Lipophilic extractives in process waters during manufacturing of totally chlorine free kraft pulp from eucalypt wood

The chemical composition of lipophilic extractives from process waters throughout a totally chlorine free (TCF) bleaching sequence after kraft pulping of eucalypt wood has been studied. These compounds are among the most problematic wood constituents for both TCF and zero liquid effluent (ZLE) processes, since they tend to accumulate in circuits resulting in the formation of the so-called pitch deposits causing serious problems in the pulp and paper industry. Pitch deposits collected at different parts of the pulp mill were also characterized and their composition compared with that of lipophilic compounds in process waters and Eucalyptus globulus wood. The identification of these compounds from process waters, wood and pitch deposits was performed by gas chromatography and gas chromatography-mass spectrometry using short- and medium-length high temperature capillary columns. Sterols, sterol esters, steroid ketones and steroid hydrocarbons were the main compounds identified. These chemical species arise from eucalypt wood extractives that survive the pulping and are released from pulp into the process waters during the bleaching process. Finally, they can deposit in pulp and on different parts of the mill or remain suspended in process waters being discharged in effluents.     

造纸污泥的电渗透脱水效果

采用电渗透脱水技术对经过带式压滤后的制浆造纸混合污泥进行深度脱水,考察了机械压力、电压梯度和污泥厚度对污泥电渗透脱水效果与能耗的影响。结果表明,机械压力从25 kPa升至76 kPa时,脱水效果也会随之提高,但是继续增大机械压力对脱水效果的提高作用就会变得不明显;随着电压梯度的增加,脱水效果会有明显的升高,但是能耗也会相应地增加;电压梯度恒定为30 V/cm且污泥厚度从0.35 cm增加到1.40 cm时,脱水效果和能耗都会相应地增加。对于所有的电脱水实验,当污泥的含水率从74.85%降至60%时所需要的能耗均在0.14～0.28 kWh/kg去除水之间。综合考虑脱水效果和能耗,可认为最优脱水条件是：机械压力为76 kPa,电压梯度为30 V/cm,污泥厚度为0.7 cm。     

Dioxin formation in pulp and paper mills of India

Samples of effluents, sludge, pulp, final products (paper) and soil were collected from the identified pulp and paper mills in India. The samples were analysed for 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD) and other dioxin congeners and precursors. Pulp and paper mills using chlorine for the bleaching process showed the presence of 2,3,7,8-TCDD in effluent samples. In the effluent and pulp samples from mills where chlorine dioxide was used as a bleaching agent, the 2,3,7,8-TCDD congener ranged from below the detection limit 0.05 to 0.12 ngL⁻¹/ngg⁻¹. The relative standard deviation of reproducibility and the percent recovery of 2,3,7,8-TCDD were 2.07 and 82.4% in pulp and 2.8 and 92% in effluent, respectively. The 1,3,6,8-TCDD was the only other major dioxin congener found in the treated and untreated effluent and sludge samples. However, dichlorobenzene, trichlorophenyl, and hexachlorobiphenyl were detected in all samples. The formation of dioxins can be minimised by replacing chlorine with chlorine dioxide in bleaching processes in pulp and paper mills.     

Isomer specific syntheses of chlorinated catechols and guaiacols relevant to pulp bleaching

A variety of chlorinated catechols and guaiacols relevant to pulp bleaching were synthesized by employing fundamental differences in the acidities of phenolic hydroxyl groups in chlorinated catechols, and directive effects in guaiacols.     

Size-exclusion chromatographic study of ECF and TCF softwood kraft pulp bleaching liquors

Background, aims, and scope  

Currently, elemental chlorine-free (ECF) and totally chlorine-free (TCF) bleaching systems are widely used for pulp production. Low and medium molecular weight lignin break-down products are known to have harmful effects on the environment. According to some recent results, also high molecular weight (HMW) material consisting mainly of lignin and carbohydrates may cause toxic effects to the environment. For these reasons, toxicity and structure studies of HMW materials are of great importance. This investigation is a part of a larger project to obtain more structure information of HMW materials and toxicity of ECF and TCF bleaching effluents. Size-exclusion chromatography (SEC) has been commonly used for the characterization of organic macromolecules such as lignin, but to our knowledge, no reports have appeared dealing with the comparison of SEC of ECF and TCF bleaching liquors. The aim of the present study was to get more information about the molecular weight distribution (MWD) of HMW fractions of waste liquors from ECF and TCF bleaching sequences by SEC.     

