Caustic Extraction Research Articles

A biorefinery scheme to fractionate bamboo into high-grade dissolving pulp and ethanol

BackgroundBamboo is a highly abundant source of biomass which is underutilized despite having a chemical composition and fiber structure similar as wood. The main challenge for the industrial processing of bamboo is the high level of silica, which forms water-insoluble precipitates negetively affecting the process systems. A cost-competitive and eco-friendly scheme for the production of high-purity dissolving grade pulp from bamboo not only requires a process for silica removal, but also needs to fully utilize all of the materials dissolved in the process which includes lignin, and cellulosic and hemicellulosic sugars as well as the silica. Many investigations have been carried out to resolve the silica issue, but none of them has led to a commercial process. In this work, alkaline pretreatment of bamboo was conducted to extract silica prior to pulping process. The silica-free substrate was used to produce high-grade dissolving pulp. The dissolved silica, lignin, hemicellulosic sugars, and degraded cellulose in the spent liquors obtained from alkaline pretreatment and pulping process were recovered for providing high-value bio-based chemicals and fuel.ResultsAn integrated process which combines dissolving pulp production with the recovery of excellent sustainable biofuel and biochemical feedstocks is presented in this work. Pretreatment at 95 °C with 12% NaOH charge for 150 min extracted all the silica and about 30% of the hemicellulose from bamboo. After kraft pulping, xylanase treatment and cold caustic extraction, pulp with hemicellulose content of about 3.5% was obtained. This pulp, after bleaching, provided a cellulose acetate grade dissolving pulp with α-cellulose content higher than 97% and hemicellulose content less than 2%. The amount of silica and lignin that could be recovered from the process corresponded to 95 and 77.86% of the two components in the original chips, respectively. Enzymatic hydrolysis and fermentation of the concentrated and detoxified sugar mixture liquor showed that an ethanol recovery of 0.46 g/g sugar was achieved with 93.2% of hydrolyzed sugars being consumed. A mass balance of the overall process showed that 76.59 g of solids was recovered from 100 g (o.d.) of green bamboo.ConclusionsThe present work proposes an integrated biorefinery process that contains alkaline pre-extraction, kraft pulping, enzyme treatment and cold caustic extraction for the production of high-grade dissolving pulp and recovery of silica, lignin, and hemicellulose from bamboo. This process could alleviate the silica-associated challenges and provide feedstocks for bio-based products, thereby allowing the improvement and expansion of bamboo utilization in industrial processes.

Integration of hemicellulose recovery and cold caustic extraction in upgrading a paper-grade bleached kraft pulp to a dissolving grade

In this study, a hemicellulose recovery process was integrated with a cold caustic extraction (CCE) process in upgrading paper-grade bleached kraft pulp to dissolving grade. Under the conditions of 15% NaOH, 10% pulp consistency, 30℃ and 1 h, a paper-grade softwood bleached kraft pulp was purified to a dissolving-grade pulp with 97.57% α-cellulose and 1.67% pentosan contents. The spent liquor from the cold caustic extraction process was sequentially extracted with ethanol to precipitate and recover the dissolved hemicelluloses, followed by evaporation to recover the ethanol. After the recovery of hemicelluloses and ethanol, the spent liquor can be reused as the caustic solution for the CCE process without compromising the resulting pulp properties. The results demonstrated that it is feasible to integrate hemicellulose production with the cold caustic extraction process of dissolving pulp production, based on the concept of biorefinery.

