反渗透膜处理含有机酸凝结水技术

采用反渗透膜对某制药厂含甲酸、乙酸、丙酸、丁酸、戊酸、己酸、异丁酸和2-甲基丁酸的凝结水进行处理,研究了进水温度、压力和pH值对凝结水中有机酸截留效果的影响,讨论了反渗透膜对有机酸的截留机理。研究结果表明：温度为20～40 ℃、压力为0.5～1.5 MPa、pH值为4～10时,产水中丁酸、戊酸、己酸和2-甲基丁酸的浓度低于检测限,甲酸、乙酸、丙酸和异丁酸的截留率随着压力和pH值增加而增大,随着温度升高而降低;产水率随着压力增大、温度升高而增大,不受pH值变化影响。说明反渗透膜对有机酸的机械筛除作用及膜与有机酸之间的电荷作用对有机酸的截留具有重要影响。     

黑曲霉产有机酸浸出铀矿石的影响因素

为了解培养基种类、培养温度和pH值等因素对黑曲霉产生的混合有机酸浸出铀矿石的影响,从铀矿山水样中分离、纯化得到了一株真菌--黑曲霉,应用马铃薯-蔗糖培养基（potato sucrose agar,PSA）和葡萄糖-玉米浆培养基(dextrose corn syrup,PCS)进行黑曲霉培养,获得了不同培养温度下产生的pH值不同的黑曲霉产混合有机酸,并将之作为浸出剂用于浸铀实验研究。研究表明,黑曲霉产生的有机酸的主要组分为草酸和柠檬酸等有机酸,培养基种类的不同会影响黑曲霉所产有机酸的浸铀效果,采用PSA培养基培养的黑曲霉产生的有机酸浸铀效果更好（p<0.05）。培养温度和混合有机酸的pH值也会对黑曲霉代谢产物的铀浸出率有显著性影响（p<0.05）,且二者具有交互效应,pH值对铀浸出率的影响相对较大。应用PSA培养基时,最佳培养温度为25℃,最佳代谢产物pH值为2.3;应用PCS培养基时,最佳培养温度为30℃,最佳混合有机酸pH值为2.0。培养基种类、温度和pH值主要通过改变黑曲霉产生的有机酸的成分和含量对铀浸出率产生影响。     

Corrosion of tin in aqueous solutions of mono-, Di- and trichloroacetic acids

The corrosion behaviour of tin in stagnant mono-, di- and trichloroacetic acids solutions in the pH range 1–6 and at concentrations 4.0 to 5 × 10^?4 M was investigated. The results indicate behaviour that is generally the same but there is some dependence on the acid concentration and the pH value. In 4.0 to 10^?2 M solutions, the corrosion rate (W) increased with increasing acid concentration and decreasing pH value from 1 to 4 as follows: log W=a+b log C, where b=0.70, 0.42 and 0.35 for tri-, di- and mono-chloroacetic acids respectively. At high concentrations 4.0 to 10^?2 M and in the pH range 1–6, the steady state corrosion potential shifted in the negative direction with increase of acid concentration accompanied by an increase in the corrosion rate, indicating that the corrosion process becomes anodically controlled by the complexing of Sn²⁺ ions with organic acid anions and that the order of aggressiveness is mono-<di-<trichloroacetic acids. In dilute solutions (10^?2 to 5.10^?4 M) in the pH range 1–6 the steady state potential shifted in the noble direction with increase of acid concentration (accompanied by a remarkable decrease in the corrosion rate). Corrosion inhibition in dilute solutions was attributed to film formation on the surface of tin which may result from the hydrolysis of tin species.     

