Recovery of high purity sulfuric acid from the waste acid in toluene nitration process by rectification

Waste sulfuric acid is a byproduct generated from numerous industrial chemical processes. It is essential to remove the impurities and recover the sulfuric acid from the waste acid. In this study the rectification method was introduced to recover high purity sulfuric acid from the waste acid generated in toluene nitration process by using rectification column. The waste acid quality before and after rectification were evaluated using UV–Vis spectroscopy, GC/MS, HPLC and other physical and chemical analysis. It was shown that five nitro aromatic compounds in the waste acid were substantially removed and high purity sulfuric acid was also recovered in the rectification process at the same time. The COD was removed by 94% and the chrominance was reduced from 1000° to 1°. The recovered sulfuric acid with the concentration reaching 98.2 wt% had a comparable quality with commercial sulfuric acid and could be recycled back into the toluene nitration process, which could avoid waste of resources and reduce the environmental impact and pollution.     

碱预处理污泥产酸效果及其生物群落研究

为了提高污泥水解酸化过程中的挥发酸产量,获取污水脱氮除磷所需的内碳源,以深圳市罗芳污水厂的二沉池污泥为研究对象,采用不同的碱量对其进行预处理。通过测定碱预处理污泥水解酸化过程中的挥发酸浓度,并采用聚合酶链式反应-变性梯度凝胶电泳(polymerase chain reaction denature gradient gel electrophoresis,PCR-DGGE)技术对参与碱预处理污泥水解酸化产酸过程的主要微生物种群进行分析,结果表明,当碱投加量为0.20 g NaOH/g VSS时,初始溶出的蛋白浓度为1 780 mg/L;水解酸化15 d时,挥发酸总量达到3 473 mg/L;参与产酸的主要细菌属于Firmicutes、Proteobacteria、Bacteroidetes三个门类。     

Comparison of hydrolysis/coagulation behavior of polymeric and monomeric iron coagulants in humic acid solution

Fluorescence quenching is commonly used to study the extent of metal binding to humic acid or fulvic acid. By studying this phenomenon, the hydrolysis and precipitation behaviors of polymeric and monomeric iron coagulants in the coagulation of humic acid were evaluated. Combined measurements of fluorescence intensity and dissolved organic carbon were performed to distinguish the hydrolysis and organic matter binding of polymeric and monomeric iron salts in coagulating high molecular weight organic compounds. Experimental results showed that ferric chloride had lower fluorescence quenching than polyferric sulfate (PFS), indicating more rapid hydrolysis of the monomeric ferric ion in the coagulation and dilution process. The less fluorescence quenching was caused by the lower residual concentration of Fe-humic acid complexes in the filtrate. There was no clear difference in adsorption ability and fluorescence quenching, which indicated that the physical and chemical properties of Fe(OH)3 flocs formed from PFS and FeCl3 coagulation were similar. From the pH study, we found that sludge formed from PFS coagulation was more stable than that from FeCl3 coagulation.     

烟草下脚料发酵制取乙醇

通过单因素实验考察了硫酸浓度、固液比和水解时间对硫酸水解的影响。结果显示最优条件为:硫酸浓度为50%(w/w),固液比为10%(w/v),时间为100 min。烟草下脚料在最佳硫酸水解条件下,经5倍稀释,中和pH值至5～6。取经过滤后的水解液(FH)用酿酒酵母(Sacchharomyces cerevisiae)发酵产生乙醇,最大的乙醇浓度和乙醇产量分别为1.09g/L和54.5 g/kg。未过滤水解液(UFH,包括水解残渣)加入纤维素酶(70 U/100 mL)和酿酒酵母(Sacchharomyces cerevisiae)进行发酵,最大的乙醇浓度和乙醇产量分别为1.23 g/L和61.5 g/kg。     

Levoglucosan,a tracer for cellulose in biomass burning and atmospheric particles

The major organic components of smoke particles from biomass burning are monosaccharide derivatives from the breakdown of cellulose, accompanied by generally lesser amounts of straight-chain, aliphatic and oxygenated compounds and terpenoids from vegetation waxes, resins/gums, and other biopolymers. Levoglucosan and the related degradation products from cellulose can be utilized as specific and general indicator compounds for the presence of emissions from biomass burning in samples of atmospheric fine particulate matter. This enables the potential tracking of such emissions on a global basis. There are other compounds (e.g. amyrones, friedelin, dehydroabietic acid, and thermal derivatives from terpenoids and from lignin—syringaldehyde, vanillin, syringic acid, vanillic acid), which are additional key indicators in smoke from burning of biomass specific to the type of biomass fuel. The monosaccharide derivatives (e.g. levoglucosan) are proposed as specific indicators for cellulose in biomass burning emissions. Levoglucosan is emitted at such high concentrations that it can be detected at considerable distances from the original combustion source.     

