Occurrence of Volatile Nitrogen-containing Compounds in Nitrogen-fixing Cyanobacterium Aphanizomenon flos-aquae

The occurrence of volatile nitrogen-containing compounds in the cyanobacterium Aphanizomenon flos-aquae has been studied. Twenty compounds belonging to four groups—amides of carboxylic and fatty acids, heterocyclic compounds and their derivatives, aromatics, and alkoxyamines and amides were identified by gas chromatography–mass spectrometry that used serially coupled capillary columns with different polarity of stationary phases. Distribution of bioactive non-toxic and toxic nitrogen-containing metabolites in cyanobacteria are discussed.     

Separation and Purification of Indole in Model Coal Tar Fraction of 9 Compounds System

Separation and purification of indole present in model coal tar fraction was examined by the combination of extraction to separate indole from the crude model coal tar fraction, distillation to obtain high concentration of indole in the extract, and solute crystallization (SC) to obtain high-purity indole present in indole-enriched distillate. The model fraction was made up of four types of nitrogen heterocyclic compounds (quinoline, iso-quinoline, 4.66% indole, and quinaldine), three types of bicyclic aromatic compounds (1-methylnaphthalene, 2-methylnaphthalene, and dimethylnaphthalene), biphenyl, and phenyl ether. Aqueous solutions of formamide and n-hexane were used as the extraction solvent and the SC solvent, respectively. Through the combination of formamide extraction, distillation, and SC using n-hexane in this work, 99.5% indole was recovered. We confirmed that the combination examined by this work was one of the very useful combinations for the high-purity purification of indole present in the coal tar fraction.     

Cottonseed extraction with mixtures of acetone and hexane

Cottonseed flakes were extracted with mixtures of n-hexane and acetone, with the concentration of acetone varying between 10 and 75%. Adding small amounts of acetone (≤25%) to n-hexane significantly increased the extraction of free and total gossypol from cottonseed flakes. Sensory testing detected no difference in the odor of cottonseed meals produced either by extraction with 100% n-hexane or by extraction with a 10∶90 (vol/vol) mixture of acetone/hexane. More than 80% of the free gossypol was removed by the 10∶90 mixture of acetone/hexane, whereas pure n-hexane extracted about 47% of the free gossypol from cottonseed flakes. A solvent mixture containing 25% acetone removed nearly 90% of the free gossypol that was removable by extraction with pure acetone; the residual meal had only a minimal increase in odor. In contrast, cottonseed meals produced by extraction with pure acetone had a much higher odor intensity. The composition of the cottonseed crude oil was insignificantly affected by the acetone concentration of the extraction solvent. The results indicate that mixtures of acetone and n-hexane can be used as extraction solvents to produce cottonseed crude oil without the concomitant development of odorous meals.     

Extraction Separation of Rhamnolipids by n-Hexane via Forming Reverse Micelles

Rhamnolipids (RL) have been regarded to be insoluble in n-hexane. Unexpectedly, we have noticed that RL could be extracted together with vegetable oil by n-hexane at analyzing oil content of fermentation broth. This paradoxic phenomenon was assumed to be due to the formation of reverse micelles. As found in this paper, the micelle size as well as conductivity increased due to water solubilization, illustrating the formation of reverse micelles of RL in n-hexane. In this reverse micellar system, the maximal water solubility was detected to be 6.26 mol H₂O/mol RL while the reverse critical micelle concentration of RL was around 3% (w/w). Hence, it seems that the presence of water could increase the dissolution of RL in n-hexane via forming the reverse micelles of RL/n-hexane/water. Lastly, the formation of reverse micelles was further applied for extraction of RL by n-hexane. Using this method, over 99.0% of RL was extracted under the appropriate pH of 4.5. This extraction separation using n-hexane instead of chloroform proposed a much cleaner and safer strategy in RL manufacture. Moreover, the capability of RL in forming reverse micelle system could benefit the future application on improving enzymatic reactions, stabilizing nanoparticles, environmental treatment, and protein folding, etc.     

