Characterization of Formacell Lignin Derived from Black Liquor as a Potential Green Additive for Advanced Biocomposites

Black liquor is obtained as a by-product of the pulping process,which is used to convert biomass into pulp by removing lignin,hemicelluloses and other extractives from wood to free cellulose fibers.Lignin represents a major constituent in black liquor,with quantities varying from 20%to 30%,of which a very low share is used for manufacturing value-added products,while the rest is mainly burned for energy purposes,thus underestimating its great potential as a raw material.Therefore,it is essential to establish new isolation and extraction methods to increase lignin valorization in the development of bio-based chemicals.The aim of this research work was to determine the effect of KOH or ethanol concentration as an isolation agent on lignin yields and the chemical characteristics of lignin isolated from formacell black liquor of oil palm empty fruit bunch(OPEFB).Isolation of lignin was carried out using KOH with various concentrations ranging from 5%to 15%(w/v).Ethanol was also used to precipitate lignin from black liquor at concentrations varying from 5%to 30%(v/v).The results obtained showed that the addition of KOH solution at 12.5%and 15%concentrations resulted in better lignin yield and chemical properties of lignin,i.e.,pH values of 3.86 and 4.27,lignin yield of 12.78%and 14.95%,methoxyl content of 11.33%and 10.13%,and lignin equivalent weights of 476.25 and 427.03,respectively.Due to its phenolic structure and rich functional groups that are favorable for modifications,lignin has the potential to be used as a green additive in the development of advanced biocomposite products in various applications to replace current fossil fuel-based material,ranging from fillers,fire retardants,formaldehyde scavengers,carbon fibers,aerogels,and wood adhesives.

A win-win technique of stabilizing sand dune and purifying paper mill black-liquor

The principle and technique were reported here to produce lignin-based sand stabilizing material （LSSM） using extracted lignin from black liquor of straw paper mills. Field tests using LSSM to stabilize and green sand dunes were started in 2002. The field experiment was carded out in August 2005 when the newly formed plant community was 3 years old. The results from the comprehensive field experiment demonstrated that unlike polyvinyl acetate or foamed asphalt commonly used for dune stabilization, LSSM was plant- friendly material and could be used in combination with seeding and planting of desert species. With the help of LSSM, the desert species （i.e., Agriophyllum squarrosum （L.） Moq. and Artemisia desertorum Spreng. etc.） could be used to form community in 2-3 yeas and to stabilize sand dune effectively. The newly formed community was sustainable under an extremely dry climate condition. The organic matter and total nitrogen in the soil increased significantly as the community were formed, while the change in P and K contents in the soil was negligible.

Treatment of black liquor from the papermaking industry by acidification and reuse

Two different kinds of black liquor from the papermaking industry were treated by acidification and reuse. The experimental parameters and conditions were discussed in detail. The experimental results indicated that the treatment process mentioned in this article is an effective process for the treatment of black liquor from the papermaking industry. By the treatment, the solid materials in black liquor are transferred into two by products and the other components are reused or evaporated. Thus, no wastewater except some condensation water would be discharged in pulping process and the problem of pollution of black liquor would be effectively solved.

Combined effect of US/PFS on the black liquor of making paper

The reed pulping black liquor is used as a sample. Researches of (1) combined effect of ultrasound(US)/polyferric sulphate(PFS)/hydrogen peroxide(H 2O 2); (2) effects of the horn tip areas; (3) effect of dose of PFS were carried. Extrapolation of these experiments indicated treatment results are possibly related to complex chemical compositions in the reed pulping black liquor.

