Removal of wood extractives as pulp (pre-)treatment: a technological review

Wood extractives usually do not exceed five percent of dry wood mass but can be a serious issue for pulping as well as for the pulp itself. They cause contamination and damages to process equipment and negatively influence pulp quality. This paper addresses not only the extractives-related problems but also different solutions for these issues. It is an extensive review of different technologies for removing wood extractives, starting with methods prior to pulping. Several wood yard operations like debarking, knot separation, and wood seasoning are known to significantly decreasing the amount of wood extractives. Biological treatment has also been proven as a feasible method for reducing the extractives content before pulping, but quite hard to handle. During pulping, the extractives reduction efficiency depends on the pulping method. Mechanical pulping removes the accessory compounds of wood just slightly, but chemical pulping, on the other hand, removes them to a large extent. Organosolv pulping even allows almost complete removal of wood extractives. The residual extractives content can be significantly reduced by pulp bleaching. Nevertheless, different extraction-based methods have been developed for removing wood extractives before pulping or bleaching. They range from organic-solvent-based extractions to novel processes like supercritical fluid extractions, ionic liquids extractions, microwave technology, and ultrasonic-assisted extraction. Although these methods deliver promising results and allow utilization of wood extractives in most cases, they suffer from many drawbacks towards an economically viable industrial-scale design, concluding that further research has to be done on these topics. Graphical abstract

Effects of residual phenolic compounds on xylanase-assisted ClO2 bleaching of hardwood kraft pulp

In both pulping and bleaching processes, lignin in the pulp fiber is degraded into smaller molecules that need to be rinsed away. However, despite the installation of automatic washing equipment, the small phenolic compounds among other lignin degradation products can hardly be completely removed from the brownstock. Among the myriad of small phenolic compounds degrading from lignin, some are water-soluble and highly reactive with bleaching reagents. To understand the impact of residual phenolic compounds from black liquor on pulp bleaching, six monomeric phenolic model compounds were tested in this study. Catechol and vanillin showed inhibitory effects on xylanase activity, while catechol, vanillin, and guaiacol interfered with the delignification reaction in the chlorine dioxide (D) and alkaline extraction (E) stages of the bleaching sequence, thereby preserving the integrity of cellulose in the pulp. Because the efficiency of xylanase and bleaching reagents is hindered by the presence of these phenolic compounds, higher operational cost and more bleaching reagents are needed, which are incompatible with modern environmental policies in the world. Nonetheless, the presence of remaining soluble phenolic compounds in the brownstock can improve the bleaching selectivity important for the production of high-quality pulp with less-degraded cellulose chains.

Minimizing the Chlorine Content in Bleached Sulfate Pulp for Sanitary Tissue products and Food Packaging

The increasing consumption of pulp for chemical processing, including production of sanitary tissue products and other medical products, food packaging, as well as fillers for food products leads to new requirements for the quality of raw materials. The task of improving the characteristics of pulp has become particularly acute in connection with the COVID-19 epidemic: the demand for disposable nonwoven materials in direct contact with the human skin has increased several times over. The elemental chlorine free (ECF) sulfate pulp bleaching process, which uses chlorine dioxide as a bleaching agent, dominates bleached pulp production worldwide. The chlorine-containing compounds formed as a result of bleaching pollute not only waste water, but also the product itself. In the near future, it is expected that paper products made with chlorine-based bleaches may be banned for the production of sanitary tissue products and food packaging. If the products of the pulp and paper industry do not meet international consumer requirements, the pulp market for these purposes may face undesirable results. The most promising direction of modernization the existing bleaching schemes, both in terms of the process consumption parameters and the quality of the produced pulp, is the use of oxygen-alkaline bleaching in the first stage. Determination of total and organically bound chlorine content in pulp materials in accordance with ISO 11480:2017 on the advanced plant has shown, that the introduction of bleaching schemes using oxygen-alkaline agents will ensure the recommended content of chlorine compounds while maintaining the necessary characteristics of pulp for the manufacture of medical and sanitary tissue products, food packaging. However, high quality of finished products that meet consumers’ requirements is possible only if the chlorine content is controlled at all stages of pulp production, since the quantitative indicators of this substance content remain close to the upper allowable limit. For citation: sofronova e.D., Lipin v.A., Dubovy v.K., Sustavova t.A. Minimizing the Chlorine Content in bleached sulfate pulp for sanitary tissue products and food packaging. Lesnoy Zhurnal [Russian Forestry Journal], 2021, no. 3, pp. 186–195. DOI: 10.37482/0536-1036-2021-3-186-195

Degradation of cellulosic key chromophores by ozone: a mechanistic and kinetic study