高温液态水中甜高粱渣半纤维素水解及其机理

为了回收甜高粱渣中的半纤维素衍生糖并了解其水解机理,在自行设计的Flowthrough反应器中对甜高粱渣进行了高温液态水水解,分别考察了不同反应温度和反应液流量下水解液中产物的生成情况。研究表明,相对葡萄糖和阿拉伯糖而言,木糖的生成受反应温度和反应液流量影响更大。温度高于195 ℃时糖降解加剧,总木糖浓度不断降低;低流量（5 ml?min-1）条件下生成的木糖不能被及时排出而进一步降解。通过产物分析可知,甜高粱渣半纤维素中含有典型的O-乙酰基-4-O-甲基葡萄糖醛酸基阿拉伯糖基木聚糖结构,木糖、葡萄糖、阿拉伯糖、各种低聚糖、乙酸和葡萄糖醛酸等是半纤维素水解的直接产物,糠醛和5-羟甲基糠醛等是糖类的降解产物, 甲酸等小分子酸是它们的进一步降解产物。     

Adsorption of dissolved organics from industrial effluents on to activated carbon

Industrial effluents usually include multicomponent organic solutes. The optimum pH for adsorption of a specific industrial effluent on activated carbon should be determined experimentally because, in general, more than one mechanism is involved. A series of experiments was conducted to establish the influence of the initial hydrogen ion concentration on carbon adsorption of organic solutes. For these studies, powdered activated carbon was used, and the water systems studied included both single component pure organic compounds as well as multicomponent organic wastes. Results indicate that the pH effect upon the effectiveness of carbon adsorption mainly depends upon the nature of the adsorbed substance. In general, the degree of ionisation is the controlling factor for adsorption of ionic organic solutes on activated carbon. Adsorption reaches a maximum at the point of least ionisation of the adsorbate. As the organic compounds become more complex (i.e. longer hydrocarbon chains, higher molecular weights, increased branching), the electrical adsorption forces between activated carbon and ionic organic solutes will govern. Anionic surfactants meet with decreased electronegative repulsive forces at low pH levels, which increase the effectiveness of carbon adsorption. However, the adsorption of a cationic surfactant is increased by an increase in the electronegative carbon surface at high pH levels. When ionic organic solutes become much more complex, like a polymer, the effects of both ionisation and electrical adsorption forces become less important. Instead, the adsorption rate will be controlled by the extent of hydrolysis caused by the pH adjustment. For non-ionic organic solutes, chemical reaction(s) between the adsorbate and the added chemical (acid or base) for pH adjustment is an important controlling factor. Again, hydrolysis is responsible for the breakdown of larger size molecules to smaller sizes. Then an increase in adsorption rate with decreasing molecular weight of adsorbate is expected.     

A Chemical Interpretation of Static Fatigue

The effect of water on the growth of cracks in glass is discussed. Crack motion is believed to result from a stress-enhanced chemical reaction between water and glass and is influenced strongly by the crack-tip OH⁻ ion concentration. This hypothesis is supported by the observation that crack-velocity data can be correlated with measurements of pH in slurries of ground glass and water. Variation of the measured pH from 5 to 12, depending on glass composition, suggests a wide pH variation at crack tips. The types of chemical reactions that establish the slurry pH are discussed, and it is noted that the slurries behave as weak acids, buffered solutions, or salts of weak acids, depending on glass composition.     

The effects of fuel washing techniques on alkali release from biomass

The influence of different washing techniques on the alkali release during pyrolysis of biomass is studied. After washing and drying, samples of wheat straw, wood waste and cellulose are subjected to a constant heating rate in a N₂ atmosphere, and the release rate of alkali compounds from the sample is measured continuously by a surface ionization technique. Alkali is released from the untreated biomass in two temperature intervals: (1) in connection with the pyrolysis process taking place at 200-500°C, and (2) from the material remaining after pyrolysis at temperatures above 600°C. Separate vacuum pyrolysis experiments show that the alkali release is dominated by potassium-containing compounds, with minor contributions from sodium-containing compounds. The effect of water washing of the biomass is compared with a more thorough acid leaching technique. In the temperature range 200-500°C, washing with water reduces the alkali emission from wood waste and wheat straw by 5-30%, while acid leaching is more effective and reduces the emission by around 70%. Above 600°C where the vaporization of alkali compounds from untreated wheat straws increases sharply, the washing procedures are sufficient for a reduction in the measured alkali release by more than 90%. Experiments with pure cellulose (ash content 0.07%) indicate that the washing methods are ineffective in removing alkali bound to the organic structure of the biomass. The results support the conclusion from earlier studies that relatively simple washing techniques can improve the combustion properties of biomass fuels with a high ash content. For fuels with a lower ash content like woody biomass, the concentration of alkali bound to the organic structure limits the effect of the washing techniques.     

