Engineering plastics from lignin. I. Synthesis of hydroxypropyl lignin

Hydroxypropylation of lignin in a batch reactor under alkaline conditions at 180°C was studied using propylene oxide (PO) by itself, and PO in combination with several ligninlike model compounds and with kraft lignin. While the PO homopolymerization rate increased rapidly at temperatures above 85°C, and was too fast to be determined accurately at 180°C, the addition of model compounds and lignin was found to delay homopolymerization in relation to the presence of ionizable functional groups. The observations are consistent with a reaction mechanism involving first order kinetics with regard to each alkoxide and PO concentrations. Where the reaction rates toward PO increase with increasing pK_a values, the reaction sequence proceeds in the order of declining basicity. Thus lignins with high acidity were found to be subject to greater degrees of modification than those with more neutral character. This explains the earlier observed beneficial effect of lignin carboxylation on the properties of lignin–PO reaction mixtures.     

Coconut husk lignin. III. Reactivity of alkaline extracts with formaldehyde

In this article we report results of the evaluation of the reactivity of polyphenolic extracts of coconut husk with formaldehyde in both acidic and alkaline media. The objective of this evaluation was to determine if the extracts could be used in the preparation of phenol–formaldehyde-type resins. Extracts were obtained using aqueous solutions of NaOH (with and without anthraquinone) and NH₄OH. Because of their low Stiasny's Number values, these extracts are not suitable for phenol–formaldehyde resin preparation in acidic conditions unless they are mixed with phenol or phenolic derivatives. Nevertheless, extracts obtained with NaOH, especially at 100 and 120°C, showed sufficient reactivity with form-aldehyde in basic conditions and may therefore be considered suitable for resin preparation in an alkaline medium. The resins were characterized using infrared spectroscopy (IR), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). A transition temperature prior to decomposition was not detected; their thermal stability was similar to phenol–formaldehyde-type resins. © 1993 John Wiley & Sons, Inc.     

蒜头果木质素提取及成分分析

采用一般碱法、超声波辅助和微波辅助从蒜头果壳和枝中提取木质素,分别测定了蒜头果壳和枝中木质素含量及木质素的提取率,并对所提取木质素进行红外和紫外光谱分析。克拉森木素定量法测得蒜头果壳和枝中木质素质量分数分别为44.41%±0.65%和34.57%±0.52%,在碱浓度0.5 mol/L、碱液量30 mL/g、超声波处理时间1 h、水浴温度40℃的提取工艺条件下,蒜头果壳和枝的木质素提取率分别为45.21%±0.59%和63.78%±0.73%。紫外和红外光谱显示超声波辅助方法提取的木质素保持了木质素原有结构,存在明显的愈疮木基和紫丁香基苯环结构;并通过黏度法比较了3种不同提取方法所得木质素的相对分子质量。     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 1: Extraction,Fractionation and Physico-Chemical Characterization

Ground spruce wood was extracted with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min. Released aromatic substances (from 2.2 to 2.5% on wood basis) were isolated on XAD-7 resin and fractionated into lignin, oligomeric aromatic substances (OAS), and compounds insoluble in methanol (IMC). The separated aromatic fractions, and the ground wood before and after extraction, were characterized by physico-chemical methods (GC, GC-MS, HPLC-SEC, TG, DSC). The major part of the aromatic substances was oligomeric aromatic substances (OAS). This fraction increased significantly with the extraction time, while the yield of dissolved lignin increased only slightly with extraction time. Isolated lignins had a lower molar mass and differed considerably from spruce milled wood lignin (MWL). The isolated lignins were more stable against oxidative thermodegradation than spruce MWL. The UV-extinction coefficients at 280 nm were lower for the isolated lignins than for MWL.     

The methanogenic toxicity of wastewater lignins and lignin related compounds

Lignin derivatives are major components of wastewater streams generated in the chemical processing of wood. The objective of this study was to evaluate the inhibitory effect of various lignins isolated from forest industry wastewaters, and selected lignin model compounds, on methanogenic bacteria. The methanogenic inhibition was determined at 30°C in standard toxicity assays, utilizing anaerobic granular sludge as inoculum. The wastewater lignins differed considerably in their inhibitory activity. Some lignin samples were nontoxic, whereas others caused 50% inhibition at concentrations ranging from 3320 to 5950 mg COD dm^?3. Experiments with ultrafiltered lignins revealed that the toxicity of the inhibitory lignin samples originated from the low molecular weight fraction. In additional studies with low molecular weight lignin model compounds, it was observed that the inhibitory activity of these compounds was related to the functional groups on the aromatic ring. Compounds with aldehyde groups or apolar substituents were highly toxic, whereas those with carboxylic groups only caused significant inhibition at high concentrations. These results indicate that low molecular weight lignin derivatives in forest industry wastewaters are potential inhibitors of anaerobic treatment systems.     