Upgrading Paper-grade Softwood Kraft Pulp to Dissolving Pulp by Cold Caustic Extraction

Upgrading Paper-grade Softwood Kraft Pulp to Dissolving Pulp by Cold Caustic Extraction

EFEITOS DA XILANA NA PRODUÇÃO DE CELULOSE DE EUCALIPTO

RESUMO A busca por uma melhor utilização da madeira na indústria de celulose tem alimentado o interesse em uma utilização mais racional dos seus componentes, em particular as xilanas. O impacto da remoção das xilanas e de sua redeposição nas propriedades da polpa solúvel e tipos de papel de imprimir e escrever (P&W), são discutidos neste trabalho. Celulose kraft (15,6% xilanas) tratamento com 10-70 g.L-1 NaOH resultou em polpas de 14,5-5,9% de xilanas. Os tratamentos diminuiu a lignina e teores de HexA e causou impacto positivo significativo na deslignificação com oxigênio e posterior branqueamento ECF. A remoção de xilanas diminuiu a refinabilidade da polpa, índice de retenção de água e índice de tração, mas aumentou a drenabilidade, a capacidade de absorção de água, a capilaridade Klemm e o bulk. No geral, polpas com baixo teor de xilanas mostrou propriedades quase ideais de polpas para dissolução. Em uma segunda etapa da pesquisa, xilanas extraída de polpa não branqueada (BXL) e polpa de eucalipto branqueada (WXL) por extração cáustica fria (CCE) foram adicionados a uma polpa marrom comercial na deslignificação com oxigênio (O-estágio) e foi branqueada. Deposição de xilanas ocorreu em grau variável (até 7% em peso de celulose), dependendo do pH da reação do O-estágio. O branqueamento da polpa não foi prejudicada por WXL deposição de xilanas, mas ligeiramente afetada negativamente por xilanas BXL. A refinabilidade da polpa celulósica foi melhorada pela deposição de xilanas. As xilanas depositadas foram bastante estáveis ao longo do branqueamento, apesar de, com as xilanas WXL ser mais estável do que com as BXL. Em baixo consumo de energia, as xilanas depositados melhorou as propriedades física e mecânicas. A extração de xilanas pelo CCE com posterior deposição em polpa no O-estágio mostrou atraente para a fabricação de polpa com alto conteúdo de xilanas tipos de papel P&W.

Characterization of dissolving pulp by fibre swelling in dilute cupriethylenediamine (CUEN) solution in a MorFi analyser

Abstract The swelling of dissolving pulps has been investigated by a new method based on the MorfiR analyser, which is measuring the width variation of thousands of fibres in a cupriethylenediamine (CUEN) solution in a few minutes. Pulps from various origins were analysed coming from softwood, birch wood, eucalyptus wood, kraft pulps, sulphite pulps and ECF and TCF bleached pulps, which were modified by several treatments including chemical (cold caustic extraction, hypochlorite) or enzymatic (cellulase) methods. The swelling was much affected by the crystalline form of cellulose and the hemicellulose content but did not depend neither on the cellulose DP nor on the fibre structure (hardwood vs. softwood). The dissolving pulp reactivity in the viscose process was also assessed by swelling in dilute solutions of cupriethylenediamine (CUEN) instead of the Fock’s method.

Desilication of bamboo for pulp production

Bamboo is one of the world’s fastest growing feedstocks. It is a promising nonwood resource that can be used in the pulp and paper industry. Among more than 1200 species of bamboo, the timber varieties can be processed much like trees, allowing current pulp mill logistical systems to be used. Bamboo can be difficult to pulp because of its high silica content, which creates issues for black liquor recovery. This study compares two methods of reducing the silica content of a common species of timber bamboo. Specifically, the dermis layer of Moso bamboo (Phyllostachys edulis) was removed through mechanical treatment and then chipped. The same species was also chipped without treatment. The two chipped materials were then alkali extracted and subjected to kraft pulping experiments. The pulps were bleached with an OD0(EP)D1 sequence. The material was then refined and formed into handsheets. The results indicate that 80% of the silica could be removed from the bamboo material through a combination of dermal mechanical treatment and caustic chip extraction. Caustic chip extraction removed a significant portion of hemicellulose materials, which in turn lowered cooking yields but had minimal effect on pulp properties.