pH effects on catalytic ozonation of carboxylic acids with metal on metal oxides catalysts

Summary The pH influence on the catalytic ozonation of small carboxylic acids (succinic (SA), chloroacetic (CAA) and pyruvic (PA) acids) was studied and compared to ozonation alone. In the acidic systems, the conversion of these carboxylic acids and total organic carbon (TOC) during the catalytic ozonation is mainly due to the catalytic effect. Experiments on SA indicate that in the pH range 3.6–5.0, in contrast to the ozone behavior, the efficiency of the catalytic ozonation system is decreased with increasing pH due to the change of charges on the catalyst surface. In the basic pH range (7.2–10.0), the effect of the ozonation alone becomes important and the reaction in the presence of the catalyst is a combined effect of ozonation alone and catalytic oxidation. Although the apparent SA conversion by the catalytic ozonation in the basic systems is higher than in the acidic systems, the Total Organic Carbon conversion is not so much higher than in the latter. During the ozonation with the same catalyst, more than 80 of the CAA converted are mineralized. The oxidation of CAA leads to almost equimolar release of chloride ions. This ion has no detrimental influence on the catalytic effects under our experimental conditions. However, in the very dilute systems with pH value lower than the pKa of CAA, when the CAA concentration is decreased to about 0.6mM, the catalytic oxidation is almost stopped. The low concentration of the dissociated CAA induces only weak adsorption and consequently small reaction rates. The total elimination of CAA with low concentration can be reached only if the pH is increased above the pKa. In addition to the distinct pH effect in the ozonation and catalytic ozonation system observed in this work, a further demonstration that separate mechanisms are involved in the two processes is provided by the analysis of oxidation by-products of pyruvic acid.     

Betaine ester-shell functionalized hyperbranched polymers for potential antimicrobial usage: Guest loading capability,pH controlled release and adjustable compatibility

Betaine ester-shell functionalized hyperbranched polyethylenimines (BEHPEI) were synthesized by Menschutkin reaction between per-N-methylated polyethylenimine (MeHPEI) and alkyl bromoacetate. BEHPEI could play dual antimicrobial roles that were, the betaine ester-shell acted as contact-based antibacterial polycations and the drug-loaded BEHPEI could controllably release the drugs due to the cleavage of the betaine ester groups under weak alkaline condition. The BEHPEI exhibited high transport capacities that per gram of BEHPEI could encapsulate 0.24–2.67 g of dyes or drugs. The model drug release experiment employing methyl orange (MO) showed that the drug release of MO-loaded BEHPEI complex occurred slowly in weak alkaline solutions and the release rate was controlled by varying pH, while the complex kept very stable under weak acid condition (pH = 3.0–7.0). BEHPEI generated from long chain alkyl bromoacetate was compatible with organic resins implying the possible usage in antimicrobial fibers and coatings. Another BEHPEI obtained from short-chain alkyl bromoacetate was water soluble and maybe used in lotion formula. The hydrolysis of BEHPEI afforded zwitterionic shell.     