Physicochemical characterization of lignins from rice straw by hydrogen peroxide treatment

Extraction of the dewaxed rice straw with 1% NaOH at 55°C for 2 h and following treatment without and with 0.5, 1.0, 2.0, 3.0, 4.0, and 5.0% hydrogen peroxide (H₂O₂) at 45°C for 12 h at pH 11.5 resulted in a dissolution of 68.3, 85.4, 89.4, 92.3, 92.3, 94.3, and 95.1% of the original lignin, respectively. Meanwhile, the two‐stage treatment together solubilized 67.2, 77.2, 78.7, 83.7, 85.5, 87.3, and 88.5% of the original hemicelluloses and degraded 2.5, 9.8, 11.8, 12.1, 15.6, 16.4, and 17.8% of the original cellulose under the conditions given, respectively. Analyses of these lignins revealed that alkali‐soluble lignin fractions did not suffer sever oxidation, but nearly 60% of the original lignin was dissolved out during the first stage of alkali treatment. In the second stage of alkaline peroxide treatment, the residual lignins were substantially released and enriched in oxidized carbonyl and carboxyl groups. In comparison, the isolated eight pure lignin samples were further characterized by both destructive methods such as alkaline nitrobenzene oxidation and nondestructive techniques such as ultraviolet (UV), Fourier transform infrared (FTIR), and carbon‐13 magnetic resonance spectroscopy (¹³C‐NMR) as well as gel permeation chromatography (GPC), and the results are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 719–732, 2001     

Waste Liquors from Cellulosic Industries. V. Cresol-Lignin Liquor as a Component in Polyphenol Formaldehyde Resins

Cresol–lignin liquors produced as waste from bagasse pulping, at different temperatures (160°–190°C) for 1.5 h and at 170°C for different times (0.75–3 h) were tested to evaluate their reactivity in both alkaline and acidic media toward preparation of cresol–lignin formaldehyde resins. The effects of different polymerization parameters—e.g., time, temperature, ratio of polyphenols to formaldehyde, and reaction medium (acidic or alkaline)—on the yield and properties of produced resins were detected. The yields of the resins produced in alkaline medium are higher than those produced in acidic medium.     

Properties of phenol‐formaldehyde resins prepared from phenol‐liquefied lignin

In this study, alkaline lignin (AL), dealkaline lignin (DAL), and lignin sulfonate (SL) were liquefied in phenol with sulfuric acid (H₂SO₄) or hydrochloric acid (HCl) as the catalyst. The phenol‐liquefied lignins were used as raw materials to prepare resol‐type phenol‐formaldehyde resins (PF) by reacting with formalin under alkaline conditions. The results show that phenol‐liquefied lignin‐based PF resins had shorter gel time at 135°C and had lower exothermic peak temperature during DSC heat‐scanning than that of normal PF resin. The thermo‐degradation of cured phenol‐liquefied lignin‐based PF resins was divided into four temperature regions, similar to the normal PF resin. When phenol‐liquefied lignin‐based PF resins were used for manufacturing plywood, most of them had the dry, warm water soaked, and repetitive boiling water soaked bonding strength fitting in the request of CNS 1349 standard for Type 1 plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Production of H2 and medium Btu gas via pyrolysis of lignins in a fixed-bed reactor

Lignins are generally used as a low-grade fuel in the pulp and paper industry. In this work, pyrolysis of Alcell and Kraft lignins obtained from Alcell process and Westvaco, respectively, was carried out in a fixed-bed reactor to produce hydrogen and gas with medium heating value. The effects of carrier gas (helium) flow rate (13.4–33 ml/min/g of lignin), heating rate (5–15°C/min) and temperature (350–800°C) on the lignin conversion, product composition, and gas yield have been studied. The gaseous products mainly consisted of H₂, CO, CO₂, CH₄ and C₂₊. The carrier gas flow rate did not have any significant effect on the conversion. However, at 800°C and at a constant heating rate of 15°C/min with increase in carrier gas flow rate from 13.4 to 33 ml/min/g of lignin, the volume of product gas decreased from 820 to 736 ml/g for Kraft and from 820 to 762 ml/g for Alcell lignin and the production of hydrogen increased from 43 to 66 mol% for Kraft lignin and from 31 to 46 mol% for Alcell lignin. At a lower carrier gas flow rate of 13.4 ml/min/g of lignin, the gas had a maximum heating value of 437 Btu/scf. At this flow rate and at 800°C, with increase in heating rate from 5 to 15°C/min both lignin conversion and hydrogen production increased from 56 to 65 wt.% and 24 to 31 mol%, respectively, for Alcell lignin. With decrease in temperature from 800°C to 350°C, the conversion of Alcell and Kraft lignins were decreased from 65 to 28 wt.% and from 57 to 25 wt.%, respectively. Also, with decrease in temperature, production of hydrogen was decreased. Maximum heating value of gas (491 Btu/scf) was obtained at 450°C for Alcell lignin.     