Enhanced removal of hemicelluloses from cellulosic fibers by poly(ethylene glycol) during alkali treatment

Enhancing removal of hemicelluloses from cellulosic fibers is of decisive importance for producing high-purity cellulose. In this study, poly(ethylene glycol) (PEG) was added to a cold caustic extraction (CCE) process to promote removal of hemicelluloses from a softwood sulfite dissolving pulp. The content of hemicelluloses was considerably decreased from 11.4 % in the original sample to 5.3 % in the PEG/CCE-treated sample under the studied conditions. This positive result of PEG addition can be explained by (1) improved inward penetration and diffusion of NaOH into the fiber structure and outward diffusion of hemicelluloses from the fiber structure to the bulk phase, and (2) enhanced fiber swelling due to inclusion of PEG in the fiber walls and improved NaOH diffusion. Moreover, the effects of PEG/CCE treatment on the distribution of hemicelluloses in the fiber walls and the molecular weight of the residual hemicelluloses in the resulting pulp were investigated.

Combination of mechanical, alkaline and enzymatic treatments to upgrade paper-grade pulp to dissolving pulp with high reactivity

A modified process consisting of an initial mechanical refining (R) followed by a low-alkali (5.5% NaOH) cold caustic extraction (CCE) and finally an endoglucanase (EG) treatment (R-5.5%CCE-EG) was investigated for upgrading paper-grade pulp to dissolving pulp. Results showed that compared to the conventional process (9%CCE-EG), the modified process can decrease the alkali concentration (from 9% to 5.5%) to achieve a similar hemicelluloses removal while simultaneously enhancing the Fock reactivity (from 62.2% to 81.0%). The improved results were due to the fact that the mechanical refining resulted in favorable fiber morphological changes, including increased pore volume/size, water retention value and specific surface area. Consequently, the hemicelluloses removal was enhanced even under the subsequent low-alkali CCE condition. A synergic effect of refining, low alkali concentration and enzymatic activation was responsible for the higher reactivity of resulting dissolving pulp.

Simultaneous bench scale production of dissolving grade pulp and valuable hemicelluloses from softwood kraft pulp by ionic liquid extraction

Ionic liquid extraction of wood pulp has been highlighted as a highly potential new process for dissolving pulp production. Coproduction with a polymeric hemicellulose fraction was demonstrated in bench scale from softwood kraft pulp using extraction with the ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIM OAc) and water. In total, the recovered pulp and hemicellulose fraction together yielded 95.5wt.% of the pulp input. The extracted pulp had a remarkably high purity with an R18-value of 97.8%. The hemicellulose fraction consisted of galactoglucomannan, arabinoxylan and some cellulose and was precipitated from the ionic liquid-water mixture. After hydroxypropylation of the hemicellulose fraction, films were prepared and barrier and strength properties were compared to films from other polysaccharides. Reduced oxygen and water vapor permeation and good strength properties were demonstrated when compared to corresponding films from hydroxypropylated xylan from cold caustic extraction. The films have potential for applications in food packaging and edible films.

Mechanical pretreatment improving hemicelluloses removal from cellulosic fibers during cold caustic extraction

Hemicelluloses removal is a prerequisite for the production of high-quality cellulose (also known as dissolving pulp), and further recovery and utilization of hemicelluloses, which can be considered as a typical Integrated Forest Biorefinery concept. In this paper, a process of combined mechanical refining and cold caustic extraction (CCE), which was applied to a softwood sulfite sample, was investigated. The results showed that the hemicelluloses removal efficiency and selectivity were higher for the combined treatment than that for the CCE alone. The combined treatment can thus decrease the alkali concentration (from 8% to 4%) to achieve a similar hemicelluloses removal. The improved results were due to the fact that the mechanical refining resulted in increases in pore volume and diameter, water retention value (WRV) and specific surface area (SSA), all of which can make positive contributions to the hemicelluloses removal in the subsequent CCE process.