Influence of process parameters on the hydrothermal decomposition and oxidation of glucose in sub- and supercritical water

Supercritical water oxidation (SCWO) of wet waste biomass for energy recovery could be an advantageous alternative to conventional combustion with preceding drying. Therefore the reactions of glucose as a model substance for cellulosic biomass were investigated in sub- and supercritical water. The results of hydrothermal and oxidative experiments carried out in a continuous high-pressure plant with a feed solution of 0.2-1.2% (g g⁻¹) glucose at 24-34 MPa, 250-480 °C and residence times of 2-35 s are presented. In the presence of a stoichiometric oxygen concentration (for total oxidation to carbon dioxide and water) glucose decomposes already at subcritical temperatures readily to carbon monoxide and low molecular liquid substances, chiefly organic acids like e.g. acetic acid and glycolic acid. In turn these are in general more stable and react only slowly with oxygen. The effect of temperature, residence time, pressure, reactant concentration and addition of zinc sulfate on the conversion and the yields of reaction products was demonstrated. Already at 350 °C (24 MPa and 30 s) 99% of the glucose are converted. With increasing temperature the production of CO₂ increases. However, even at 480 °C (34 MPa and 4 s) significant amounts of CO are formed and the reaction of glucose to CO₂ and H₂O is not complete. Higher temperatures or greatly longer residence times are needed for a total combustion of the glucose.     

Biocatalytic production of ricinoleic acid from castor oil: augmentation by ionic liquid

Abstract

In present study involving castor oil hydrolysis catalyzed by porcine pancreas lipase, organic solvent, and ionic liquid were applied to augment production of ricinoleic acid. Toluene was the best organic solvent (30.18% hydrolysis in 2?h). In presence of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]), an ionic liquid, the optimal conditions were, 0.12?g ionic liquid/g oil, 4?mg enzyme/g oil, 2?g buffer/g oil, pH of 8, and 2.5?h. Under this condition, ricinoleic acid recovery was 43.41 and 52% at 25?°C and 35?°C, respectively. Organic solvent concentration, enzyme concentration, buffer concentration and time had significant impacts on lipase catalyzed hydrolysis in the presence of organic liquid; whereas, pH and speed remained insignificant. In hydrolysis involving ionic liquid, time had most important effect on ricinoleic acid production. Interaction between enzyme and buffer concentration was most significant. Interactions of ionic liquid concentration with all other variables were also significant besides buffer concentration–time interaction.     

Investigation on the effect of oxalic acid,succinic acid and aspartic acid on the gas hydrate formation kinetics

Gas hydrate reserves are potential source of clean energy having low molecular weight hydrocarbons trapped in water cages. In this work, we report how organic compounds of different chain lengths and hydrophilicities when used in small concentration may modify hydrate growth and either act as hydrate inhibitors or promoters. Hydrate promoters foster the hydrate growth kinetics and are used in novel applications such as methane storage as solidified natural gas, desalination of sea water and gas separation. On the other hand, gas hydrate inhibitors are used in oil and gas pipelines to alter the rate at which gas hydrate nucleates and grows. Inhibitors such as methanol and ethanol which form strong hydrogen bond with water have been traditionally used as hydrate inhibitors. However, due to relatively high volatility a significant portion of these inhibitors ends up in gas stream and brings further complexity to the safe transportation of natural gas. In this study, organic additives such as oxalic acid, succinic acid and L-aspartic acid (all three) having—COOH group(s) with aspartic acid having an additional—NH₂ group, are investigated for gas hydrate promotion/inhibition behavior. These compounds are polar in nature and thus have significant solubility in liquid water; the presence of weak acidic and water loving (carboxylic/amine groups) moieties makes these organic acids an excellent candidate for further study. This study would pave ways to identify a novel(read better) promoter/inhibitor for gas hydrate formation. Suitable thermodynamic conditions were generated in a stirred tank reactor coupled with cooling system; comparison of gas hydrate formation kinetics with and without additives were carried out to identify the effect of these acids on the formation and growth of hydrates. The possible mechanisms by which these additives inhibit or promote the hydrate growth are also discussed.     

Kinetics and mechanism of N-substituted amide hydrolysis in high-temperature water

N-methylacetamide (NMA) served as a model to investigate the hydrolysis kinetics and mechanism of N-substituted amides in high-temperature water. The major products are acetic acid and methylamine, and the reaction is reversible. The hydrolysis reaction is first order in water and first order in NMA at both subcritical and supercritical conditions. The hydrolysis rate is also pH dependent, and three distinct regions of pH dependence exist. At low and high pH, the conversion increased rapidly with added acid and base, respectively. At near-neutral pH, however, the rate was essentially insensitive to changes in pH. Further investigation revealed that the hydrolysis rate constant was very sensitive to the size of the substituent on the carbonyl carbon atom. An S_N2 mechanism with water as the nucleophile appears to be a likely candidate for the hydrolysis mechanism in high-temperature water at near-neutral conditions.     