磷钨酸催化氧化吸附脱除模拟油中氮化物研究

将磷钨酸、质量分数30%双氧水负载于介孔硅胶吸附剂孔中制备成脱氮剂,脱氮剂中硅胶与磷钨酸、质量分数30%双氧水的质量比为50%∶26.7%∶23.3%。以喹啉、吲哚和咔唑为模型氮化物,二甲苯及二甲苯和十二烷的混合溶液作溶剂,配制成含氮模拟油。在间歇反应器中,对磷钨酸、氧化剂的作用进行了研究,考察了温度、氮化物质量浓度和性质对脱氮反应速率的影响。结果显示:磷钨酸可以深度脱除碱性氮化物和低浓度非碱性氮化物,氧化剂能强化脱氮速率和吸附剂对氮化物的选择性。脱氮剂在温度50℃,脱氮剂与喹啉、吲哚模拟油质量比在3∶30,脱氮剂与咔唑模拟油质量比在3∶25条件下,模拟油中的氮化物90 min内被深度脱除。脱氮剂具有良好的再生性能,再生后脱氮剂的脱氮能力下降很小。     

Study of the sorption and acidic properties of MTW-type zeolite

The acidity of H-MTW-type zeolite has been investigated using infrared spectroscopy of adsorbed pyridine. Pore volume has been measured by nitrogen andn-hexane adsorption. The zeolite exhibits infrared signals at 3612 and 3580 cm^–1 tentatively attributed to bridging hydroxyl groups vibrating in the main channel and in the six-membered rings of the structure, respectively. Both hydroxyl groups possess high acid strength and are readily accessible to pyridine. H-MTW shows an-hexane cracking activity at 350°C comparable to that obtained with MFI and BEA-type materials with a product selectivity between medium and large pore structural types.     

Extraction of Thiophene with Methyl Ether of Polyethylene Glycol 350

Theoretical Foundations of Chemical Engineering - The efficiency of polyethylene glycol methyl ether 350 (PEG ME-350) in the process of extracting thiophene from model motor fuel has been studied...     

An Improved Catalytic Cracking of n-hexane via Methanol Coupling Reaction Over HZSM-5 Zeolite Catalysts

The coupling transformation of n-hexane and methanol over HZSM-5 has been investigated with a pulse-reaction system. In the temperature range of 400–500 °C, kinetic data was collected and reaction order was determined. Compared with the pure n-hexane cracking, the increased rate constant and the lowered apparent activation energy clearly demonstrate an improvement of n-hexane activation using methanol as co-reactant and an increased contribution of faster bimolecular mechanism to the n-hexane transformation due to methanol introduction. Similarly, the results of coupling transformation performed over HZSM-5 with different Al content further confirm the transition between reaction mechanisms of n-hexane on account of the introduction of methanol. Moreover, the further investigation suggests that the enhancement of n-hexane activation and the change of reaction mechanism are attributed to the presence of intermediate species evolved from methanol. Thus, a proposed reaction pathway of n-hexane activation with methanol as co-reactant was put forward.     

Separation of Hydrocarbons by Means of Liquid-Liquid Extraction with Deep Eutectic Solvents

Liquid-liquid equilibria for six ternary systems with choline chloride urea or choline chloride glycerol (molar ratio, 1:2) as selective solvent were experimentally determined at atmospheric pressure and 25°C. Equilibrium data were presented with tie lines. Extraction experiments with three-component systems were performed. The suitability of deep eutectic solvents for the separation of pyridine and toluene from n-hexane, and n-butanol from toluene was evaluated in terms of properties of solvents, solute distribution ratio, and extraction efficiency. Choline chloride glycerol has a better potential for separation of pyridine from its mixture with n-hexane. The equilibrium data were well described with the NRTL model.     