Depolymerization of cellulose during cold acidic chlorite treatment

Abstract A cold holocellulose treatment (cHolT) was studied on a bleached kraft pulp (BKP) of Eucalyptus to observe the degradation of polysaccharides in pulp by chlorite at room temperature under conditions of slightly acidic pH and high chlorine charge (313% of active chlorine on BKP). Based on literature data, cellulose depolymerization is expectable by chlorite treatments at 70°C and reinforced chlorite charge, while the addition of dissolved lignin could protect cellulose. In the present study, polysaccharide degradation was followed by TAPPI viscosity, size-exclusion chromatography coupled to multidetectors, pulp yield, kappa number, elemental sugar analysis of pulps, and total organic carbon detection in filtrates. cHolTs were repeated several times without significant polysaccharide degradation, but the insertion of a caustic extraction stage at 70°C induced little degradation. This study opens the way to the setup of inert delignification procedures to be applied on raw or processed lignocellulosic samples from biorefinery studies.

Enhancing hemicelluloses removal from a softwood sulfite pulp

Hemicelluloses removal is highly desirable in many biomass processes, including the pretreatment steps of the bioconversion for ethanol production, production of high-quality dissolving pulps. In this study, a sequential treatment consisting of pulp fractionation, followed by caustic treatment to remove hemicelluloses from a softwood sulfite pulp, was investigated. The long-fiber fraction obtained after pulp fractionation, had a lower hemicelluloses content and smaller specific surface area, but larger pore diameter than the short-fiber fraction. The fiber fractions were subsequently treated in a cold caustic extraction (CCE) or hot caustic extraction (HCE). Results showed that hemicelluloses removal in the long-fiber fraction was more pronounced than the short-fiber fraction in both CCE and HCE processes. Other parameters, such as hemicelluloses removal selectivity, yield were studied. The underlying explanations were given.

Comparative evaluation of the action of two different endoglucanases. Part II: On a biobleached acid sulphite pulp

A TCF sulphite pulp, bleached at the laboratory scale with a laccase–violuric acid system and complemented with a pressurized hydrogen peroxide stage, was treated with two endoglucanases, one obtained from Paenibacillus barcinonensis (B) and the other one produced from Cerrena unicolor (F) to improve cellulose reactivity. The treated pulps were evaluated in terms of brightness, viscosity, α-cellulose, water retention value, fibre morphology, Fock solubility, NMR and carbohydrate composition of pulps and liquors. Results revealed that both endoglucanases improved cellulose reactivity, albeit in a different way; thus, B caused no scissions in the cellulose chain and no significant reduction in fibre length, whereas F decreased viscosity and shortened fibre length, leading to lower reactivity value. The liquor composition of soluble carbohydrates released by the enzymatic treatments revealed the B had a processive mode of action since short oligosaccharides, cellobiose and glucose, were obtained. F hydrolysed, from high to low concentration, cellobiose, glucose and cellotriose. Importantly, environmentally friendly dissolving pulp with 90 % Fock solubility was obtained, combining two enzymatic treatments: a laccase–mediator system and then a cellulase from P. barcinonensis (B). In order to improve the quality of final dissolving pulp, a pulp purification step was introduced before the B endoglucanase treatment. The cold caustic extraction lead to reduce the amount of hemicelluloses by 42 % with respect to biobleached pulp, but Fock solubility was also reduced. However, complementing the purification step with F treatment, reduced the amount of hemicelluloses but also improved Fock solubility by 17 %, although some presence of cellulose II was detected by NMR.

