Totally chlorine‐free bleaching of Acetosolv pulps: a clean approach to dissolving pulp manufacture

Eucalyptus globulus wood samples were delignified in media containing concentrated acetic acid, water and hydrochloric acid (Acetosolv process) under optimized conditions, and the pulps were subjected to totally chlorine‐free (TCF) bleaching. Alkaline extractions, oxygen delignification, ozone treatment, enzymatic xylan removal and hydrogen peroxide oxidation in alkaline media were investigated as individual steps in selected bleaching sequences. Under the best conditions, fully bleached pulps with favourable characteristics for dissolving pulp manufacture were obtained. © 2001 Society of Chemical Industry     

Elemental chlorine-free bleaching halfa pulp

Halfa, also known as Stipa tenacissima, is grown in North Africa and south Spain. Due to its short fiber length, paper of halfa remains bulk and takes the block letters well. In this study halfa was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were pulped by conventional Kraft process: one from the original halfa material and the other from halfa pretreated by diluted acid. The pulp produced from halfa pretreated by diluted acid was bleached by elemental chlorine-free sequences, DEPD and DEDP. Yield, Kappa number, brightness and α-cellulose contents of bleached and unbleached pulps were evaluated. The results show that during the chemical pulping process, treated halfa was easily cooked than that original halfa. Treated halfa pulp also showed very good bleaching, showing brightness level of 94.8% ISO, yield 93.6% and α-cellulose content 96.8% with DEDP bleaching sequence compared to 83.2% ISO brightness level, 92.8% yield and 95.1% α-cellulose content for bleached pulp with DEPD bleaching sequence. On the other hand, the physicomechanical properties of pulp were not notably reduced by the bleaching process. Breaking length, tear and burst index of paper sheets were acceptable. Therefore, this halfa material could be a worthwhile choice for cellulosic fiber supply.     

麦草浆二氧化氯与氧气脱木素效率及相应漂白流程的对比

对麦草浆二氧化氯与氧气脱木素效率及相应的漂白流程进行了对比研究。结果表明,ClO2脱木素(D0)对木素的修饰和改性效果好于氧脱木素(O),在脱木素率低于及接近氧脱木素率的条件下,D0浆的可漂性均大于O浆。在D0段和O段脱木素率相同的条件下,采用D0A/QP、D0EP漂白流程漂后纸浆白度分别比OA/QP漂白流程高11.2和10.3个百分点。D0段废液和相应D0A/QP漂白流程三段混合废水的CODCr负荷均比O段和OA/QP漂白流程混合废水的CODCr负荷轻。D0段和O段废液的紫外光谱都呈现出木素苯环的特征吸收。纸浆的FT-IR谱图分析表明,D0浆和O浆中的羟基和羰基数量增多,随着漂白的进行,羰基等主要发色基团逐渐消除,纸浆白度得到提高。纸浆纤维形态的SEM分析显示,D0段和相应的D0A/QP漂白流程对纤维表面的破坏和损伤较O段和相应的OA/QP漂白流程轻。     

Simulating the impact of kraft pulping and bleaching parameters on Eucalyptus camaldulensis pulp properties using MATLAB

In this work, Eucalyptus camaldulensis was evaluated as the raw material for chemical pulp under different pulping and bleaching conditions. The pulping was carried out at different H‐factors, and at different effective alkalis. The resulting pulps were then oxygen delignified and bleached using various dosages of bleaching chemicals in a D₀EpD₁ sequence. The effect of independent variables (pulping or bleaching variables) on dependent variables (pulp properties) was analysed based on the multivariable least square method via MATLAB software. An agreement was found between the results predicted from the models and the experimental data. To obtain a kappa number of 15, the optimum pulping conditions were a temperature of 155°C, a time of 225 min, and an EA of 23%. Also, the hexenuronic acid (HexA) content of cooked pulp was significantly decreased in the chlorine dioxide bleaching stages, and was only marginally related to the final HexA content of bleached pulps.     