Effect of Operating Parameters on Oil and Phenolic Extraction Using Supercritical CO<Subscript>2</Subscript>

Supercritical fluid extraction (SFE) with carbon dioxide was used to extract oil from canola press cake. Different operating conditions, e.g. pressure, temperature, and co-solvent % were investigated to optimize extraction parameters to yield canola meal with <4% oil. The residual oil content in the extracted canola meal reduced to 2.1–2.9% in our experimental trials. Residues of the optimum conditions based on oil yield were compared for the total phenolic content and the main phenolic compounds. Sinapine (the choline ester of sinapic acid) was the major phenolic constituent in both the SFE and n-hexane extracted canola meals and press cakes. n-Hexane extracted residues showed the retention of the highest sinapic acid, sinapine, sinapoyl glucose and total phenolic contents (mg/g) while the SF-extracted residues showed the lowest values for these compounds.     

Separation of heterocyclic nitrogen compounds from coal tar fractions via ionic liquids: COSMO-SAC screening and experimental study

Ionic liquids (ILs) have been applied as a promising solvent for the separation of different kinds of compounds. But the enormous combination possibilities of the cations and anions make it a challenging task to screen an appropriate IL for a specific application. Thus, the method for screening IL candidates based on the COSMO-SAC model is presented and illustrated to extract heterocyclic nitrogen compounds, indole and carbazole, from coal tar fractions. Also, the σ-profile analysis is used to evaluate the effect of different types of cations and anions, and systematically confirmed the structure–activity relationships for the extraction process. Then, 22 cations and 19 anions are screened as the initial structures of the potential extractants from a σ-profile database (containing 39 cations and 29 anions). Along with the rigorous evaluation criterion proposed in this work, three IL extractants are adopted. Afterwards, the extractive ability of the candidates is experimentally investigated.     

Effect of the nitrogen heterocyclic compounds on hydrodesulfurization using in situ hydrogen and a dispersed Mo catalyst

The hydrodesulfurization (HDS) of the highly refractory sulfur-containing compounds, dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), and the effect of the basic and non-basic nitrogen heterocyclic compounds, such as quinoline and carbazole, on HDS using a dispersed unsupported Mo catalyst and in situ generated hydrogen were studied. Experimental results indicated that the dispersed unsupported Mo catalyst was effective for the HDS of 4,6-DMDBT in a mixture containing DBT. The direct desulfurization pathway (DDS) was the preferred pathway for the HDS of DBT while the hydrogenation pathway (HYD) was the preferred pathway for the HDS of 4,6-DMDBT under our experimental conditions. A strong inhibitive effect of the basic quinoline or the non-basic carbazole on the HDS of each of the sulfur-containing compounds was observed. The DDS and HYD pathways in the HDS of the refractory sulfur-containing compounds were affected to a different extent by the nitrogen-containing compounds, suggesting that different active sites were involved in these two reaction pathways.     

Asymmetric hydrogenation of heteroaromatic compounds

Asymmetric hydrogenation of heteroaromatic compounds has emerged as a promising new route to saturated or partially saturated chiral heterocyclic compounds. In this Account, we outline recent advances in asymmetric hydrogenation of heteroaromatic compounds, including indole, quinoline, isoquinoline, furan, and pyridine derivatives, using chiral organometallic catalysts and organocatalysts.     

Separation of liquid mixtures by using polymer membranes. I. Permeation of binary organic liquid mixtures through polyethylene

