styrene-divinylbenzene and acrylic resins (EXA 90, EXA 118, XAD 7, and XAD 16) was investigated regarding their equilibria, kinetics and surface-energy heterogeneity, and mechanisms of adsorption. The experimental equilibrium data were very well fitted to Langmuir and Freundlich models (R ² > 0.900). Three kinetic models (pseudo-first-order, pseudo-second-order, and an intra-particle diffusion model) were suitable for describing the experimental data, the pseudo-second-order kinetic model being the best one (p < 0.001). The adsorption energy values were low (<19.00 kJ/mol), suggesting a physical adsorption process. Driving forces involved in the adsorption of the phenolic compounds onto the resins were hydrogen bonding, π ? π stacking and hydrophobic interactions.     

Adsorption and desorption behaviour of taurine on macroporous adsorption resins

Adsorption of taurine on S‐8, NKA2 and Amberlite XAD‐1 resins was measured with respect to time and the results indicated that equilibrium was reached in 50 min. The adsorption isotherms of taurine on D4006, AB‐8, S‐8, NKA2 were recorded and compared with those using Amberlite XAD‐1, XAD‐3, XAD‐6 and XAD‐7 at 28 °C. For an aqueous concentration range of 0–100 mg g^?1, each isotherm could be represented as a straight line. S‐8 and XAD‐1 resins had the highest solid/liquid distribution coefficients of 0.92 and 0.9. Since the locally produced S‐8 resin is less expensive than XAD‐1 resin, it was selected for further studies with adsorption isotherms being measured over the aqueous concentration range of 0–160 mg g^?1. These experimental results could be fitted by the Langmuir equation. The effects of pH, salting‐out and temperature on the adsorption were studied with the results showing that the influence of temperature was the most important. A temperature‐swing adsorption process was then tested to separate taurine from aqueous solutions and gave a overall yield >90% when taurine was adsorbed at 28 °C and eluted by deionized water at 70 °C. © 2001 Society of Chemical Industry     

大孔树脂对喹乐霉素的静态吸附

考察了9种不同极性的大孔树脂对喹乐霉素的静态吸附解吸效果,探讨了吸附过程中树脂静态吸附动力学和25℃时的等温吸附过程,并用Langmuir与Freundlich方程分别对吸附过程进行了拟合。结果表明,XAD-16和D101树脂对喹乐霉素的吸附解吸效果较好,比较两种树脂等温吸附的Langmuir和Freundlich参数,D101树脂对喹乐霉素的吸附解吸作用最好,吸附量最大,达到0.976 mg/g干树脂,吸附过程更易发生。因此,D101树脂更适用于从标桩菌WXNXJ-B发酵液中吸附并解吸喹乐霉素。     

大孔吸附树脂纯化草木樨香豆素的动力学和热力学

通过静态吸附和解吸实验筛选出纯化草木樨香豆素的大孔吸附树脂,确定了HPD300树脂纯化香豆素的吸附动力学模型、等温吸附模型和热力学参数,并通过动态吸附和解吸实验优化其工艺条件。结果表明:HPD300树脂对香豆素的吸附量大、解吸率高、吸附速度快,其吸附动力学可用拟二级动力学方程很好地描述,等温吸附过程可用Langmu ir方程较好地拟合,其吸附是一个自发、放热的物理吸附过程,在优化的条件下产物中香豆素的纯度大于90%,回收率高于90%。研究表明:HPD300树脂是一种分离纯化草木樨香豆素的理想树脂,可用于大规模分离纯化草木樨香豆素。     

Application of heterogeneous adsorbents in removal of dimethyl phthalate: Equilibrium and heat

Aminated resin (NDA‐101) and oxidized resin (NDA‐702) were synthesized to remove Dimethyl phthalate (DMP) from the contaminated water. The equilibrium and heat properties in the course of adsorption process were examined and compared with two commercial heterogeneous adsorbents, namely an acrylic ester resin (Amberlite XAD‐7) and a coal‐based granular activated carbon (AC‐750). The associated equilibrium isotherms can be well fitted by Freundlich equation and the adsorption capacities for DMP followed the order: NDA‐702 > NDA‐101 > AC‐750 > XAD‐7. The surface of XAD‐7 was demonstrated to be relatively homogeneous through surface energy heterogeneity analysis, offering the sole hydrogen bonding interaction. Contrarily, heterogeneous surface of oxidized resins NDA‐702 and the aminated resins NDA‐101 exhibited a promising adsorption capacity and affinity toward DMP probably derived by multiple hydrogen bonding, π–π stacking, and micropore filling interactions. © 2010 American Institute of Chemical Engineers AIChE J, 2010