High‐quality cellulose triacetate prepared from bamboo dissolving pulp

Cellulose triacetate (CTA) was prepared from high‐grade bamboo dissolving pulp in general acetylation medium of acetic acid/acetic anhydride/sulfuric acid system. Despite its properties being improved compared with these of CTA prepared from viscose bamboo pulp, many insoluble residues still remained in its acetylation medium, which resulted in the decrease of the brightness and thermal stability of prepared CTA. Characterization of the insoluble residue indicated that its formation was associated with a higher content of xylan and ash in high‐grade bamboo pulp than in high‐grade hardwood pulp, in which insoluble residue was negligible. Because of the poor solubility of xylan diacetate (XDA) in acetylation medium, the insoluble residue formed through the aggregation of XDA and CTA by ultrastructural effects of the pulps during the precipitation of XDA. An addition to the good solvent of XDA, such as 1,2‐dichloroethane to acetylation medium of high‐grade bamboo pulp, could release the aggregation of XDA and CTA and dissolve the insoluble residue, which could lead to the improvement of the transmittance of reaction solution, as well as the properties of CTA prepared such as brightness and thermal stability. This study showed that high‐quality CTA could be prepared from high‐grade bamboo dissolving pulp in acetylation with an addition of solvent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A new electrochemical technique for bleaching cellulose pulp

A study of electrochemical bleaching of cellulose pulp was carried out in an electrolyte cell composed of a horizontal graphite anode and a parallel stainless screen steel cathode, using NaCl as electrolyte. Variables studied were: current density, sodium chloride concentration, pulp concentration, pH and temperature. The rate of bleaching was found to increase with increasing current density, salt concentration and temperature. The rate of bleaching was found to decrease with increasing pH and pulp concentration. Energy consumption ranged from 0.1 kWh kg^?1 (pulp) to 1.75 kWh kg^?1 (pulp), depending on current density and degree of bleaching. The quality of electrochemically bleached pulp was found to compare favourably with that of chemically bleached pulp.     

Strategies to reduce the brightness reversion of industrial ECF bleached Eucalyptus globulus kraft pulp

BACKGROUND: Brightness stability is a key property of bleached chemical pulps and is primarily determined by wood species and bleaching process conditions. Eucalyptus globulus is becoming a very important raw material for hardwood pulp production. In spite of this importance, there is a relative lack of systematic studies in the literature dealing with the subject. This research aims to study the effect of some of the foremost bleaching parameters of a DEDD bleaching sequence as well as the effect of a final P stage (DEDP instead of DEDD) in the brightness stability of bleached E. globulus kraft pulps. RESULTS: The increase of the D₀ stage temperature from 55 °C to 90 °C caused an increase in brightness stability. Increasing the ClO₂ charges from 2.8% to 3.2% also improved significantly the brightness stability. A high H₂SO₄ charge in the D₀ stage (10 kg tonne^?1 pulp) diminished the brightness stability. The combination of H₂O₂ addition to the E stage and ClO₂ reduction in the two final D stages does not affect brightness reversion. Raising the D₂ stage temperature from 65 °C to 82 °C decreased the brightness reversion, while an increase was obtained when the temperature rose above 82 °C. Substitution of the last ClO₂ stage in the DEDD sequence by a H₂O₂ stage (DEDP) significantly reduced the brightness reversion. CONCLUSION: For an existing pulp mill in which the implementation of new technologies to improve brightness reversion is considered, the results obtained showed that brightness stability can be improved without any significant capital investment. Copyright © 2007 Society of Chemical Industry     

One-Step Fractionation of the Main Components of Bamboo by Formic Acid-based Organosolv Process Under Pressure

To promote the efficient utilization of lignocellulosic materials, one-step fractionation by formic acid-based organosolv process under pressure has been studied for converting lignocellulose in its main components. Lignin and hemicelluloses were selectively dissolved, while cellulose was not obviously degraded. Under optimized conditions (85% formic acid, a liquor-to-solid ratio of 7:1, and a temperature of 145°C for 45 min), this process provided a high efficient way to separate the main components of bamboo, obtaining 42.2% cellulose pulp, 31.5% lignin, 8.5% hemicellulose-rich fraction, 3.56% furfural and 3.80% acetic acid. Cellulose pulp with satisfying viscosity could easily be bleached to a high brightness of over 87% ISO with a short bleaching sequence, and had an acceptable paper strength properties. The recovered lignin fraction contained a small amount of carbohydrates and a considerable part of proteins and p-hydroxycinnamates. Additionally, the organic substances in hemicellulose-rich fraction obtained was composed of 95% carbohydrates, most of which was monosaccharides, as well as 5% lignin.     