The permeation characteristics and the separation behavior of 25 combinations of binary liquid mixtures through low-density polyethylene membrane have been investigated. The organic compounds studied were members of the homologous series of liquid aliphatic hydrocarbons between n-pentane and n-nonane as well as some aromatic and cyclic compounds. A special permeation cell was designed in order to study permeation rates at different temperatures ranging from 25 to 45°C. The rate of permeation increased with temperature, and it was found that the temperature dependence of the permeation rate for both pure compounds and mixtures could be expressed by Arrheniustype relationships. The efficiency of separation, however, decreased with increasing temperature. Activation energies of permeation rànged from 16–22 kcal/mol for pure compounds and binary mixtures of benzene, n-hexane, cyclohexane, and 2–2-dimethylbutane. The effects of chemical nature, molecular size, and molecular shape of the diffusing species on the permeation and separation were studied and qualitative guidelines were suggested. The effect of the composition of the binary mixtures on the permeation rate has been investigated for several systems. Permeation enhancement effects were observed in which the mixtures permeate considerably faster than either of the pure components. Maximum permeation rates occurred at about 50 wt-% mixtures for the systems benzene–n-hexane and benzene–cyclohexane. This phenomenon is explained in terms of a combined internal plasticizing and solubility effect.     

Comparison of Methanol with Formamide on Separation of Nitrogen Heterocyclic Compounds from Model Coal Tar Fraction by Batch Cocurrent Multistage Equilibrium Extraction

The separation of nitrogen heterocyclic compounds (NHC) contained in a model coal tar fraction comprising four kinds of NHC [indole (In), quinoline (Q), iso-quinoline (iQ), quinaldine (Qu)], three kinds of bicyclic aromatic compound (BAC) [1-methylnaphthalene (1MN), 2-methylnaphthalene (2MN), dimethylnaphthalene (DMN) mixture with ten structural isomers (DMNs; regarded as one component)], biphenyl (Bp), and phenyl ether (Pe) was examined by batch cocurrent three stages equilibrium extraction. The model coal tar fraction used as a raw material in this work was prepared according to the components and compositions contained in coal tar fraction (distilled temperature ranges: 240–265°C). An aqueous solution of formamide and that of methanol were used as solvent, respectively. The distribution coefficient of the entire NHC (NHCs) summed four kinds of NHC was much larger than that of the entire BAC (BACs) summed three kinds of BAC, Bp, and Pe. Irrespective of solvent used in this work, the NHCs was recovered more than 90% through three stages of the equilibrium extraction. The selectivity of NHCs based on BACs obtained through the 3 stages equilibrium extraction using an aqueous solution of formamide was higher 3.6–8 times than that using an aqueous solution of methanol. Furthermore, we investigated the recovery process of NHCs contained in coal tar fraction using the formamide experimental results obtained from this work.     

Cottonseed extraction with a new solvent system: Isohexane and alcohol mixtures

A solvent system, consisting of isohexane and 5 to 25% alcohol, either ethanol (EtOH) or isopropyl alcohol (IPA), was tested for extracting gossypol and oil from cottonseed. The test results indicate that this new solvent system not only is effective in removing free and total gossypol but also is as efficient as n-hexane when extracting oil. The amino acid analysis of cottonseed meal, produced by the new solvent system, is similar to that produced by commercial n-hexane. Present commercial cottonseed extraction and downstream processing of cottonseed oil refining may need little change to adopt this new solvent system. This new solvent system may lead to a solution to the gossypol problem of cottonseed extraction.     

Optimization of enzymatic pretreatment for n-hexane extraction of oil from Silybum marianum seeds using response surface methodology

An investigation on enzymatic pretreatment for n-hexane extraction of oil from the Silybum marianum seeds was conducted. The optimum combination of extraction parameters was obtained with the response surface methodology (RSM) at a four-variable and five-level central composite design (CCD). The optimum parameters of enzymatic pretreatment were as follows: enzyme concentration of 2.0% (w/w), temperature of 42.8 °C, reaction time of 5.6 h, and pH of 4.8. After enzymatic pretreatment, the oil was extracted by n-hexane for 1.5 h, and the oil yield on a dry basis was 45.70%, which well matched with the predicted value (45.86%). The results of the effects of the enzymatic pretreatment for n-hexane extraction of oil from the aspects of oil yield, microstructure and the fatty acid compositions showed that the enzymatic pretreatment had not affected on the fatty acid compositions, but could cause structure breakage of the S. marianum seeds and accelerate releasing extra oil, which increased the oil yield by 10.46% compared with n-hexane extraction for 1.5 h without enzymatic pretreatment, and confirmed the efficacy of enzymatic pretreatment for n-hexane extraction of oil from the S. marianum seeds.     