Determination of dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) in paper pulp mill defoamer additives and in paper pulp samples

An analytical procedure has been developed for quantitatively measuring dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) present at part-per-billion levels in paper mill defoamers and paper pulp using gas chromatography coupled with either low resolution mass spectrometry (GC-LRMS) or high resolution mass spectrometry (GC-HRMS).     

蔗渣浆酶促漂白预处理对纤维形态性质和污染物发生的影响

采用Pulpzyme HC木聚糖酶对蔗渣纸浆进行酶促漂白处理。试验结果表明,酶处理的最佳纸浆浓度为5％,处理时间为60min．酶用量为1．0IU／g。酶处理后纸浆的得率下降不多．强度略有升高,但纸浆白度增加。试验结果还表明,酶处理对纸浆纤维不具有破坏性。对酶处理后纸浆的扫描电镜观察说明,随酶处理时间和酶用量的增加,蔗渣中木聚糖的溶出量加大。酶处理使木聚糖降解溶出,使木质素充分暴露出来,有利于后续漂白剂与之反应．同时可减少后续化学漂白剂的使用量,从而减少有毒氯化有机污染物的产生。随处理时间增长和酶用量增加,处理液中CODcr,和BOD5呈上升趋势。酶用量超过1．5IU／g后．BOD5增长较缓慢,表明酶的作用对纤维表面生物可降解成分的溶出较彻底。     

自由氯、一氯胺和二氧化氯对饮用水中粪肠球菌的消毒动力学研究

以粪肠球菌为研究对象,研究了自由氯、一氯胺和二氧化氯在不同pH值和温度下的消毒效果,并将灭活速率常数表示为pH和温度的函数,对Chick—Watson模型进行了修正。结果表明,随着pH的上升,自由氯和一氯胺的灭活率减小,二氧化氯的灭活率则增大。温度对一氯胺的影响较小,对自由氯和二氧化氯的影响较显著。修正后含有pH和温度两参数的消毒动力学模型可以很好地模拟消毒过程,增强了模型的通用性。     

草制浆造纸中段废水处理及回用技术分析研究

中段废水是制浆造纸工业的主要污染源之一，从工程设计的角度出发，对草制浆造纸中段废水处理及回用提出一套可行适用的工艺方案；对主要工艺环节参数、设备备有说明，以供同行借鉴。     

草制浆造纸中段废水处理及回用技术分析研究

中段废水是制浆造纸工业的主要污染源之一,从工程设计的角度出发,对草制浆造纸中段废水处理及回用提出一套可行适用的工艺方案;对主要工艺环节参数、设备备有说明,以供同行借鉴.     

制浆造纸废水生化出水的混凝处理研究

研究了硫酸铝和三氯化铁对制浆造纸废水生化出水的处理效果.研究发现,不调节原水pH值,硫酸铝投加量为600 mg/L或三氯化铁投加量为300mg/L时,混凝后废水的COD＜150 mg/L,色度＜50倍,出水均符合现阶段排放标准.混凝剂比较发现,在最佳反应条件下,2种混凝剂的处理效果相当,但硫酸铝混凝的成本低于三氯化铁....     