Rapid nitric acid cooking of rice straw

A rapid and mild nitric acid pulping of rice straw was developed and different grades of pulp were produced. A satisfactory nitric chemimechanical rice straw pulp was obtained in a yield of 80% by two stage pulping. In the first stage 5% HNO₃ was used at 80°C and a 6:1 liquor ratio for 30 min, followed by a second alkali stage, 3% NaOH at 95°C for 30 min. The pulp had a satisfactory strength and high opacity and it was bleached by an HP sequence to a 67% general electric brightness (GE). Semichemical pulp of 65% yield was produced by cooking with 10% HNO₃ and 10% NaOH at 20:1 liquor ratio. The pulp had superior strength and it was bleached to a 61% GE by a chlorination-alkali extraction hypochlorite (CEH) sequence. Nitric bleached chemical pulp of 48% and 82% GE was produced by cooking with 6% HNO₃ and 7% NaOH at 10:1 liquor ratio and bleached by a CEH sequence. The chemical pulp is of higher yield and strength than soda pulp. Newsprint that fulfils all the requirements was produced on an experimental paper machine from a furnish composed of 80% bleached nitric chemimechanical rice straw pulp, 10% bleached softwood pulp and 10% clay.     

Integrating laccase–mediator treatment into an industrial‐type sequence for totally chlorine‐free bleaching of eucalypt kraft pulp

Enzymatic delignification using the high‐redox potential thermostable laccase from the fungus Pycnoporus cinnabarinus and a chemical mediator (1‐hydroxybenzotriazole) was investigated to improve totally chlorine‐free (TCF) bleaching of Eucalyptus globulus kraft pulps. Different points of incorporation of the enzyme treatment into an industrial‐type bleaching sequence (consisting of double oxygen, chelation and peroxide stages) were investigated in pressurized laboratory reactors. The best final pulp properties were obtained using an O? O? L? Q? PoP sequence, where a laccase–mediator stage (L) was incorporated between double oxygen and chelation. The worse results, when the enzymatic and chelation treatments were combined in a unique stage, seemed related to partial inhibition of laccase‐mediator activity by the chelator. The new TCF sequence including the laccase stage permitted to improve eucalypt pulp delignification to values around kappa 5 (hexenuronic acid contribution over 50%) compared to kappa 7 using only TCF chemical reagents. In a similar way, the final brightness obtained, over 91% ISO, was 3–4 points higher than that obtained in the chemical sequences. Although technical and economic issues are to be solved, the results obtained show the feasibility of integrating a laccase–mediator treatment into a TCF sequence for bleaching eucalypt kraft pulp. Copyright © 2006 Society of Chemical Industry     

Behavior of Eucalyptus Kraft Pulp Extractives Components across ECF Bleaching and Their Impact on Brightness Reversion

Abstract

This study investigated the chemical composition of the dichloromethane and acetone extracts of eucalypt pulp across D(EP)DP and AZDP bleaching sequences by gas chromatography-mass spectrometry (GC-MS). The bleaching stages led to the partial removal and to several oxidative transformations of fatty acids and sterols, the main lipophilic extractives found in the unbleached pulp. The pulp samples were bleached to 90–91% ISO by D(EP)DP and AZDP sequences and their brightness stability and chemical characteristics determined. The effect of aging on brightness was investigated. The AZDP bleaching sequence resulted in pulps of higher brightness stability. Furoic structures representing the main acid degradation products of HexA are suggested as the actual intermediates that cause yellowing by forming colored compounds. The AZDP process removed larger amounts of HexA across bleaching.     

Radiation Synthesis of Carboxymethyl Cellulose Hydrogels for Removal of Organic Contaminants from Its Aqueous Solution

Preparation of hydrogels based on carboxymethyl cellulose (CMC) using direct radiation grafting technique for removal of organic contaminant such as 4‐chlorophenol and 2,4‐dichlorophenoxyacetic acid (2,4‐D) was carried out. The prepared hydrogels which are composed of individual radiation grafting of methacrylic acid onto CMC to form poly(CMC/MAA) the other hydrogel composed of binary acrylamide/methacrylic acid grafted onto CMC to form poly(CMC/MAA:AAm) hydrogels. The two selected composition poly(CMC/MAA:AAm) (1/60:40 wt%) poly(CMC/MAA) (1:20) wt% hydrogels due to its high chelating properties obtained from our previous work by the same authors. The properties of the selected two prepared hydrogels were evaluated by using different analytical tools such as Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and thermogravimetric analysis (TGA). The gel (%) and the swelling behavior of poly(CMC/MAA:AAm) is higher than poly(CMC/MAAc) hydrogel. It is found that the adsorption capacity of poly(CMC/MAA) hydrogel (1:20 wt%) toward 4‐chlorophenol and 2,4 dichlorophenoxy acetic acid was higher than that of poly(CMC/MAA:AAm) (1/60:40 wt%) hydrogel. Also The obtained results showed that the adsorption capacity of both poly(CMC/MAA:AAm) (1/60:40 wt%) and poly(CMC/MAA) (1:20) wt% hydrogels toward 2,4 dichlorophenoxy acetic acid was higher than of 4‐chlorophenol. J. VINYL ADDIT. TECHNOL., 26:362–369, 2020. © 2019 Society of Plastics Engineers     