The Effect of Aliphatic Carboxylic Acids on Olfaction-Based Host-Seeking of the Malaria Mosquito <Emphasis Type="Italic">Anopheles gambiae sensu stricto</Emphasis>

The role of aliphatic carboxylic acids in host-seeking response of the malaria mosquito Anopheles gambiae sensu stricto was examined both in a dual-choice olfactometer and with indoor traps. A basic attractive blend of ammonia + lactic acid served as internal standard odor. Single carboxylic acids were tested in a tripartite blend with ammonia + lactic acid. Four different airflow stream rates (0.5, 5, 50, and 100 ml/min) carrying the compounds were tested for their effect on trap entry response in the olfactometer. In the olfactometer, propanoic acid, butanoic acid, 3-methylbutanoic acid, pentanoic acid, heptanoic acid, octanoic acid, and tetradecanoic acid increased attraction relative to the basic blend. While several carboxylic acids were attractive only at one or two flow rates, tetradecanoic acid was attractive at all flow rates tested. Heptanoic acid was attractive at the lowest flow rate (0.5 ml/min), but repellent at 5 and 50 ml/min. Mixing the air stream laden with these 7 carboxylic acids together with the headspace of the basic blend increased attraction in two quantitative compositions. Subtraction of single acids from the most attractive blend revealed that 3-methylbutanoic acid had a negative effect on trap entry response. In the absence of tetradecanoic acid, the blend was repellent. In assays with MM-X traps, both a blend of 7 carboxylic acids + ammonia + lactic acid (all applied from low density polyethylene-sachets) and a simple blend of ammonia + lactic acid + tetradecanoic acid were attractive. The results show that carboxylic acids play an essential role in the host-seeking behavior of An. gambiae, and that the contribution to blend attractiveness depends on the specific compound studied.     

Production of fuel ethanol from steam-explosion pretreated olive tree pruning

This work deals with the production of fuel ethanol from olive tree pruning. This raw material is a renewable, low cost, largely available, and lacking of economic alternatives agricultural residue. Olive tree pruning was submitted to steam explosion pre-treatment in the temperature range 190-240 °C, with or without previous impregnation by water or sulphuric acid solutions. The influence of both pre-treatment temperature and impregnation conditions on sugar and ethanol yields was investigated by enzymatic hydrolysis and simultaneous saccharification and fermentation on the pretreated solids. Results show that the maximum ethanol yield (7.2 g ethanol/100 g raw material) is obtained from water impregnated, steam pretreated residue at 240 °C. Nevertheless if all sugars solubilized during pre-treatment are taken into account, up to 15.9 g ethanol/100 g raw material may be obtained (pre-treatment conditions: 230 °C and impregnation with 1% w/w sulphuric acid concentration), assuming theoretical conversion of these sugars to ethanol.     

Identification of minor cyclic fatty acids in fractionated tall oil

The structure of several minor cyclic fatty acids present in Finnish tall oil fatty acids are elucidated by gas chromatography-mass spectrometry. The origin and mechanism of formation of these cyclic fatty acids are discussed. The cyclic fatty acids identified in tall oil fatty acids are: 4-(5-pentyl-3a,4,7,7a-tetrahydro-4-indanyl)butanoic acid,ω-(o-alkylphenyl)alkanoic acid, 2,6-dimethyl-9-(3-isopropylphenyl)-6-nonenoic acid, 4-(5-pentyl-4-indanyl)butanoic acid, and 4-(2-hexyl-1,2,4a,5,6,7,8,8a-octahydro-1-naphthyl)butanoic acid. In addition, three different branched or cyclic unsaturated C₁₉ fatty acids are reported to be present in tall oil.     