Modelling the absorption and desorption of cadmium on paper pulp using kinetic approaches

The presence of toxic metals on paper pulp and the migration of these metals to food from the food package is receiving significant attention. The final exposure levels for consumers depend on two main processes. First the potential of metals to bind paper pulp during manufacture. Second, the metal potential to migrate from paper to food during storage and use. Binding and unbinding processes are modelled for cadmium kinetics through kinetic approaches. The cadmium concentration in paper pulp is estimated from the cadmium concentration in the water-pulp liquor during manufacture, the temperature, and contact time. Two food simulants have been employed for desorption studies, water and acetic solution (3%, w/w). As expected, under acidic conditions desorption is total and rapid (close to 100% desorption reached in a few minutes). However, the desorption of cadmium into the neutral food simulant depends on the initial cadmium concentration in the paper pulp, temperature and contact time. Surface response curves for each combination are presented. Temperature did not affect cadmium binding, but played a significant role for the desorption processes into the neutral food simulant. The proposed equations offer a good fitting of the experimental values, with p < 0.001 and residuals within a factor of 3 for over 99% of the measured data. These models allow estimations of the expected exposure levels in consumers, on the basis of manufacture and use conditions. Linking the expected exposure with toxicity thresholds, such as the admissible daily intake (ADI), would allow a scientific assessment of the maximum acceptable cadmium levels in water-pulp liquors during manufacture and in the final paper pulp on the basic of the use patterns of each food packaging material.     

造纸中段废水的混凝-臭氧氧化深度处理研究

就混凝-臭氧氧化组合工艺对造纸中段废水生物处理出水的净化效果进行了研究.结果表明,Ca(OH)2对废水色度、TOC、COD和254 nm的紫外吸收值(UV254)的去除效果均优于聚合氯化铝/聚丙烯酰胺(PAC/PAM);Ca(OH)2-O3组合工艺的处理效果也优于PAC/PAM-O3工艺.当Ca(OH)2投加量为1 g/L、臭氧投加量为50 mg/L时,废水色度降低至10倍以下,COD小于150 mg/L.经Ca(OH)2混凝处理后,相对分子量在0.5～1.0 ku和10.0 ku以上的有机物显著减少;进一步臭氧氧化处理后,除0.5 ～1.0 ku范围的有机物大幅度增加外,其余分子量有机物显著减少.由于对色度贡献很大的大分子量物质的去除,废水的色度显著下降直至无色.     

Determining algal-available phosphorus in pulp and paper mill effluents: algal assays vs routine phosphorus analyses

We determined the potentially algal-available P (P(aa)) in pulp and paper mill effluents by two bioassay techniques (a dual-culture assay and a batch approach) and compared it with chemically analysed P (total P, total dissolved P, reactive P, dissolved reactive P and dissolved hydrolysable P). The mean P(aa) given by the dual-culture assay was within a 40% range of that given by the batch approach. The P(aa) obtained by both bioassays differed from total P. Dissolved reactive P appeared to be the most readily available chemical P fraction, but other P fractions also contributed to P(aa). The analysis of reactive P, which involves direct staining of an unfiltered sample, best approximated the P(aa) given by the dual-culture assay (relative error 9%). The results suggest that assessment of eutrophying effluent P can be improved by analysing simple chemical P fractions in wastewater. The fractions to be analysed, however, may be site specific.     

Betulinol and wood sterols in sediments contaminated by pulp and paper mill effluents: dissolution and spatial distribution

The goal was to determine dissolution potency of betulinol and wood sterols (WSs) from pulp and paper mill-contaminated sediments and the current stratification for assessment the load due to potential erosion in the river-like watercourse. Both compounds are wood extractives, which may be toxic to benthos and fish. This research continues a study in which other wood extractives, resin acids and their derivative, retene, were analysed. Sediments were collected from 1, 3.5, 12, 15, and 33 km downstream from the pulp and paper mills, and from 2 upstream reference sites. The dissolution potency into sediment–water elutriates (1?+?4?v/v) was studied by two agitation times and temperatures. The vertical amounts of extractives were determined from the uppermost 20 cm of sediment. The amounts of extractives potentially released were estimated from the sediment layers 0–2 and 2–5 cm by using spatial interpolation. According to the interpolation, the total amount of betulinol and β-sitosterol was calculated as kg/ha in the whole sediment area. Significant concentrations of betulinol (1,666 μg/g, dw) and WSs (2,886 μg/g, dw) were measured from the sediments. According spatial interpolation, the highest calculated amount of betulinol (4,726 kg/ha) and that of the most abundant WS, β-sitosterol (3,571 kg/ha), were in the lake where the effluents were discharged. In the dissolution experiment, the highest concentration of betulinol in sediment (0–10 cm) and elutriate was 412 μg/g (dw) and 165 μg/l, respectively. For WSs, concentrations were 768 μg/g (dw) in sediment and 273 μg/l in elutriate. In a worst-case scenario, betulinol may be desorbed to water in concentrations which are hazardous to aquatic animals. Instead WSs are not a risk in this study area. The amount of desorption varied depending on the concentration of contaminants in sediment, the nature of disturbance, and the sediment organic carbon content.     