Catalytic Activity of the Black Liquor and Calcium Mixture in CO2 Gasification of Fujian Anthracite

CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressure. When the coal was impregnated with an appropriate quantity of Ca and BL mixture, the catalytic activity of CO2 gasification was enhanced obviously. With a loading of 8%Na-BL＋2%Ca, the carbon conversion of three coal samples tested reaches up to 92.9%-99.3% at 950℃ within 30min. The continuous formation of alkali surface compounds such as （[-COM], [-CO2M]） and the presence of exchanged Ca, such as calcium phenolate and calcium carboxylates （COO）2Ca, contribute to the increase in catalytic efficiency, and using BL＋Ca is more efficient than that adding BL only, The homogeneous model and shrinking-core model were applied to correlate the data of conversion with time and to estimate the reaction rate constants under different temperature. The corresponding reaction activation energy （Ea） and pre-exponential factor of three anthracites were estimated. It is found that Ea is in the range from 73.6 to 121.4kJ·mol^-1 in the case of BL＋Ca, and 74.3 to 104.2kJ·mol^-1 when only BL was used as the catalyst, both of which are much less than that from 143.5 to 181.4kJ·mol^-1 if no catalyst used. It is clearly demonstrated that both of BL＋Ca mixture and BL could be the source of cheap and effective catalyst for coal gasification.

Investigation on Steam Gasification of High-metamorphous Anthracite Using Mixed Black Liquor and Calcium Catalyst

The catalytic effects of single and mixed catalysts, i.e. single 3%Ca and 5%Na-BL（black liquor） catalysts and mixed 3%Ca＋5%Na-BL catalyst, on carbon conversion, gasification reaction rate constant and activation energy, relative amount of harmful pollutant like sulphur containing gases have been investigated by thermogravimetry in steam gasification under temperature 750℃ to 950℃ at ambient pressure for three high-metarnorphous anthracites （Longyan, Fenghai and Youxia coals in Fujian Province）. The mixed catalyst of 3%Ca＋5%Na-BL increases greatly the carbon conversion and gasification rate constant by accelerating the gasification reaction C＋H2O→CO＋H2 due to presence of alkali surfacecompounds [COM], [CO2M] and exchanged calcium phenolate and calcium carboxylate （-COO）2. By adding CaCO3 into BL catalyst in gasification, in addition to improving the catalyst function and enhancing the carbon conversion, the effective desulphurization is also achieved, but the better operating temperature should be below 900℃. The homogenous and shrinking core models can be successfully employed to correlate the relations between the conversion and the gasification .time .and to estimate the reaction rate constant, The reaction acUvaUon energy and pre-exponential factor are estimated and the activation energy for mixed catalyst is in a range of 98.72-166.92 kJ·mol^-1, much less than 177.50-196.46 kJ·mol^-1 for non-catalytic steam gasification for three experimental coals.

Hydraulic and carbonizing actions of sulfuric acid to straw pulp and paper black liquor

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Electrochemical degradation of acidified reed pulp black liquor with three-dimensional electrode reactor

The electrochemical degradation of reed pulp black liquor containing lignin pretreated by acidification method was investigated using a three-dimensional electrode reactor. Using activated carbon as particle electrode, the effects of p H value, reaction temperature, electrolysis time and current on residual concentration of total organic carbon(TOC) were discussed in detail. The optimal conditions were obtained: pH 2.5, influent flow rate of 200 mL/min, 25 °C, 300 mA and 2h of electrolysis time, and the removal efficiency of TOC maintains at 35.57 %. The results of the electrochemical method indicate that ·OH radicals are produced in activated carbon anode in the electrolysis process and then adsorbed on the activated carbon surface. Microcell consists of ·OH radicals and the absorbed lignin. With the microcell reaction, the lignin is degraded, while the anodic polarized curve illustrates that the lignin is obviously oxidized in the anode. The contributions of direct and indirect electrolyses to the TOC removal ratio are about 50%, respectively.

Preparation of adhesive for bamboo plywood using concentrated papermaking black liquor directly

Adhesive for bamboo plywood prepared directly using lignin existing in the black liquor as a kind of material replacing phenol was proposed on the basis of the same structural properties of lignin and phenol. The results indicate that the reaction time of black liquor methylating is 30min, when the ratio of alkali to formaldehyde is controlled at approximately 0.20, decomposition rate of formaldehyde is the lowest and the effect of black liquor methylating is the best, the optimal molar ratio of phenol： formaldehyde to NaOH to H2O of preparing phenolic resin is 1.00 ： 1.50 ： 0.50 ： 9.00, and the suitable viscosity is 27 - 30 Pa· s. At different mass ratios of methylated black liquor to phenolic resin, all terms of performance of black liquor phenolic resin are excellent and satisfy the requirement. All terms of performance of bamboo plywood prepared using this technique are hetter than that of excellent bamboo plywood of national criteria. Using this technique, the cost is depressed by 28.69% without altering the traditional adhesive producing technique flow, and without using additional equipment.