烟草下脚料发酵制取乙醇

通过单因素实验考察了硫酸浓度、固液比和水解时间对硫酸水解的影响。结果显示最优条件为：硫酸浓度为50%（w/w）,固液比为10%（w/v）,时间为100 min。烟草下脚料在最佳硫酸水解条件下,经5倍稀释,中和pH值至5～6。取经过滤后的水解液（FH）用酿酒酵母（Sacchharomyces cerevisiae）发酵产生乙醇,最大的乙醇浓度和乙醇产量分别为1.09g/L和54.5 g/kg。未过滤水解液（UFH,包括水解残渣）加入纤维素酶（70 U/100 mL）和酿酒酵母（Sacchharomyces cerevisiae）进行发酵,最大的乙醇浓度和乙醇产量分别为1.23 g/L和61.5 g/kg。     

城市生活垃圾中纤维素含量测定方法优化

对传统硫酸法进行改进,建立适用于城市生活垃圾纤维素含量的测定方法。以脂肪抽提时间、硫酸浓度、水解反应温度、水解反应时间、稀释硫酸浓度、回流时间为考察因素进行6因素5水平正交实验。结果表明,测定纤维素含量的最佳条件为：脂肪抽提时间4h、硫酸浓度70％、水解反应温度30℃、水解反应时间5h、稀释硫酸浓度5％、回流时间3h。优化后纤维素测定条件RSD均小于1．69％,平均回收率98．76％,表明该方法的精度高,可靠行强。     

Recovery and characterization of the humate-like salified polymeric organic fraction (lignimerin) from Kraft cellulose mill wastewater

A dark and complex salified organic polymeric mixture, named lignimerin, was for the first time recovered from Kraft cellulose mill wastewater (KCMW) and characterized by chemical, spectroscopic and relative molecular weight (RMW) analysis. Lignimerin proved to be composed of polyphenols (57.00%), carbohydrates (22.26%) and proteins (7.42%). It also contained metals (6.93%), mainly Ca and, to much lower extent, Mg, Na, Al, Fe, K, Mn, Zn and Cu, bound to the carboxylate and phenate groups. The distribution of lignimerin RMW was assessed to be approximately between 1000 and 8600Da, as well as to consist of lignin and tannin, protein and polysaccharide moieties, strongly aggregated each other. H-lignimerin, its acid derivative, revealed a chemical composition and a RMW distribution very close to that of lignimerin, but a marked metal cations decreasing (1.60%) with respect to lignimerin (6.93%). The humic acid-like nature of both the polymers was assessed. Their potential use as bio-adsorbents of heavy metals is briefly discussed.     

生活污水中糖类测试方法研究

分别用蒽酮比色、苯酚-硫酸及气相色谱法3种测试方法测试了上海市某生活小区生活污水的糖类组成.试验结果表明,蒽酮比色法测试糖类浓度的准确性与精确性优于苯酚-硫酸法,但不能得出污水中糖类的详细组成情况;与蒽酮比色法和苯酚-硫酸法相比,气相色谱法不仅能得出污水中糖类的详细组成,而且还具有较高的精密度.气相色谱法测得的生活污水中各种单糖,如木糖、甘露糖、葡萄糖、半乳糖、鼠李糖、核糖、岩藻糖的质量浓度分别为8.25、 6.02、5.52、4.80、4.44、4.41、2.66 mg/L.     

