Kaarlo Nieminen

Degradation kinetics of the main carbohydrates in birch wood during hot water extraction in a batch reactor at elevated temperatures

Hot water extraction of wood at elevated temperatures may be a suitable method to produce hemicellulose-lean pulps and to recover xylan-derived products from the water extract. In this study, water extractions of birch wood were conducted at temperatures between 180 and 240 °C in a batch reactor. Xylan was extensively removed, whereas cellulose was partly degraded only at temperatures above 180 °C. Under severe extraction conditions, acetic acid content in the water extract was higher than the corresponding amount of acetyl groups in wood. In addition to oligo- and monosaccharides, considerable amounts of furfural and 5-hydroxymethylfurfural (HMF) were recovered from the extracts. After reaching a maximum, the furfural yield remained constant with increasing extraction time. This maximum slightly decreased with increasing extraction temperature, suggesting the preferential formation of secondary degradation products from xylose. Kinetic models fitting experimental data are proposed to explain degradation and conversion reactions of xylan and glucan.

Cellulose degradation in alkaline media upon acidic pretreatment and stabilisation

The present study reports on a revised kinetic model for alkaline degradation of cellulose accounting for primary peeling/stopping reactions as well as for alkaline hydrolysis followed by secondary peeling. Oxalic acid pretreated cotton linters was utilised as the model substrate for the prehydrolysis-soda anthraquinone process. The main emphasis was investigating the effect of end-group stabilising additives such as sodium borohydride (BH), anthraquinone (AQ), and anthraquinone-2-sulphonic acid sodium salt (AQS) on the rates of the yield loss reactions. BH and AQS ensured a cellulose yield gain of 13% and 11%, respectively, compared to the reference. Both stabilisation agents decreased the content of the reducing end groups in the samples, while in the case of AQS stabilisation a 25% increase in carboxyl group content compared to the reference was also observed. As expected, the addition of end group stabilisers resulted in a significant decrease in the peeling-to-stopping rate constants ratio.

Profiles of alkali concentration and galactoglucomannan degradation in kraft impregnation of Scots pine wood: Experimental observations and modeling

Abstract A deep understanding of alkali impregnation including the profiles of alkali concentration and hemicellulose degradation is necessary to analyze the optimization of current and innovative processes. In this paper, the impregnation of Scots pine (Pinus sylvestris L.) wood is analyzed and modeled under consideration of deacetylation, reactions of acidic group, and galactoglucomannan (GGM) degradation. The immobile anionic groups activated by the ionization of lignin-derived OH groups are also considered for the assessment of the Donnan effect. Predicted profiles of sodium and hydroxide ions and acetyl group concentrations are compared to experimental results. The balance between impregnation and hemicellulose degradation levels is discussed based on the developed models. Expectedly, higher concentrations and temperatures speed up the impregnation process. Nevertheless, a higher OH-concentration has two benefits for the same impregnation front position – the alkali charge inside the chip is higher and the GGM degradation is lower.

Assessing the reactivity of cellulose by oxidation with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxo-piperidinium cation under mild conditions

The accessibility and reactivity of cellulose are key parameters in its conversion into various products. Several indirect measures, such as water retention value (WRV), fiber saturation point (FSP) and specific surface area (SSA), are often used to characterize cellulosic samples for their reactivity. In this paper, we report on using oxidation with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxo-piperidinium cation (4-AcNH-TEMPO+) as a probe reaction for the reactivity of cellulose in mild conditions (pH 9, room temperature). 4-AcNH-TEMPO+ is able to selectively convert hydroxymethyl groups into carboxylate groups. The time dependence of the conversion was monitored by iodometric quantification of the residual 4-AcNH-TEMPO+. Soluble substrates, such as 1-propanol and maltose, were quantitatively oxidized in ca. 1min while 3-16% of cellulose was oxidized in ca. 15min depending on its origin. Extrapolation of the slow residual oxidation to zero time allowed quantification of the easily reactive or accessible cellulose. The 4-AcNH-TEMPO+ reactivity was correlated with several pulp characteristics, including WRV, FSP, SSA, chemical composition, crystallinity, the pulping process and the drying history.

Understanding the role of water in the interaction of ionic liquids with wood polymers

Hemicellulose lean pulps are a raw material source for numerous high value products. We have previously presented the IONCELL-P(ulp) process, a hemicellulose extraction method, based on a binary mixture of ionic liquid and water. The IONCELL-P process does not suffer from yield losses or polymer degradation and retains the Cellulose I crystalline form. In this paper, a selection of cellulose dissolving ionic liquids is tested, in order to compare their applicability in the process. We demonstrate that the extraction selectivity towards low molar mass polymers is related to the anions ability to accept hydrogen bonds (Kamlet-Taft β-value), if divided by the water molar fraction of the solvent system. Pulp consistency, solvent system viscosity and pH are investigated in order to identify the factors affecting the extraction efficiency. The results show that all the tested ionic liquid-water mixtures were able to dissolve hemicelluloses, but there were differences in their efficiency, selectivity and the ability to process high pulp consistencies.