Experimental study on carboxymethylation of cellulose extracted from Posidonia oceanica

The production of carboxymethylcellulose (CMC) from bleached cellulose pulps obtained from Posidonia oceanica was explored. The optimal reaction conditions were studied for the carboxymethylation of cellulose in organic liquids. The carboxymethylation reaction was carried out with NaOH and monochloroacetic acid (MAC) as the reagent. Different alcohols were compared in terms of the degree of substitution (DS). The highest DS was obtained with n‐butanol. For this alcohol, the effects of the temperature, alkali concentration, and MAC concentration were studied. The reaction was also carried out in three consecutive steps. The resulting CMC had a DS of about 2.75. The functionalization of cellulose was checked using FTIR spectroscopy and ¹³C‐NMR. The X‐ray analysis showed that the crystalline structure of cellulose decreased when the DS increased and the structure was totally amorphous in high DS material. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1808–1816, 2006     

Synthesis of Gemini‐Like Methyl Acrylate‐Acrylic Acid‐Methyl Acrylate Triblock Copolymers Surfactants by RAFT Polymerization in Solution and Investigation of their Behavior at the Air–Water Interface

A series of methyl acrylate‐acrylic acid amphiphilic triblock copolymers (PMA‐PAA‐PMA) were prepared by solution polymerization using S,S′‐bis (α,α‐dimethy1acetic acid) trithiocarbonate (BDAT) as a reversible addition fragmentation chain transfer (RAFT) agent and methyl acrylate (MA) as the first monomer. The triblock copolymers and their common MA homopolymer precursors were characterized in terms of their compositions, molecular weights and behavior at the air–water interface using ¹H‐NMR spectroscopy, thermogravimetric analysis, gel permeation chromatography, surface tension, transmission electron microscopy (TEM) and dynamic light scattering respectively. The results indicated that PMA‐PAA‐PMA was successfully synthesized through RAFT polymerization. The polydispersity index (PDI) decreased when the molar ratio [n(MA)/n(AA)] increased, the lowest PDI was obtained at 5.23 wt% RAFT and the molecular weights were consistent with the theoretical value as the RAFT agent percentage varied. The polymer neutralized by sodium hydroxide solution shows a low critical micelle concentration (CMC), which was <10^?2 mol L^?1 in water. The A_min values increased and showed a maximum with decreased AA chain length. TEM showed that the neutralized polymer formed a special vesicle structure with large pore structure which led to a low CMC and surface tension of water.     

A modified method of nitric acid pulping of bagasse

Pulping of bagasse by a rapid and mild nitric acid process was successfully carried out to produce different grades of pulp. Nitric chemimechanical bagasse pulp was produced in a high yield of 91 % on pulping depithed bagasse with 4% HNO₃ for a period of 30 min at 80°C, followed by alkali pulping with 2% NaOH at 95°C for 30 min. The pulp had a satisfactory strength and high opacity. On increasing the strengths of nitric acid to 7% and alkali to 7% a nitric semichemical pulp of 65% yield was obtained. The pulp had a superior strength and high opacity. The pulp was easily bleached to 71% general electric brightness (GE) with the chlorination-alkali-extraction-hypochlorite (CEH) sequence. With 15% HNO₃ and 8% NaOH, nitric chemical bagasse pulp was produced. The pulp was easily bleached to a high brightness of 82% GE with one stage hypochlorite. The pulp had a higher strength than kraft bagasse pulp. A satisfactory newsprint paper was produced on an experimental paper machine with a furnish composed of 80% bleached nitric semichemical bagasse pulp, 10% bleached softwood pulp and 10% clay.     

Water‐Soluble Amphiphilic O‐(Carboxymethyl)cellulose Derivatives – Synthesis and Properties

Summary: Water‐soluble, partially hydrophobized derivatives of O‐(carboxymethyl)cellulose (CMC) were prepared by esterification of CMC in its ‘gel suspension’ form. The classical esterification method (A) using stearoyl chloride/pyridine as well as two unconventional methods based on reaction with mixed anhydrides (B) and transesterification with vinyl laurate (C) respectively, were compared in terms of the structural, molecular and performance properties of the obtained derivatives. The classical esterification and method B yielded water‐soluble simple fatty acid esters, whereas mixed acetic‐fatty acid esters were obtained by method C. In all cases, molecular degradation of CMC was observed. ¹H and ¹³C NMR spectroscopy of the acetyl‐lauroyl derivatives of CMC with a degree of esterification DS_E of 0.20 indicated a prevalence of the lauroyl groups (DS_Ac:DS_La = 0.03:0.17). Most of the water‐soluble derivatives exhibited excellent emulsifying efficiency. They represent polysaccharide‐based surfactants with effective anti‐redeposition properties as well as good washing power. Suitable derivatives can be prepared under mild reaction conditions by both unconventional methods which implies that they have potential as substitutes for the expensive and invasive conventional method.