Lignin Extraction from Black Liquor and its Application Prospects in Pulp Mills

This paper summarizes the possible application of lignin extraction from black liquor and the development of lignin extraction technology.Lignin extraction from black liquor is an important,economical method to resolve the bottleneck associated with the recovery boiler and achieve the targeted capacity expansion in pulp mills.A few of key issues must be taken into cosideration when lignin extraction technology is adopted on the industrial scale.

Study on Synthesis of Nanometer SiC Precursors with Sol-Gel of SiO_2-Lignin in the Pulp Black Liquor

In the process of synthesis of nanometer SiC precursors with sol-gel of SiO2 and lignin , the products of all sizes required can be controlled by the concentration of reac-t ants , pH, temperature, reaction and ageing time , and so on . The best conditions in this research are : the concentration of Na2SiO3 and organic matters are 4. 50% and 26.4% respectively, pH = 3.3 , T = 65℃ , ageing time is 30min , dried at 150 ℃ , the size of SiC precursors is about 2.0μm .

Form transition of sodium during combustion of black liquor coal slurry

Several typical ash samples from a 0.25 MW test furnace fired black liquor coal slurry were selected for investigation. The phases and compounds containing sodium in ash samples were acquired from X-ray diffraction analyses. As well, detailed analyses of the amounts of major mineral elements along thickness gradients of representative ash samples were carried out. The elements, including Na, Si, A1, S and C1 were analyzed by the advanced electron probe microanalyzer equipment, which provid evidence and interpretation for the analytical results of XRD. The findings indicate that the occurrence form of sodium has experi- enced important changes during the combustion of black liquor coal slurry, which translated into nepheline, thenardite, sodium sulfate, sodium chloride, sodium silicoaluminate, hanyne and other phases containing sodium, from NaOH, Na2CO3 and Na2S in raw fuel. Of all the sodium compounds, nepheline, thenardite and sodium sulfate are the most important forms of Na in solid com- bustion residues. Such a transformation of Na during the combustion of black liquor coal slurry resulted in a considerable impact on ash deposition and is not only different from the raw coal and papermaldng black liquors, but is also affected by local circum- stances in the combustion furnace. Amounts of Na, S and C1 in ash deposits from low temperature zones were larger than those from high temperature zones. Our findings should provide important theoretical instructions for industrial applications of black liquor coal slurry.

Novel Magnetically Interconnected Micro/Macroporous Structure of Monolithic Porous Carbon Adsorbent Derived from Sodium Alginate and Wasted Black Liquor and Its Adsorption Performance

The novel and facile preparation of magnetically interconnected micro/macroporous structure of monolithic porous carbon adsorbent(MPCA)were designed and presented herein.The synthesis was achieved via conventional freezedrying and pyrolysis processes.In this study,sodium alginate and wasted black liquor were employed as starting precursors.Sodium alginate acts as a template of materials,whereas black liquor,the wasted product from the paper industry with plentiful of lignin content and alkaline solution,played an essential role in the reinforcement and activation of porosity for the resulting materials.Moreover,both the precursors were well dissolved in Fe^(3+) solution,providing a simple addition of a magnetic source in a one-pot synthesis.The interconnected micro/macroporous structures were generated through freeze-drying and,subsequently the pyrolysis process.The obtained cylindricalshaped monolithic porous carbon adsorbent(MPCA-700)showed high mechanical stability,a high BET specific surface area(902 m^(2)/g).Such aforementioned features were considered suitable to make the synthesized monolith as an adsorbent for the removal of heavy metal ions.The maximum adsorption capacity of MPCA-700 towards Pb^(2+) ions was 76.34 mg/g at pH 5.The adsorption studies illustrated that adsorption kinetics and isotherm perfectly fitted with the pseudo-second-order kinetics model and Langmuir isotherm,respectively.This work presents a promising protocol to reduce the overall costs in the preparation of renewable adsorbents with good adsorption efficiency and regeneration.