Analysis of oil obtained from mild hydrogenation of coal. 1. structural analysis of fractionated oil

Shin Yubari coal (86.7% C) was mildly hydrogenated repeatedly at 340–385°C under an initial hydrogen pressure of 10 MPa for 1 h, using Adkins catalyst. The product was extracted with benzene at 200°C and the residue was again reacted. Finally, benzene solubles were extracted with n-hexane, and n-hexane insolubles were hydrogenated under similar conditions at 380°C; the product was then extracted with n-hexane. The yield of total n-hexane solubles was 52.5%. Acid and base were extracted with sulfuric acid and NaOH, and the neutral part (50.2%) was chromatographed using an alumina column with 2.5% water and separated into 12 fractions. UV and IR spectra, ultimate analysis and ¹H-NMR spectra were obtained for each fraction and a structural analysis was carried out to obtain an image of each average structure. The aromatic ring numbers estimated from UV spectra and from structural analysis for each fractions agree well with each other; the average value was 3.2.     

Electrochemistry of Biomass-Derived Materials I. Characterization,Practionation, and Reductive Electrolysis of Ethanol-Extracted Explosively-Depressurized Aspen Lignin

The chemical characterization (functional group distribution) and spectroscopic properties (¹³C, ¹H, IR, UV-Vis) of a number of lignins obtained from ethanol extraction of explosively-decompressed aspen (Populus tremuloides) lignin (EEEDAL) are described. In this process mod is heated to ～240°C by direct steam and fiberized by sudden decompression. Both mechanical and chemical degradation occur which lead to a decrease of the molecular weight of all of the natural polymers. The lignin fraction is soluble in alcohols; it has a low number average molecular weight (925) and is very reactive. EEEDAL was subjected to fractionation by differential solubility prior to and after electrolyses on mercury cathodes at ?2.6 V vs. Ag/AgCl in methanol/tetraethyl-ammonium perchlorate. After recovery of 85–90% of the original weight of material used by precipitation with acid, followed by a series of extractions, the chemical and spectroscopic properties of each fraction were determined. The acid-insoluble fractions are more condensed than the acid-soluble fractions and have lower phenolic OH and lower aliphatic OH contents than the acid-soluble fractions. The acid-soluble fractions phenolic OH content approaches one per phenylpropane (5) unit of the Lignin. Electrolyses increase the amount of lower molecular weight, high phenolic content, acid-soluble lignins and changes the molecular weight distribution by decreasing the polydispersity of the resulting lignins. These low-molecular-weight lignins are chemically reactive (for instance, with formaldehyde) and can be used in the partial replacement of phenol in phenol-formaldehyde thermosetting resins.     

Comparative study of lignins from ultrasonic irradiated sugar‐cane bagasse

After ultrasonic irradiation of sugar‐cane bagasse (SCB) in distilled water at 55 °C for 40 min and continuing stirring for 80 min, the irradiated SCB was sequentially treated with 0.5 M NaOH, 0.5 %, 1.0 %, 1.5 %, 2.0 % and 3.0 % H₂O₂ at pH 11.5, and 2 M NaOH at 55 °C for 2 h, which solubilized 3.3, 59.7, 15.5, 4.4, 5.5, 1.7, 0.6 and 0.6 % of the original lignin, and 13.4, 38.2, 11.9, 4.5, 9.0, 2.4, 1.2, and 11.3 % of the original hemicelluloses, respectively. In total, the sequential extractions resulted in a release of 91.2 % of the original lignin and 91.9 % of the original hemicelluloses, which were higher than in the case of corresponding extractions without ultrasound pre‐treatment. The eight lignin fractions were comparatively characterized by chemical composition, structural features, molecular weights, and thermal stability using alkaline nitrobenzene oxidation, acid hydrolysis, UV, FT‐IR, ¹H and ¹³CNMR spectroscopy, GPC, and thermal analysis. Compared to the lignins obtained without ultrasound, the lignin fractions prepared with the assistance of ultrasound had the same primary structure, composition, and similar or slightly higher purity. Copyright © 2004 Society of Chemical Industry     