Comparative evaluation of the action of two different endoglucanases. Part I: On a fully bleached, commercial acid sulfite dissolving pulp

A fully bleached commercial acid dissolving pulp was treated with two endoglucanases, one obtained from Paenibacillus barcinonensis (B) and the other one produced from Cerrena unicolor (F) with the intention to improve cellulose reactivity and processability in the viscose process. B cellulase was tested under 120 U/g oven dry pulp (odp) and the F cellulase under two conditions, 12 and 60 U/g odp. In addition, a purification stage, consisting in a cold caustic extraction (CCE) of 9 % w/v NaOH, was applied before or after the enzymatic treatment in order to reduce the amount of hemicellulose and improve the action of enzymes. The treated pulps were evaluated in terms of brightness, viscosity, water retention value, fibre morphology, carbohydrate composition, Fock solubility and NMR. In general, results revealed that both endoglucanases improved cellulose reactivity, albeit in a different way; thus, B caused no scissions in the cellulose chain and no significant reduction in fibre length, whereas F strongly decreased viscosity, shortened fibre length and increased considerably the amount of fines. The result of applying two different doses of F cellulase was reflected on Fock solubility and fibre morphology. F60 treatment was found to give the highest value of Fock solubility and the biggest reduction of fibre length. The effect of both endoglucanases on Fock solubility was increased by introducing an earlier CCE stage. Finally, a CCE_B120 pulp with 3 % of hemicellulose and 69 % of Fock solubility was obtained.

Improved Cellulose Yield in the Production of Dissolving Pulp from Bamboo Using Acetic Acid in Prehydrolysis

Despite increasing demand for dissolving pulps from raw material, production costs remain quite high compared to regular paper pulp. Research literature to date has focused on improving performance and quality but has not simultaneously explored how to improve yield, which typically falls below 35%. Dissolving pulp from bamboo, as a widely available, high-quality raw material, was investigated with dilute acetic acid pre-hydrolysis before cooking and cold caustic extraction prior to bleaching. It was found that dilute acetic acid in the pre-hydrolysis stage could speed up the degradation of hemicellulose in bamboo and improve the diffusion of the cooking liquor in bamboo fiber compared with hot-water treatment. The dissolving pulp from bamboo was produced with 93% α-cellulose, 90% ISO brightness, 959 mL/g viscosity, 5.23% xylans, and 0.17% ash. The overall yield on the basis of raw material was 37%, which was higher than other documented processes using other agents in pre-hydrolysis.

Cellulose acetate from biomass waste of olive industry

In the present work cellulose powder was extracted from olive industry solid waste and then converted into cellulose acetate. The cellulose powder was extracted from olive industry solid waste by kraft pulping process and multistep bleaching p sequences. An elemental chlorine-free chemical bleaching sequence chlorine dioxide (D)-cold caustic extraction (E)-hypochlorite (H)-hydrogen peroxide (P) was used. Cellulose powder was obtained in about 35 % yield. The extracted cellulose and cellulose acetate made from thereof were extensively characterized using Fourier transform infrared spectroscopy, electron microscopy sciences, gel-permeation chromatography/high-performance liquid chromatography, and viscometry. Our key finding in this study was that olive industry solid waste is a valuable source of cellulose powder and its derivatives. This is important, since our results show how lignocellulosic agricultural wastes could be utilized and converted into cellulose products with high value.

Upgrading softwood bleached kraft pulp to dissolving pulp by cold caustic treatment and acid-hot caustic treatment

Two chemical processes for hemicellulose extraction have been applied on a softwood kraft pulp in an attempt to convert paper pulp into dissolving grade pulp. The cold caustic extraction process (CCE) was performed under conventional and unconventional conditions. Alkali concentration ranged from 3% to 12% and temperature from 25 to 110°C. As expected, the results showed that NaOH concentration had a predominant effect on xylan and glucomannan removal. The effect of temperature was more complex since the best removal was observed below 40°C or above 80°C. The unexpected good results obtained at high temperature would be due to the contribution of some alkaline degradation. Under the best conditions, 80% of the xylan and 60% of the glucomannan were removed. The cellulose II content was measured by solid state NMR spectroscopy. Formation of cellulose II increased with the concentration of caustic soda and was correlated to the extraction of hemicellulose. A second process consisting in an acid stage at high temperature (up to 150°C) followed by a hot caustic extraction (A-HCE) was also tested. Promising results in terms of hemicellulose removal were obtained when temperature in A was above 140°C. This might be due to a combination of acidolysis during A and peeling reactions during HCE. However, cellulose was partly depolymerized because of the severity of the A step. The two processes were compared in the context of getting to a viscose grade dissolving pulp.