Combustion and Sulfur-fixing Performance of Pulping Black Liquor Coal-water Slurry

The effects of adding pulping black liquor and other additives to coal-water slurry(CWS) on the sulfur-fixing performance of the resultant mixture(pulping black liquor coal-water slurry) were evaluated. The experimental results demonstrated that the ash content of the black liquor coalwater slurry decreased as the addition of pulping black liquor in the mixture increased. Nevertheless, the addition amount should be appropriately selected to ensure that the black liquor coal-water slurry had a moderate calorific value. Addition of black liquor improved the combustion performance of CWS by lowering the ignition point and stabilizing the combustion process; moreover, the sulfur-fixation ratio after combustion increased by 12 to 16 percentage points than that of CWS, and the content of high-melting-point salt in the ash from CWS after adding black liquor was low. The sulfur-fixing ratio of CWS after adding a sulfur-fixing agent was effectively increased by 25 to 30 percenatge points, but with compromise of the fluidity and stability of the CWS; thus, the addition amount of a sulfur-fixing agent should be optimized.

DECOMPOSITION OF BLACK LIQUOR BY ULTRASOUND PROCESS

Ultrasound (US)-induced cavitation is an effective way in oxidizing organic contaminants in wastewater either as the independent operation unit or in combination with other oxidation methods. In this paper, black liquor and filtrate after acidifying and settling were sonicated. The effect of working parameters on ultrasonic degradation of black liquor, such as different combination methods, frequency, power supply, initial concentration, pH, duration time, ionic strength and catalyst were studied. The results were as follows: (1) At the conditions of 40kHz, 100W, 4h, pH at 6 and temperature 30?℃, utilizing US/US-H2O2/US-Fenton, weak-orange filtrate turned to colloid with the increase of time and little sediment produced after settling. Especially filtrate came to be milk white collides and upper water approached to nearly achromatic by US-Fenton. Compared with the US, US-H2O2/US-Fenton COD (Chemical oxidation demand) removal ratio can increase 15%, 30% respectively. Because of more hydroxyl radicals produced in the reaction process; (2) At the condition of 100W and 4h, the degradation efficiency of black liquor was better at 40kHz over at 20kHz. Moreover black liquor can be biodegraded easily. Those based on that the big molecule of contaminants in aqueous solution can be changed into the little molecule with ultrasound (3) At the condition of 40kHz and 4h, the COD removal ratio of black liquor was more higher at 60W than at 80W, while the removal ratio of COD at 60W was nearly close to the ratio at 100W; (4) The initial concentration of black liquor influenced the effect of sonochemical degradation; (5) The variation of pH had no effect on degradation; (6) The longer the duration time, the greater the removal ratio of COD. But this ratio increased slowly after 4h; (7) Adding 0.2g/L NaCl to change the ionic strength of the black liquor, the COD removal ratio can increase 10%; (8) The degradation rates increased by the coexistent catalysts of TiO2, Co2+ and Ag+.

New Advanced Technology on Waste Resourcelization of the Black Pulping Liquor

Combining the characteristics of the black pulping liquor that contains a lot of lignin and other biomass resources, the technology of comprehensive waste utilization is employed. The reconstructive preparation of modified urea-formaldehyde glue by adding black pulping liquor and the application in extruding the medium density fibre board using this modified urea-formaldehyde glue is researched. Results show that when applying the preparation technology that alkaline reaction and then weak acid reaction, the appropriate preparation process is as follows： the adding urea process is divided into three stages （proportion 2 ： 1 ： 1） ; the pH value is 8.0, and the reaction time is 40 min in the addition reaction stage; the pH value will be naturally reduced to 3.5 -5.0, and the reaction time is 45 min in the aggregation reaction stage; the pH value is 8.0 in the urea complement stage. And the optimal condition of the reconstructive preparation the modified ureaformaldehyde glue is adding the condensed black pulping liquor after hydroxymethylation in the beginning of polycondensation reaction by 5% proportion. The application in extruding medium density fibre board with this modified urea-fosmaldehyde glue is proved feasible.