Lipase-catalyzed enrichment of long-chain polyunsaturated fatty acids

Lipase hydrolysis was evaluated as a means of selectively enriching long-chain ω3 fatty acids in fish oil. Several lipases were screened for their ability to enrich total ω-3 acids or selectively enrich either docosahexaenoic acid (DHA) or eicosapentaenoic acid (EPA). The effect of enzyme concentration, degree of hydrolysis, and fatty acid composition of the feed oil was studied. Because the materials that were enriched in long-chain ω3 acids were either partial glycerides or free fatty acids, enzymatic reesterification of these materials to triglycerides by lipase catalysis was also investigated. Hydrolysis of fish oil by eitherCandida rugosa orGeotrichum candidum lipases resulted in an increase in the content of total ω3 acids from about 30% in the feed oil to 45% in the partial glycerides. The lipase fromC. rugosa was effective in selectively enriching either DHA or EPA, resulting in a change of either the DHA/EPA ratio or the EPA/DHA ratio from approximately 1:1 to 5:1. Nonselective reesterification of free fatty acids or partial glycerides that contained ω3 fatty acids could be achieved at high efficiency (approximately 95% triglycerides in the product) by using immobilizedRhizomucor miehei lipase with continuous removal of water.     

Mass transfer of long chain fatty acids through liquid–liquid interface stabilized by porous membrane

Long chain fatty acids are usually undesirable contaminants in food oils and removal of these acids is an important task for the oil industry. In this paper the mechanism of transfer of fatty acids from liquid organic phase through flat porous membrane into water was investigated. The membrane pores initially were filled with the same organic solvent without fatty acid. It was demonstrated that the rates of transfer from octane into aqueous solution at pH 4 are inversely proportional to the distribution coefficients (K_d) and are mostly determined by diffusion in aqueous unstirred layers. Increase of pH of aqueous solutions from four to 12 results in a 20-fold increase of transfer rate for octanoic acid, and more than 1000-fold increase for oleic acid. Time lag values necessary for the kinetics of fatty acid transfer to reach the steady state were very small for the transfer from octane, but they were much higher in the case of viscous mineral oil. These last values were in good agreement with Barrer’s equation for diffusion through two unstirred layers. In both cases, there is no significant interface resistance for the transfer of relatively long chain fatty acids from organic solvent into water. Ion exchange processes take place in the aqueous phase and the thickness of the corresponding reaction layer decreases to zero at high pH. This final state is equivalent to the reaction, taking place at the interface. This method could be used for kinetic separation of short and long chain fatty acids at acidic pH and non-selective removal of different fatty acids into alkaline aqueous solutions. The membrane-based process does not need elevated temperature and probably is less energy consuming than distillation.     

碱性条件促进纺织印染污泥厌氧发酵产挥发性脂肪酸

系统研究了酸性（pH值5、pH值6）、中性（pH值7）和碱性（pH值8～10）条件下,纺织印染污泥厌氧发酵产挥发性脂肪酸（VFA）的发酵类型,比较了总酸及主要酸的最高发酵浓度及分布、总酸及乙酸的产率和生产速率,并揭示了碱性条件有利于有机酸发酵的机制。研究结果表明,不同pH值条件下,乙酸型均为主要发酵类型,但较低的pH值利于丁酸累积。总酸及乙酸的浓度随着pH值的升高而增加,且碱性条件能够促进纺织印染污泥发酵产酸,原因为高pH值能促进有机物的降解并提高转化效率,同时较高的pH值抑制了有机酸的降解。pH值为10是厌氧发酵产酸并累积乙酸的最佳pH值。该条件下,乙酸和总酸的质量浓度达最高,为8.21 g/L和14.08 g/L;乙酸和总酸产率也达最高,为34.97%和75.72%;同时乙酸和总酸的生产速率达最高值,为2.41 g/(L·d)和3.48 g/(L·d)。pH值为6比较适合丁酸发酵,丁酸的最高浓度为1.89 g/L。