Structural characterisation of humic acid-bound PAH residues in soil by 13C-CPMAS-NMR-spectroscopy: evidence of covalent bonds

The fate of 13C-labelled phenanthrene and fluoranthene in different soil systems during biodegradation was studied. The soil humic acid fraction was isolated followed by structural characterisation using 13C-cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy (13C-CPMAS-NMR). It could be demonstrated that especially the ratio between the concentrations of polycyclic aromatic hydrocarbons (PAHs) and soil humus matrix limits the usefulness of this analytical tool. Based on these results a ratio of 13C-activity(PAH)/13C-activity(soil) approximately 1.5/1.0 in the test material was suggested. The chemical transformation of a PAH and its bound residue formation in a soil system detected by changes of chemical shifts in the 13C-NMR spectrum was proven for the first time. Structural information obtained by NMR spectra were verified by alkaline hydrolysis of PAH/humus-associations and following identification of cleavage products. Ester-bound phenanthrene metabolites such as 1-hydroxy-2-naphthoic acid, ortho-phthalic acid and 3,4-dihydroxybenzoic acid were detected. Additional structural assignments indicated the presence of ether-bound phenanthrene derivatives as well. Using isotopic labelling techniques a quantitative evaluation of bound residue distribution was undertaken. Fifty to seventy percent of phenanthrene metabolites which could be related to the added 13C(1)-phenanthrene were ester bound via their carboxyl groups.     

Natural products: repellency and toxicity of wild tomato leaf extracts to the two-spotted spider mite, Tetranychus urticae Koch

The potential of using phytochemicals from leaves of wild tomato for controlling the two-spotted spider mite, Tetranychus urticae Koch, is explored in this study as a promising alternative to the use of synthetic pesticides. Wild tomato accessions of Lycopersicon hirsutum plants that are not consumed by humans were planted under greenhouse conditions for mass production of leaves. Crude extracts from leaves of three accessions of L. hirsutum, six accessions of L. hirsutum f. glabratum, and one accession each of L. pennellii and L. pimpinellifolium were prepared in chloroform, ethanol and hexane. Two spider mite bioassays, one a measure of antibiosis and the other a measure of repellency, were utilized to determine the acaricidal performance of the crude extracts. The bioassay for antibiosis was a 6-h no-choice test. The bioassay for repellency utilized a ring bioassay. Chloroform leaf extracts of L. hirsutum f. glabratum accessions (PI-251304, PI-134417, PI-134418, and PI-126449) exhibited greatest antibiotic activity on two-spotted spider mites; the hexane extracts exhibited greatest repellency. Extracts from PI-251304, PI-126449, PI-134417, and PI-134418 were especially lethal (chloroform) or repellent (hexane). We investigated differences in chemical composition of the crude leaf extracts that may explain the observed differences in mortality and repellency among the different accessions. Major chemical compounds (alpha -curcumene, alpha -zingiberene, trans-caryophyllene, 2-undecanone, and 2-tridecanone) known to have pesticidal efficacy were detected and quantified in the crude leaf extracts using a gas chromatograph (GC) equipped with a mass spectrometer (GC/MS). Lethality of extracts was mainly associated with the presence of high concentrations of 2-tridecanone; repellency of extracts was mainly associated with the presence of trans-caryophyllene. Leaf extracts of L. hirsutum f. glabratum accessions that contain significant quantities of 2-tridecanone and/or trans-caryophyllene could be useful for managing populations of spider mites, which could reduce reliance on synthetic pesticides.     

Investigations of the determination and transformations of diazinon and malathion under environmental conditions using gas chromatography coupled with a flame ionisation detector

Degradation of two model insecticides, diazinon and malathion, and their degradation products 2-isopropyl-6-methyl-4-pyrimidinol--IMP (diazinon hydrolysis product) and malaoxon (malathion oxidation product) was compared and studied in the environment. The pesticides and their metabolites were extracted from samples (water, soil, chicory) with ethyl acetate and subsequently the extracts were analyzed by GC/FID. It was shown that hydrolysis is the major process in the degradation of these pesticides in water. In fact, 95% of diazinon was degraded, and only 10% of malathion was oxidised. In soil 30% of diazinon exposed to the sunlight was decomposed by photolysis, whereas in soil left in the darkness no degradation products were observed. In soil left under environmental conditions, 90% of diazinon was degraded and 40% from its initial concentration was transformed into IMP. The concentrations of the pesticides after 21 days on chicory were under maximal allowable concentration, which is 0.5 ppm for malathion and for diazinon. The concentration of malaoxon was more than twice as high as the allowable value, which is for the sum of malathion and malaoxon 3 ppm.     