Kinetics of the low-temperature isomerization of <Emphasis Type="Italic">n</Emphasis>-hexane on the NIP-3A catalyst in an isothermal flow reactor

Low-temperature n-hexane isomerization kinetics was studied in an isothermal fixed-bed flow reactor on the chlorinated platinum-alumina catalyst NIP-3A under conditions of the coexistence of liquid and vapor phases. Optimum n-hexane isomerization conditions have been determined. Kinetic equations for the process are suggested.     

Characterization and supercritical carbon dioxide extraction of walnut oil

Walnut (Juglans regia L.) oil was extracted with compressed carbon dioxide (CO₂) in the temperature range of 308 to 321 K and in the pressure range of 18 to 23.4 MPa. The influence of particle size was also studied at a superficial velocity of 0.068 cm/s, within a tubular extractor of 0.2 L capacity (cross-sectional area of 16.4 cm²). FFA, sterol, TAG, and tocopherol compositions were not different from those of oil obtained with n-hexane. The main FA was linoleic acid (56.5%), followed by oleic acid (21.2%) and linolenic acid (13.2%). The main TAG was LLL (linoleic, linoleic, linoleic) (24.4%), followed by OLL (oleic, linoleic, linoleic) (19.6%) and LLLn (linoleic, linoleic, linolenic) (18.4%). The main component of sterols was β-sitosterol (85.16%), followed by campesterol (5.06%). The amount of cholesterol was low (0.31 and 0.16% for oils extracted by n-hexane and supercritical fluid extraction, respectively. The CO₂-extracted oil presented a larger amount of tocopherols (405.7 μg/g oil) when compared with 303.2 μg/g oil obtained with n-hexane. Oxidative stability determined by PV and the Rancimat method revealed that walnut oil was readily oxidized. Oil extracted by supercritical CO₂ was clearer than that extracted by n-hexane, showing some refining. A central composite, nonfactorial design was used to optimize the extraction conditions using the software Statistica, Version 5. The best results were found at 22 MPa, 308 K, and particle diameter (Dp) −0.1 mm.     

Transformation of propane,n-butane and n-hexane over H3PW12O40 and cesium salts. Comparison to sulfated zirconia and mordenite catalysts

Over H₃PW₁₂O₄₀ and its acidic cesium salts at 250°C, alkane transformations occur through the mechanisms previously proposed for sulfated zirconia and mordenite catalysts: propane is mainly transformed into butanes through a trimerization–isomerization–cracking process, n-butane into isobutane, propane and pentanes through a dimerization–isomerization–cracking process, n-hexane into methylpentanes and 2,3-dimethylbutane through a monomolecular mechanism. With all the samples, n-butane transformation is initially much faster than propane transformation, the difference in rate increasing significantly with the Cs content: from 25 times with H₃PW₁₂O₄₀ to 350 times with Cs_2.4H_0.6PW₁₂O₄₀. On the other hand, n-hexane transformation is 2.3 to 7 times faster than n-butane transformation. A decrease in acid strength and in acid site density with Cs introduction is proposed to explain the increase in the rate ratios. For all the reactions, sulfated zirconia pretreated at 600°C is 2–3 times more active than the heteropolycompounds. HMOR10 which is the most active catalyst for n-hexane transformation is the least active for n-butane and especially propane transformation. This very low activity of mordenite for these bimolecular processes can be related to particularities of its pore system: bimolecular reactions are strongly unfavoured in the narrow non-interconnected channels of this zeolite. This revised version was published online in August 2006 with corrections to the Cover Date.