Chromophores, colored substances of rather high stability that reduce brightness, are present in all kinds of cellulosic products, such as pulp, fibers, aged cellulosic material, and even in very low concentrations in highly bleached pulps. Thus, they are the prime targets of industrial pulp bleaching. In this study, the three cellulosic key chromophores 2,5-dihydroxy-1,4-benzoquinone (DHBQ, 1), 5,8-dihydroxy-1,4-naphthoquinone (DHNQ, 2), and 2,5-dihydroxyacetophenone (DHAP, 3) were bleached with ozone at pH 2 resembling industrial conditions (Z-stage). Bleaching kinetics were followed by UV/Vis spectrophotometry. The chemical structures of the degradation products were analyzed using NMR spectroscopy as well as GC/MS and confirmed by comparison with authentic reference compounds. The main, stable intermediates in the ozonation reactions have been elucidated by employing ozone not in excess but roughly stoichiometric amounts: mesoxalic acid (4) from DHBQ (1), rhodizonic acid (5) from DHNQ (2), and hydroxy-[1,4]-benzoquinone (8) from DHAP (3). As the final products at a large excess of ozone, a complex mixture of carboxylic acids (C1 to C4) was obtained, with the C4 acids being formed by subsequent condensation of smaller fragments (malonic acid and mesoxalic acid) rather than directly as ozonation products. At shorter reaction times and lower ozone excess, some aldehydes and ketones (C2 and C3) were contained in addition. The mixture of the degradation products was not completely stable but tended to undergo further changes, such as decarboxylation and condensation reactions. The reaction mechanisms of degradation by ozone, intermediate formation and re-condensation are described and discussed. Graphic abstract

STUDY ON MEASUREMENT MODEL OF LIGNIN CONTENT IN PULP AFTER ALKALINE EXTRACTION

Because kappa number cannot accurately represent the lignin content in the pulp after alkaline extraction, lead to the excessive dosage of bleaching chemicals added and the pollutant content increases. In order to accurately determine the dosage of bleaching agent, reduce pollutant emissions, a prediction model of lignin content of pulp was established by analyzing the correlation between lignin content and alkaline extraction conditions in this paper. The results show that the established soft sensor model can accurately measure lignin content, it is helpful to determine the amount of bleaching agent more accurately, reduce pollutant generation after pulp bleaching.

Studi Kelayakan Penggunaan Air Kondensat dan Air Pendingin sebagai Pengencer pada Tahap Awal Proses Pemutihan Pulp

Penggunaan fresh water di industri pulp sangat besar yaitu sekitar 25,000 galon per 1 ton kertas. Hal ini menuntut adanya inovasi terkait penghematan penggunaan air yang diambil langsung dari alam (fresh water). Inovasi terbaru terkait mengurangi atau mengganti fresh water adalah dengan menggunakan condensate water atau cooling water pada proses pemutihan pulp (bleaching). Condesate water diambil dari hasil samping proses di Evaporation Plant. Air pendingin (cooling water) yang digunakan dari Cooling Tower. Cooling water memiliki range yang rendah sehingga tidak efektif dalam pertukaran panas di Cooling Tower. Pada penelitian ini dilakukan variasi pencampuran condensate water yang akan diaplikasikan pada proses bleaching tahap awal dari serangkain pemutihan pulp (D0) yaitu : condensate water 10% + fresh water 90%, condensate water 20% + fresh water 80%, condensate water 30% + fresh water 70%, condensate water 40% + fresh water 60%, condensate water 50% + fresh water 50% dan fresh water 100%. Pada pencampuran cooling water yang akan diaplikasikan pada proses bleaching tahap D0 yaitu : cooling water 100%, cooling water 80% + fresh water 20%, cooling water 60% + fresh water 40%, cooling water 40% + fresh water 60%, cooling water 20% + fresh water 80%, dan fresh water 100%. Data brightness cooling water 100% yaitu 65,49% tidak berbeda dengan nilai brightness fresh water 100% yaitu 65,27% sedangkan nilai brightness condensate water 64,46% pada konsentrasi 10%. Dari penelitian ini dapat disimpulkan bahwa mengganti fresh water dengan cooling water tidak mempengaruhi pulp yang dihasilkan sedangkan menggunakan condensate water sebagai pengencer pulp menyebabkan pulp yang dihasilkan mengalami penurunan brightness. Cooling water dapat menjadi pengganti fresh water sebagai pengencer pulp diproses bleaching.

A 30-Year Study of Impacts, Recovery, and Development of Critical Effect Sizes for Endocrine Disruption in White Sucker (Catostomus commersonii) Exposed to Bleached-Kraft Pulp Mill Effluent at Jackfish Bay, Ontario, Canada

Jackfish Bay is an isolated bay on the north shore of Lake Superior, Canada that has received effluent from a large bleached-kraft pulp mill since the 1940s. Studies conducted in the late 1980s found evidence of reductions in sex steroid hormone levels in multiple fish species living in the Bay, and increased growth, condition and relative liver weights, with a reduction in internal fat storage, reduced gonadal sizes, delayed sexual maturation, and altered levels of circulating sex steroid hormones in white sucker (Catostomus commersonii). These early studies provided some of the first pieces of evidence of endocrine disruption in wild animals. Studies on white sucker have continued at Jackfish Bay, monitoring fish health after the installation of secondary waste treatment (1989), changes in the pulp bleaching process (1990s), during facility maintenance shutdowns and during a series of facility closures associated with changing ownership (2000s), and were carried through to 2019 resulting in a 30-year study of fish health impacts, endocrine disruption, chemical exposure, and ecosystem recovery. The objective of the present study was to summarize and understand more than 75 physiological, endocrine, chemical and whole organism endpoints that have been studied providing important context for the complexity of endocrine responses, species differences, and challenges with extrapolation. Differences in body size, liver size, gonad size and condition persist, although changes in liver and gonad indices are much smaller than in the early years. Population modeling of the initial reproductive alterations predicted a 30% reduction in the population size, however with improvements over the last couple of decades those population impacts improved considerably. Reflection on these 30 years of detailed studies, on environmental conditions, physiological, and whole organism endpoints, gives insight into the complexity of endocrine responses to environmental change and mitigation.