Enhanced excess sludge hydrolysis and acidification in an activated sludge side-stream reactor process with single-stage sludge alkaline treatment: a pilot scale study

A pilot-scale side-stream reactor process with single-stage sludge alkaline treatment was employed to systematically investigate characteristics of excess sludge hydrolysis and acidification with alkaline treatment and evaluate feasibility of recovering a carbon source (C-source) from excess sludge to enhance nutrient removal at ambient temperature. The resulting C-source and volatile fatty acid specific yields reached 349.19 mg chemical oxygen demand (COD)/g volatile suspended solids (VSS) d⁻¹ and 121.3 mg COD/g VSS d⁻¹, respectively, the process had excellent C-source recovery potential. The propionic-to-acetic acid ratio of the recovered C-source was 3.0 times that in the influent, which beneficially enhanced biological phosphorus removal. Large populations and varieties of hydrolytic acid producing bacteria cooperated with alkaline treatment to accelerate sludge hydrolysis and acidification. Physicochemical characteristics indicated that recovered C-source was derived primarily from extracellular polymeric substances hydrolysis rather than from cells disruption during alkaline treatment. This study showed that excess sludge as carbon source was successfully recycled by alkaline treatment in the process.

     

Evaluating peats for their capacities to remove odorous compounds from liquid swine manure using headspace "solid-phase microextraction".

This paper reports on research designed to investigate the capacities of different highly characterized peats to remove odorous compounds from liquid swine manure (LSM). Peat types representing a wide range of properties were tested in order to establish which chemical and physical properties might be most indicative of their capacities to remediate odors produced by LSM. Eight percent slurries (of peat/LSM) were measured for odor changes after 24 hours using odor panel and GC/MS-Solid-phase microextraction (GC/MS-SPME) analysis. The GC/MS-SPME and odor panel results indicated that, although all peats tested in this study were found to be effective at removing odor-causing compounds found in LSM, some peats tended to work better than others. Overall, the peats that were the most effective at removing odor-causing compounds tended to have lower bulk densities, ash contents, fulvic acids contents, and guaiacyl lignins contents, and higher water holding capacities, hydraulic conductivities, "total other lignins" contents, hydrogen contents, carbon contents, and total cellulose contents. GC/MS-SPME analysis was found to be a reasonably inexpensive and efficient way of conducting this type of research. It allows one to identify a large number of the odor-causing compounds found in LSM, and more importantly, to detect with some precision specific differences in the amounts of these compounds between peat types.     

Mechanism-based quantitative structure-activity relationships for the inhibition of substituted phenols on germination rate of Cucumis sativus

Comparative inhibition activity (GC50) of 42 structurally diverse substituted phenols on seed germination rate of Cucumis sativus was investigated. Quantitative structure-activity relationships (QSARs) were developed by using hydrophobicity (1-octanol/water partition coefficient, logKow) and electrophilicity (the energy of the lowest unoccupied molecule orbital, Eluma) for the toxicity of phenols according to their modes of toxic action. Most phenols elicited their response via a polar narcotic mechanism and a highly significant log Kow-based model was obtained (GC50 = 0.92 log Kow + 1.99, r2 0.84, n = 29). The inclusion of E(lumo) greatly improved the predictive power of the polar narcotic QSAR (GC50 = 0.88 log Kow - 0.30E(lumo) + 1.99, r2 = 0.93, n = 29). pKa proved to be an insignificant influencing factor in this study. Poor correlation with hydrophobicity and strong correlation with electrophilicity were observed for the nine bio-reactive chemicals. Their elevated toxicity was considerably underestimated by the polar narcotic logKow-dependent QSAR. The nine chemicals consist of selected nitro-substituted phenols, hydroquinone, catechol and 2-aminophenol. Their excess toxic potency could be explained by their molecular structure involving in vivo reaction with bio-macromolecules. Strong dissociation of carboxyl group of the four benzoic acid derivatives greatly decreased their observed toxicity. In an effort to model all chemicals including polar narcotics and bio-reactive chemicals, a response-surface analysis with the toxicity, logKow and E(lumo) was performed. This resulted in a highly predictive two-parameter QSAR for most of the chemicals (GC50 = 0. 70 logKow - 0.66E(lumo) + 2.17, r2 = 0.89, n = 36). Catechol and 2,4-dinitrophenol proved to be outliers of this model and their much high toxicity was explained.     