Ionic liquid extraction method for upgrading eucalyptus kraft pulp to high purity dissolving pulp

High purity cellulose from wood is an important raw material for many applications such as cellulosic fibers, films or the manufacture of various cellulose acetate products. Hitherto, multi-step refining processes are needed for an efficient hemicellulose removal, most of them suffering from severe cellulose losses. Recently, a novel method for producing high purity cellulose from bleached paper grade birch kraft pulp was presented. In this so called IONCELL process, hemicelluloses are extracted by an ionic liquid–water mixture and both fractions can be recovered without yield losses or polymer degradation. Herein, it is demonstrated that bleached Eucalyptus urograndis kraft pulp can be refined to high purity acetate grade pulp via the IONCELL process. The hemicellulose content could be reduced from initial 16.6 to 2.4 wt% while persevering the cellulose I crystal form by using an optimized 1-ethyl-3-methylimidazolium dimethylphosphate-water mixture as the extraction medium. The degree of polymerization was then reduced by a sulfuric acid treatment for subsequent acetylation of the pulp, resulting in a final hemicellulose content of 2.2 wt%. When pre-treating the pulp enzymatically with endoxylanase, the final hemicellulose content could be reduced even to 1.7 wt%. For comparison, the eucalyptus kraft pulp was also subjected to cold caustic extraction and the same subsequent acid treatment which led to 3.9 wt% of residual hemicelluloses. The performance in acetylation of all produced pulps was tested and compared to commercial acetate grade pulp. The endoxylanase-IONCELL-treated pulp showed superior properties. Thus, an ecologically and economically efficient alternative for the production of highest value cellulose pulp is presented.

Xylan enriched viscose fibers

In this study, a new xylan enriched viscose fiber was developed. A high molecular weight xylan with a degree of polymerization of 150–200 was added during a late stage of the viscose production process. The xylan deriving from a cold caustic extraction (CCE) of an eucalypt paper pulp was introduced to the process after xanthation and thus neither objected to any degradation conditions during alkalization nor to the xanthation step. About 90 % of the added xylan was transferred to the final fiber. A xylan content of up to 7.5 % was achieved. Fiber properties like strength showed a comparable level to the reference fibers while the water retention value was clearly raised due to the higher content of hemicelluloses. The hemicellulose distribution over the fiber cross section was investigated by enzymatic peeling. Even though a segregation of the different polysaccharides was observed, the goal of a good blending of CCE-xylan into cellulosic fibers with new interesting features was achieved.

SO2–ethanol–water (SEW) fractionation process: production of dissolving pulp from spruce

SO2–ethanol–water (SEW) fractionation process is a highly attractive platform for future lignocellulosic Biorefineries. Its governing advantages include high flexibility in the selection of the raw material, simple and efficient recovery of fractionation chemicals, absence of carbohydrate degradation (both cellulose and hemicelluloses), and high reaction rates. The process is suitable for production of various carbohydrate- and lignin-based products including papermaking pulp, glucose, bioalcohols and lignosulfonates. The present paper addresses the possibility of producing dissolving pulp from spruce using SEW fractionation followed by ECF bleaching with and without hot caustic extraction. Comprehensive characterisation of chemical and macromolecular properties of the SEW dissolving pulps was complemented by determining the quality of viscose. The comparison with conventional viscose-grade acid sulfite pulps revealed close proximity in all properties. Therefore, considering the advantages of SEW process, it is suggested as a possible replacement for acid sulfite process in dissolving pulp manufacturing.