Preparation of Adsorbent with Magnesium Sulfate and Straw Pulp Black Liquor and Its Phenol Adsorption Properties

A magnesia adsorbent was prepared from straw pulp black liquor and magnesium sulfate for the first time, and its adsorption of phenol from aqueous solution was examined. The characteristics of the adsorbent were tested through chemical analysis, surface analysis, X-ray diffraction and FT-IR spectroscopy. The effects of various factors, such as dose, adsorption time and adsorption temperature, on phenol adsorption behavior were studied. The results show that the adsorption processes can be fitted to the isotherm Langmuir model very well. It was found that the adsorption process was strongly influenced by temperature and the optimal temperature for phenol removal was 40 ℃. The optimum adsorption time was 10 min, and desorption would happen afterwards. Between the models of Langmuir and Freundlich, the adsorption process of phenol onto magnesia fitted the Langmuir equation better.

Production of high-purity hydrogen from paper recycling black liquor via sorption enhanced steam reforming

Environmentally friendly and energy saving treatment of black liquor(BL),a massively produced waste in Kraft papermaking process,still remains a big challenge.Here,by adopting a NieCaOeCa_(12)Al_(14)O_(33) bifunctional catalyst derived from hydrotalcite-like materials,we demonstrate the feasibility of producing high-purity H_(2)(~96%)with 0.9 mol H_(2) mol^(-1) C yield via the sorption enhanced steam reforming(SESR)of BL.The SESRBL performance in terms of H_(2) production maintained stable for 5 cycles,but declined from the 6th cycle.XRD,Raman spectroscopy,elemental analysis and energy dispersive techniques were employed to rationalize the deactivation of the catalyst.It was revealed that gradual sintering and agglomeration of Ni and CaO and associated coking played important roles in catalyst deactivation and performance degradation of SESRBL,while deposition of Na and K from the BL might also be responsible for the declined performance.On the other hand,it was demonstrated that the SESRBL process could effectively reduce the emission of sulfur species by storing it as CaSO_(3).Our results highlight a promising alternative for BL treatment and H_(2) production,thereby being beneficial for pollution control and environment governance in the context of mitigation of climate change.

MICROBIAL STRENGTHEN OF COTTON PULP BLACK LIQUOR ANAEROBIC TREATMENT AND BMP MEASUREMENT

This paper illustrates the general experiment principle of anaerobic biological cotton pulp black liquor microbial degradation, including the process and result of experiment. The result shows that the decrement of COD may arrive at 80% by the strengthen effect of Photosynthetic Bacteria. The biochemical methane Potential (BMP) and Chemical Oxygen Demand (COD) of cotton pulp black liquor are also measured during the experiment using improved measure method. The equivalent of COD and BMP is verified as a result. Finally analysis is done based on the experiment result.

ANALYSIS ON COMPOSITION OF FOULANTS FROM ALKALINE WHEAT STRAW BLACK LIQUOR AND DISCUSSION ON ITS FOR MING MECHANISM

Analysis on foulants shows that: the elements (except for C, H and O) in foulants formed during evaporating alkaline wheat straw black liquor are Si, Ca , K, Na, Mg and Al; Si and Ca account for about 36% of the weight of foulants; The organic ingredients amout to about 20% of the foulant; Rhodesite (Ca,K,Na)8Si16O40·11H2O is the main composition in foulants. The fouling mechanism of wheat black liquor is quite different from that of soft/hard wood black liquor, because the content of Si inside wheat straw black liquor is much more than that of soft/hard wood black liquor. Complex chemical reactions occur when evaporating wheat straw black liquor. The author considers that colloid H2SiO3 plays an important role in the process. The minerals produced by reactions between H2SiO3, with anion charges and positive ions, such as Ca2+, K+, Na+, etc. Further investigation on the process should be done.The fractal theory is used to analyze the fouling geometric texture. The fractal dimension values D of foulants are also calculated.