BEHAVIOR OF EUCALYPTUS GLOBULUS LIGNIN DURING KRAFT PULPING. II. ANALYSIS BY NMR,ESI/MS,AND GPC

ABSTRACT

Residual and dissolved lignin from different phases of kraft delignification of Eucalyptus globulus wood were isolated and characterized by 1D and 2D ¹H NMR, ¹³C NMR, Electrospray Ionization Mass Spectrometry (ESI/MS), and gel permeation chromatography (GPC). During the temperature rise period, below 70°C, about 20% of the lignin was dissolved without significant structural changes. Above 70°C, the lignin suffered significant degradation/fragmentation in the cell wall prior to dissolution. The lignin ether-linked syringyl units were the most susceptible to alkaline degradation. Through the course of pulping, the residual lignin (RL) revealed a gradual increase of aliphatic moieties of unknown structure, as well as a decrease of native structures such as phenylcoumaran and pino-/syringaresinol lignin units. A significant decrease of the β-O-4 structures content in RL was detected only at the final cooking temperature. The lignin dissolved in the black liquor (BL) consisted of highly branched oligomers with rather low molecular weight (average mass 800–1000 u). A part of BL (about 30%) was chemically linked to carbohydrates and possessed a large molecular weight distribution (500–4000 u). BL showed a progressive decrease in β-O-4 and pino-/syringaresinol structures and formation of enol ether and stilbene structures. The GPC analyses showed a continuous decrease of the molecular weight of both the residual and dissolved lignins during the pulping process, particularly in the residual stage.     

Production of H2 and medium heating value gas via steam gasification of lignins in fixed‐bed reactors

In this work, steam gasification of Alcell and Kraft lignins were carried out in a fixed‐bed reactor in order to produce H₂ and medium heating value gas. The conversion of lignins increased from a low of 64 wt% for Alceil lignin to a high of 88 wt% for Kraft lignin with increasing steam flow rate and temperature. Maximum H₂ production of 60.7 mol% was obtained at 800°C and at a steam flow rate of 15 g/h/g of Kraft lignin, whereas maximum heating value of 18000 kl/m³ of the product gas was obtained at 650°C and at 5 g/h/g of Alcell lignin. Also, the performance of a Ni‐based steam reforming catalyst for the production of H₂ was studied for both types of lignin in a dual fixed‐bed reaction system. A maximum H₂ production of 63 mol% was obtained at a catalyst bed temperature of 750°C and at a catalyst loading of 0.3 g for Alcell lignin. The sulfur present in Kraft lignin had detrimental effect on the catalyst performance.     

Engineering Plastics from Lignin. VIII. Phenolic Resin Prepolymer Synthesis and Analysis

A sequential derivatization of lignin with formaldehyde and phenol was investigated as a means of enhancing lignin's reactivity in phenol-formaldehyde resins. Kraft lignin (KL) and two novel biocon version lignins, steam explosion (SEL) and acid (H₂SO₄) hydrolysis lignin (AHL), were chemically modified by sequential reaction with formaldehyde and phenol. The results with regard to the chemical structure of the phenolic resin prepolymers showed that the ability to hydroxymethylate and phenolate is related to lignin structure. KL from pine proved to be more amenable to chemical modification with formaldehyde and phenol than was either SEL from aspen or AHL from pine. Degrees of substitution were determined by H-NMR spectroscopy and by oxidative analysis with alkaline permanganate. H-NMR spectroscopy revealed degrees of phenolation of 0.42, 0.29 and 0.21 per average C₉-unit for KL, AHL, and SEL, respectively; and permanganate oxidation illustrated that approximately 90%, 60%, and 60% of all available unsubstituted phenolic guaiacyl units in KL, AHL and SEL, but none of the corresponding non-phenolic or syringyl entities, had become derivatized.     