Preparation of CMC derivatives.     

Experimental evaluation of alternative fermentation media for L‐lactic acid production from apple pomace

BACKGROUND: A variety of nitrogen sources were tested for lactic acid production. Corn steep liquor is a low‐cost by‐product that could replace some of the expensive nutrients of the general lactobacilli media. This work deals with the optimisation of the composition of a low‐cost medium for lactic acid production from apple pomace by Lactobacillus rhamnosus CECT‐288. RESULTS: Corn steep liquor (CSL) and yeast extract (YE) were evaluated as nutrient sources for lactic acid production from apple pomace. In comparison with media containing CSL, experiments with YE led to higher volumetric productivities but lower lactic acid concentrations and product yields. The presence of YE increased the production of acetic acid. In media containing 0.2 g CSL g^?1 potential sugars, 29.5 g lactic acid L^?1 was obtained after 24 h, at good yield (35.5 g per 100 g dry apple pomace) and productivity (1.23 g L^?1 h^?1), with a lactic acid/acetic acid mass ratio of 98 g g^?1. CONCLUSION: The experimental results proved that CSL is a suitable nutrient source for lactic acid production from apple pomace, even though the volumetric productivity was lower than in experiments employing YE. Considered as a nutrient supplement, CSL presents advantages over YE not only in terms of cost but also in terms of product yield, final lactic acid concentration and lactic acid/acetic acid mass ratio. The utilisation of apple pomace as the raw material and CSL as the sole nutrient source (both cheap by‐products) enables the production of lactic acid by an economical, environmentally friendly process. Copyright © 2008 Society of Chemical Industry     

Influence of pulp bleaching and compatibilizer selection on performance of pulp fiber reinforced PLA biocomposites

This article focuses on the effect of pulp bleaching and emerging commercial compatibilizers on physical performance of pulp fiber reinforced poly(lactic acid) (PLA) biocomposites. Industrially bleached and unbleached hardwood kraft pulp fibers are treated with several additive types, and compounded with PLA to fiber content of 30 wt %. After injection molding, the produced biocomposites are evaluated by their mechanical performance and fiber–matrix adhesion. For selected materials, fiber surface and fiber properties are reflected to composite performance by analyzing the compositions, dimensions, and lignin coverage of original fibers, as well as fiber dispersion and dimensions after melt processing. As a conclusion, unbleached kraft pulp fibers provide significant improvement in physical properties of PLA/pulp fiber composites. Of the screened compatibilizers, epoxidated linseed oil has a clear positive effect on performance when bleached kraft pulp fibers are used. The improvements correspond to enhanced fiber–matrix adhesion and differences in remaining fiber length distributions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47955.     

Thermal properties of cellulose triacetate as prepared from low-grade dissolving pulp

Because cellulose triacetate is prepared from low-grade dissolving pulp, a considerable amount of the insoluble residue was present in the acetylation medium of the acetic acid/acetic anhydride/sulfuric acid system. To reduce the insoluble residues, a solvent, such as nitromethane, nitroethane, or dichloroacetic acid, added to the acetylation medium was found to be very effective for its reduction. By exploring the optimum conditions for acetylation with these solvents, nitromethane added and dichloroacetic acid added systems with solvent/acetic acid = 3/7 (v/v) were found to have a particularly high transmittance at λ = 670 nm in their acetylation solution with a low insoluble residue. The obtained acetates revealed good thermal properties similar to that from high-grade dissolving pulps. Therefore, a high quality cellulose triacetate can be manufactured from acetylation systems with even low-grade dissolving pulps with an appropriate solvent added. © 1996 John Wiley & Sons, Inc.     

Delignification of Bagasse with Acetic Acid and Ozone. II. Ozone Stage

Ozone gas was applied as second stage in delignification of bagasse pulp obtained with acetic acid. The kappa number was reduced from 44 to 10 with 3% ozone (based on dry pulp). Because bagasse was pulped with an aqueous solution of acetic acid (80% volume), selectivity of the ozone stage was favored and does not necessary acidulate pulp, which had pH = 1.7. Consistency of pulp for ozonation was 40% and this stage was carried out at room temperature. Physical properties of pulp were improved with ozone treatment.