Recovery of aliphatic low-molecular-mass carboxylic acids from hardwood kraft black liquor
Abstract During alkaline pulping of wood, substantial amounts of carbohydrates-derived aliphatic carboxylic acids (formic and acetic acids together with various hydroxy acids) are formed and dissolved into the cooking liquor (“black liquor”). These acids with low heating values are considered to be potential feedstocks for the chemical industry but, due to many factors, their straightforward recovery as free acids from black liquor (pH 13–14) is difficult. In this paper, we outlined the partial recovery of volatile formic and acetic acids from the acidified birch ( Betula pendula ) kraft black liquor (pH approximately 2.5) by distillation, and the partial recovery of significant low-molecul…
Novel concepts on the recovery of by-products from alkaline pulping
Innovative biorefinery concepts were developed for the separation and utilization of organic materials, especially aliphatic carboxylic acids, lignin, and extractives, which are formed as by-products during wood-based alkaline delignification processes. The partial recovery of sodium as NaOH and aliphatic carboxylic acids from hardwood soda-AQ black liquor was studied via electrodialysis. The lignin was partly (about 59 % of the initial lignin) precipitated from black liquor by carbonation (pH to about 8.5) followed by electrodialysis or H2SO4 (pH to about 2), with subsequent precipitation of more lignin and the liberation of aliphatic acids. The Na2SO4 formed was successfully separated fro…
Microwave-assisted catalytic esterification of α-glucoisosaccharino-1,4-lactone with tall oil fatty acids
Background: Carbohydrates-rich materials are partly degraded during alkaline kraft pulping into a complex mixture of aliphatic carboxylic acids consisting of α-glucoisosaccharinic acid as one of the main acids. On the other hand, crude tall oil, containing significant amounts fatty acids, is obtained as a by-product from kraft pulping. One interesting novel approach is to utilize chemically both these side-streams by producing renewable surfactants from aliphatic carboxylic acids and fatty acids via esterification. Results: In this paper, lauric (C12:0) and oleic (C18:1) acids as well as a mixture of tall oil fatty acids were esterified with α-glucoisosaccharino-1,4-lactone in a microwave-a…
Microwave-Assisted Esterification of Tall Oil Fatty Acids with Methanol Using Lignin-Based Solid Catalyst
During alkaline pulping significant amounts of lignin, carbohydrates (mostly hemicelluloses), and extractives (tall oil soap and turpentine) are removed from wood feedstock. In this study, the catalytic esterification of fatty acids in tall oil with methanol to produce fatty acid methyl esters under microwave irradiation was performed at 100 °C for 10–60 min. A novel heterogeneous acid catalyst tested for this purpose was synthesized from the hardwood alkali lignin that was precipitated by acidification from the black liquor from soda-AQ pulping. The comparative reaction data were obtained by using other solid catalysts, Amberlyst 15, and p-toluenesulfonic acid. The results showed the highe…
Partial Recovery of Aliphatic Carboxylic Acids and Sodium Hydroxide from Hardwood Black Liquor by Electrodialysis
The partial recovery of sodium as NaOH and sodium-free aliphatic carboxylic acids (formic and acetic acids together with various hydroxy carboxylic acids) from alkaline hardwood black liquor (BL, pH about 14) was studied by using electrodialysis (ED). In the first phase, the lignin was partly (about 59% of the initial lignin) precipitated from BL by carbonation (pH to 8.5). Furthermore, the carbonated liquor, mainly containing NaHCO3/Na2CO3 and Na salts of aliphatic carboxylic acids and lignin, was subjected to ED for recovering NaOH and sodium-free aliphatic acids. In the second phase, the carbonated BL was further acidified with H2SO4 (pH to about 2.5) for precipitating more lignin (about…
A thermo-alkaline lipase from a new thermophileGeobacillus thermodenitrificansAV-5 with potential application in biodiesel production
BACKGROUND A thermophilic lipase-producing Geobacillus thermodenitrificans strain AV-5 was isolated from the Mushroom Spring of Yellowstone National Park in WY, USA and studied as a source of lipase for transesterification of vegetable oils to biodiesel. RESULTS A maximum activity of 330 U mL−1 was produced on 2% (v/v) waste cooking oil at 50 °C, pH 8, aeration rate of 1 vvm and agitation speed of 400 rpm. However, the higher lipase productivity (14.04 U mL−1 h−1) was found at a volumetric oxygen transfer coefficient (kLa) value of 18.48 h−1. The partially purified lipase had a molecular weight, temperature and pH optimum of 50 kDa, 65 °C and pH 9, respectively, and was thermo-alkali stable…
Clean and Sustainable Biodiesel Production
To date, the majority of world's primary energy is derived from fossil fuels. However, the fossil fuel recourses are in an inevitable decline as energy demand continues to grow exponentially with population growth, urbanization, and improved standards of living. Crude oil prices have recently risen several times and their current annual volatility exceeds 30%. The potential scarcity of fossil fuels has prompted a global search for alternative energy resources. Biodiesel fulfills the major requirements for production of alternative fuels such as feedstock availability, technical feasibility, and economic competitiveness. Together with other renewable biofuels, the use of biodiesel as a subst…
Characterization of Hardwood Soda-AQ Lignins Precipitated from Black Liquor through Selective Acidification
In the development of integrated biorefinery process alternatives to produce value-added by-products, various black liquors from sulfur-free pulping processes offer potential feedstocks for recovering their main chemical constituents, lignin and aliphatic carboxylic acids. In this study, lignin fractions were obtained from silver birch (Betula pendula) soda-anthraquinone black liquor by carbonation (pH to about 8.5) or by acidification (pH to about 2) with H2SO4 after carbonation or directly. These fractions were characterized by Fourier transform infrared (FTIR), ultraviolet (UV), energy dispersive X-ray fluorescence (ED XRF), and 13C nuclear magnetic resonance (13C NMR) spectroscopy. In a…
Enzymatic biodiesel: Challenges and opportunities
The chemical-catalyzed transesterification of vegetable oils to biodiesel has been industrially adopted due to its high conversion rates and low production time. However, this process suffers from several inherent drawbacks related to energy-intensive and environmentally unfriendly processing steps such as catalyst and product recovery, and waste water treatment. This has led to the development of the immobilized enzyme catalyzed process for biodiesel production which is characterized by certain environmental and economical advantages over the conventional chemical method. These include room-temperature reaction conditions, elimination of treatment costs associated with recovery of chemical…