Filament spinning of unbleached birch kraft pulps: Effect of pulping intensity on the processability and the fiber properties

Man-made lignocellulosic fibres were successfully prepared from unbleached birch kraft pulps by using the Ioncell-F technology. Pulps with different lignin content were produced by tailored kraft pulping with varying intensity. The degree of polymerization of the pulps was adjusted by acid-catalyzed hydrolysis and electron beam treatment. All substrates were completely soluble in 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) and the respective solutions were spinnable to yield fibres with good to excellent mechanical properties despite the use of only mildly refined wood pulp. The tensile properties decreased gradually as the lignin concentration in the fibres increased. Changes in the chemical composition also affected the structure and morphology of the fibres. Both the molecular orientation and the crystallinity decreased while the presence of lignin enhanced the water accessibility. The effects of the crystallite size and lignin content on monolayer water adsorption are discussed.

Novel insight in carbohydrate degradation during alkaline treatment

Abstract A mathematical model is presented, in which the yield loss (YL) and the decline in polymerization of carbohydrates is comprehended. The model is applicable to the treatment of cellulose and hemicelluloses in alkaline media, and it features the actions of peeling, stopping, and alkaline hydrolysis of the polymer chains. The peeling reaction is further subdivided into primary and secondary peeling depending on whether it originates from an initial reducing end-group (REG) or from an REG created by alkaline hydrolysis. Fitting the model to experimental data provides estimates of the various reaction rate constants. When available, simultaneous observations of the YL and the decrease in chain length contribute to the evaluation of the parameters. Alternatively, if the data are limited to the YL, the obtained parameter estimates allow for a projection of the time development of chain length. The model has been applied on data from two types of experiments: soda-anthraquinone treatment of cotton linters and kraft treatment of Scots pine. It was possible to evaluate the impact of the different processes on degradation as well as the portions of polymer chains possessing active or stabilized REGs.

Comparative evaluation of different kinetic models for batch cooking: A review

Abstract The purpose of this study was to review some of the existing models for delignification in kraft cooking. Data and results from earlier studies were utilized to evaluate the performance of the models of Gustafson (MG), Purdue (MP), Andersson (MA) and Bogren’s method “continuous distribution of reactivity” (MBcdr) in terms of their ability to give a realistic description for delignification of softwood and hardwood. The MG, MP and MBcdr were tested on lignin data obtained from cooks of Eucalyptus globulus. In this case, MP seemed to perform best, whereas the MBcdr failed in the range of low residual lignins. MA considers the lignin subunits with various reaction speeds, and this feature improves the performance in the case of low residual lignins and helps to reflect sudden changes in cooking conditions, but the difference to the ordinary MP is moderate.

From vapour to gas: optimising cellulose degradation with gaseous HCl

A cellulose degradation technique utilizing a pressurized HCl gas (up to 100 kPa) device is introduced. High pressure HCl quickly degraded cellulose in purified cotton linters, reaching the so-called levelling-off degree of polymerisation (LODP) in less than 1.5 h. LODP marks the point where the disordered portions of cellulose microfibrils have been degraded and only the crystalline portions remain, generally signalling the end of cellulose degradation unless remarkably high concentrations are used. In the present high pressure system, however, continued hydrolysis following the LODP was detected by incremental release of sugars from the hydrolysate after its exposure to water, supposedly caused by erosion from the cellulose crystallite ends. With minimal water consumption and the ease of recycling the gaseous acid, the technique could be a potential candidate for pre-treatment considering the future production of cellulose nanomaterials, particularly cellulose nanocrystals.

The Role of Various Chlorides on Xylose Conversion to Furfural: Experiments and Kinetic Modeling

In this paper, the catalytic activity of thirteen different metal chlorides in aqueous solution for the conversion of xylose into furfural was studied in comparison with both the auto‐ and HCl‐catalyzed reactions. A maximum furfural yield of 60.3 mol % was reached with the addition of FeCl3 to the aqueous xylose solution. However, the catalytic efficiency of FeCl3 decreased on use of birch hydrolysate as a raw material, resulting in 43.5 mol % furfural yield. The obtained experimental results were incorporated in a kinetic modeling study. The assessed reaction rates for xylose dehydration to furfural and xylose decomposition to byproducts, in the presence of AlCl3 and CrCl3 are significantly higher than during acid‐catalyzed conversion. The logarithms of the reaction rates show a linear correlation with the ionization energy as well as with the acidity of the metal ions.