制浆造纸业各工段节水减排技术研究

中国制浆造纸业近年来在节水减排方面取得了一定的进展,但相对于国际水平还有很大的差距,而且远没达到造纸行业取水定额指标。通过对我国制浆造纸业各个用水工段普遍使用的技术与国际先进技术进行了比较,为新建、改建和重组造纸工厂提供技术依据。结果表明,废纸浆比非木浆节约用水约100 m3/t,废水排放量减少约100 m3/t;化学热磨机械制浆比化学制浆少用水约100 m3/t,废水排放量可减少约100 m3/t;封闭洗涤比开式洗涤少用水至少50 m3/t,废水排水量减少至少54 m3/t;采用中浓技术比传统的低浓技术节约用水约30 m3/t,废水排放量减少约30 m3/t;制浆废水经处理后回用,可使用水量减少约60 m3/t,废水排放量减少约40 m3/t;造纸产生的白水通过膜分离技术处理后再回用到生产过程中,可减少新鲜水用量约150 m3/t,减少废水排放量约120 m3/t。由此可知,采用先进技术,不仅降低了取水压力,降低取水成本,而且减少了废水的排放,减少了排污费,能取得显著的经济和环境双重效益。     

Investigation of pathogenic Escherichia coli and microbial pathogens in pulp and paper mill biosolids.

Biosolids produced from pulp and paper mill wastewater treatment have excellent properties as soil conditioners, but often contain high levels of Escherichia coli. E. coli are commonly used as indicators of fecal contamination and health hazard; therefore, their presence in biosolids causes concern and has lead to restrictions in land-spreading. The objectives of this study were to determine the following: (1) if E. coli from the biosolids of a wastewater-free pulp and paper mill were enteric pathogens, and (2) if other waterborne microbial pathogens were present. E. coli were screened for heat-labile and heat-stable enterotoxin and verocytotoxin virulence genes using a polymerase chain reaction. Ten isolates were also screened for invasion-associated locus and invasion plasmid antigen H genes. None of the 120 isolates carried these genes. Tests for seven other microbial pathogens were negative. Effluents and biosolids from this mill do not contain common microbial pathogens and are unlikely to pose a health hazard.     

Assessing the biological status of fish in a river receiving pulp and paper mill effluents

This study compared the use of sentinel species- and community-based field approaches for assessing the biological status of fish living in a river receiving pulp and paper mill effluents. Three approaches were compared. Two approaches used sentinel species. One of these involved an internal/external examination of the fish that leads to the calculation of a fish health assessment index (HAI) and the other involved biochemical measurements of hepatic mixed function oxidase (MFO) activity and plasma steroid levels. The third approach characterized the fish community structure according to an index of biotic integrity (IBI). The comparison focused on how the methods respond to the hypothesis that recent process modifications/effluent treatment changes, resulting in demonstrable improvements in effluent quality, have beneficial effects on fish. Neither of the approaches using sentinel fish indicated clear mill-related influences either before or after the process modifications/effluent treatment changes. There was no evidence of depressed plasma steroids and increased MFO activity in fish frequently associated with mill effluent exposure in previous studies. While the HAI was higher at stations downstream from two mills, this could not be linked to effluent exposure alone. In contrast, the study of community structure showed a substantial improvement in fish assemblages at all the mill sites.     

Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions

In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.