Reactivity Toward Phenol of Lignin from the Hydrolysis of Sweetgum Wood with Concentrated Sulfuric Acid

Sweetgum wood was hydrolyzed at 20°C and 50°C for different time periods with 68% sulfuric acid. The lignin residues obtained were subjected to a phenolation reaction. For lignin prepared at the lower temperature the maximum phenol uptake was 9.5%, and at the higher temperature only 5–6%. When wood prehydrolyzed with dilute acid was used the phenol uptake rose to 12.5%. However, all the sulfuric acid hydrolysis lignins showed much lower reactivity toward phenol than the 20% phenol uptake exhibited by lignin isolated using concentrated hydrochloric acid.     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 2: Structural Characterization

Extraction of ground spruce sapwood with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min resulted in isolation of galactoglucomannans and aromatic substances, including lignin. The isolated lignin preparations were characterized by spectrometric (UV, FT-IR, ¹H NMR, liquid and solid-state ¹³C NMR), chromatographic (RP-HPLC, HP-SEC, GC-FID, and GC-MS), conventional pyrolysis, thermally assisted hydrolysis, and methylation techniques in tandem with GC-MS, and classical wet chemistry (methoxyl groups, total and phenolic hydroxyl groups, derivatization followed by reductive cleavage—DFRC). The content of β-O-4 bonds in isolated lignins was similar to that in MWL and their proportion decreased with extraction time. The oxidation of isolated lignins and content of total hydroxyl groups were significantly increased with extraction time. The lignin structure underwent condensation and demethylation reactions during hot-water extraction. The induction of new phenylcoumaran substructures was proposed in isolated lignins.     

Coconut kernel-derived activated carbon as electrode material for electrical double-layer capacitors

Carbonization of milk-free coconut kernel pulp is carried out at low temperatures. The carbon samples are activated using KOH, and electrical double-layer capacitor (EDLC) properties are studied. Among the several samples prepared, activated carbon prepared at 600 °C has a large surface area (1,200 m² g^?1). There is a decrease in surface area with increasing temperature of preparation. Cyclic voltammetry and galvanostatic charge–discharge studies suggest that activated carbons derived from coconut kernel pulp are appropriate materials for EDLC studies in acidic, alkaline, and non-aqueous electrolytes. Specific capacitance of 173 F g^?1 is obtained in 1 M H₂SO₄ electrolyte for the activated carbon prepared at 600 °C. The supercapacitor properties of activated carbon sample prepared at 600 °C are superior to the samples prepared at higher temperatures.     

Temperature dependence of the tensile properties of lignin/paper composites

The mechanical properties of dioxane lignin (DL)/paper and kraft lignin (KL)/paper composites were investigated as functions of temperature and strain rate. The tensile properties of the lignin/paper composites were governed by the viscoelastic properties of lignins used as a matrix. In the temperature dependence of the tensile properties, the strength of DL/paper composite decreased at 70° and 130°C at which the elongation had maxima. This behaviour was caused by the viscoelastic properties of DL having two relaxations in the primary dispersion region at 120° and 160°C. In the case of KL/paper composite, a drastic decrease in the strength and maximum of elongation were observed at the glass transition of KL (140°C). The strain rate dependence of the strength of DL/paper composite showed behaviour typical of viscoelastic materials. The strength increased with increase of the strain rate and then decreased after reaching a maximum, which showed a transition from a brittle to a ductile type of fracture.     

Contents of α-O-4 and β-O-4 Bonds in Native Lignin and Isolated Lignin Preparations

An analytical calculation method for the estimation of the contents of alkyl aryl ether bonds (α-O-4 and β-O-4) in lignin was developed. In the framework of the method, Alkyl–O–Aryl type bonds are described as coupled phenolic hydroxyls (OH_phen). The method is based on the balance equation including the free and coupled OH_phen contents in dissolved and residual lignins, on the one hand, and their respective contents in native lignin, on the other. The free OH_phen content is calculated on the basis of the OH_phen contents of dissolved and residual lignin, determined by the aminolysis method in the course of kraft cooking of softwood. The calculation results for soluble lignin preparations are in good agreement with the 13C NMR (nuclear magnetic resonance) spectral data for the solutions. The content of Alkyl–O–Aryl bonds in native softwood (pine, spruce) lignin was estimated at 79/100 PPU (phenylpropane unit). In isolated lignin preparations, the contents of these bonds decrease in the sequence: Freudenberg lignin (71/100 PPU)> Bjorkman lignin (61/100 PPU)> Pepper lignin (44/100 PPU). Dissolved alkaline lignin still contains small amounts of Alkyl–O–Aryl bonds (36/100 PPU in soda lignin and an average of 23/100 PPU in soda-AQ lignin, kraft lignin, and kraft-AQ lignin). Residual lignin which represents the fraction of native lignin with inter-unit bonds resistant to kraft pulping contains 66/100 PPU of such bonds. A relatively high content of Alkyl–O–Aryl bonds (61/100 PPU) is preserved in technical hydrolysis lignins.