生化-臭氧-曝气生物滤池组合工艺处理制药园区综合废水

针对某制药工业园区综合废水污染物成分复杂、难降解、毒性大、色度深等特点,提出了水解酸化／好氧-臭氧-曝气生物滤池（H／O-O3-BAF）的工艺流程。通过现场实验研究对处理流程以及各个处理单元的运行参数进行了优化。系统稳定运行期间,处理出水化学需氧量（COD）小于50mg／L,色度小于4倍,出水水质达到《城镇污水处理厂污染物排放标准》（GB18918—2002）中一级A标准。发光菌毒性的测试表明,该工艺流程可有效削减废水中的生物毒性。     

酸碱联合调节剩余污泥对有机质的释放和脱水性能的影响

为了研究酸碱联合调节剩余污泥水解酸化过程中溶解性蛋白质(SPN)和溶解性碳水化合物(SPS)的释放规律以及对脱水性能的影响,采用3个反应器,其中,1#为先酸(pH 3.0)后碱(pH 10.0)、3#为先碱(pH 10.0)后酸(pH 3.0)的两段控制方式(每段8 d),同时以2#pH不调作为对比实验。结果表明,3个反应器中SPN和SPS的释放情况是调节为碱性>酸性>空白,在相同的控制阶段,SPN的释放量明显高于SPS的释放量;SPN和SPS的最大释放量出现在1#的碱性阶段(后8 d),SPN在碱性阶段的第2天达到最大释放量(883.618 mg/L),SPS在碱性阶段的第8天达到最大释放量(165.922 mg/L)。1#在实验的整个过程中比阻值较低,说明先酸后碱调节方式更利于污泥脱水;在调节为碱性第4天时污泥比阻(SRF)达到最小值(0.342×1013m/kg),处于中难度脱水范围内。与2#相比,3#中的SRF虽稍有改善,但始终处于难脱水范围内。     

Trace organic and heavy metal pollutants in the Mississippi River

A study was conducted to characterize and measure organic and heavy metal pollutants in the Mississippi River. Water samples were collected along the entire length of the river, and were screened for semivolatile organics by capillary GC and for heavy metals by atomic absorption spectrophotometry. Four water samples were further examined for semivolatile organics by capillary GC/MS. Eight heavy metals and more than sixty distinct organic chemicals were identified including alkylbenzenes, various halogenated organics, five herbicides or derivatives, plasticizers, polynuclear aromatic hydrocarbons (PAHs), saturated hydrocarbons, and three miscellaneous organics. All organic compounds were detected at the parts-per-trillion (pptr) level. In spite of the limited nature of the sampling effort, the large number of data derived from this study suggests the need for a more rigorous monitoring of the river for a wide spectrum of chemical pollutants.     

Single-solute and bi-solute sorption of phenanthrene and pyrene onto pine needle cuticular fractions

To better understand interaction mechanisms of pine needles with persistent organic pollutants, single-solute and bi-solute sorption of phenanthrene and pyrene onto isolated cuticular fractions of pine needle were investigated. The structures of cuticular fractions were characterized by elemental analysis, Fourier transform infrared spectroscopy and solid-state ¹³C NMR. Polymeric lipids (cutin and cutan) exhibited notably higher sorption capabilities than the soluble lipids (waxes), while cellulose showed little affinity with sorbates. With the coexistence of the amorphous cellulose, the sorption of cutan (aromatic core) was completely inhibited, so the cutin components (nonpolar aliphatic moieties) dominated the sorption of bulk needle cuticle. By the consumption of the amorphous cellulose under acid hydrolysis, sorption capacities of the de-sugared fractions were dramatically enhanced, which controlled by the exposed aromatic cores and the aliphatic moieties. Furthermore, the de-sugared fractions demonstrated nonlinear and competitive sorption due to the specific interaction between aromatic cores and polycyclic aromatic hydrocarbon.     

Particulate organic compounds emitted from experimental wildland fires in a Mediterranean ecosystem

Fine (PM_2.5) and coarse (PM_2.5–10) smoke particles from controlled biomass burnings of a shrub-dominated forest in Lousã Mountain, Portugal, enabled the quantification by chromatographic techniques of several molecular tracers for the combustion of Mediterranean forest ecosystems, which could be conducive to source apportionment studies. The major organic components in the smoke samples were pyrolysates of vegetation cuticles, mainly comprising steradienes and sterol derivatives, carbohydrates from the breakdown of cellulose, aliphatic lipids from vegetation waxes and methoxyphenols from the lignin thermal degradation. Most of these compounds are chiefly found in fine particles. Polycyclic aromatic hydrocarbons (PAH) were also present as minor constituents. Anhydrosugar and PAH molecular diagnostic ratios were applied as source assignment tools. Some biomarkers are reported for the first time in biomass burning smoke.