Conversion of rice husk into fermentable sugar and silica using acid-catalyzed ionic liquid pretreatment.

Rice husk is a bulky byproduct with a high silica content from rice milling. In this study, the application of an acid-catalyzed ionic liquid (IL) pretreatment was studied for processing rice husks with a rugged structure. The pretreatment conditions were 130°C for 30 min with 1.2 wt% HCl. The results of enzymatic hydrolysis demonstrated that cellulose conversion of HCl-BMIMCl-treated at 48 h was increased by 660.05%, 538.81%, and 376.55% compared with the untreated, HCl-treated, and BMIMCl-treated rice husks, respectively. Composition analysis demonstrated that most of the hemicellulose was removed in the acid-IL combined treatment. Moreover, scanning electron microscopy, X-ray diffraction (XRD), and Fourier transform infrared analyses indicated that the crystalline structure and outer silica layer of the rice husks were efficiently broken up. The results revealed that the HCl-catalyzed dissolution is highly favorable for the industrial application of rick husks in the production of fermentable sugar and high-purity silica.

Accelerated crystallization of magnetic 4A-zeolite synthesized from red mud for application in removal of mixed heavy metal ions.

To cope with the increasing environmental issues of red mud, an integrated technological route for its comprehensive utilization was developed through the extraction of valuable components and the synthesis of magnetic 4A-zeolite. To accelerate the crystallization process of the synthesized 4A-zeolite, sodium chloride (NaCl) was innovatively employed under hydrothermal treatment. The effects of various parameters, including mass ratio of red mud/NaOH, alkali fusion temperature, alkali fusion time and molar ratio of NaCl/Al2O3, were systematically investigated. The results showed that approximately 81.0% Al, 76.1% Si and 95.8% Fe were utilized from red mud using alkali fusion and acid leaching methods. The optimal conditions of the alkali fusion process were determined as: mass ratio of red mud/NaOH = 1/2, alkali fusion temperature of 800 °C, and time of 90 min. Furthermore, when the molar ratio of NaCl/Al2O3 was kept at 1.5, the crystallization time reduced from 240 min to 150 min, and particle size distributions narrowed from 20-100 µm to 1-10 µm. The practical applications in removal of mixed heavy metal ions (Zn2+, Cu2+, Cd2+, Ni2+, and Pb2+) from wastewater indicated that the as-synthesized magnetic 4A-zeolite is a promising candidate for heavy metals adsorption.

Enhanced Enzymatic Hydrolysis of Rice Straw Pretreated by Oxidants Assisted with Photocatalysis Technology.

This work evaluated the effectiveness of rice straw pretreatment using a TiO2/UV system in the presence of oxidants. The effects of TiO2 concentrations, pH and photocatalysis time were investigated. Inorganic oxidants including H2O2, K2S2O8, and KIO4 were added to further enhance the effect on enzymatic hydrolysis of rice straw. The TiO2/UV/ H2O2 pretreatment showed a higher amount of released reducing sugar (8.88 ± 0.10 mg/mL, compared to 5.47 ± 0.03 mg/mL in untreated sample). Composition analyses of rice straw after the TiO2/UV/H2O2 pretreatment showed partial lignin and hemicellulose removal. Moreover, structural features of untreated and pretreated rice straw were analyzed through FE-SEM, FT-IR, and XRD. This work suggests that H2O2 is an efficient addition for photocatalysis pretreatment of rice straw.

Characterization of a thermophilic cellulase from Geobacillus sp. HTA426, an efficient cellulase-producer on alkali pretreated of lignocellulosic biomass.

A themophilic cellulase-producing bacterium was isolated from a hot spring district and identified as Geobacillus sp. HTA426. The cellulase enzyme produced by the Geobacillus sp. HTA426 was purified through ammonium sulfate precipitation and ion exchange chromatography, with the recovery yield and fold purification of 10.14% and 5.12, respectively. The purified cellulase has a molecular weight of 40 kDa. The optimum temperature and pH for carboxymethyl cellulase (CMCase) activity of the purified cellulase were 60°C and pH 7.0, respectively. The enzyme was also stable over a wide temperature range of 50°C to 70°C after 5 h of incubation. Moreover, the strain HTA426 was able to grow and produce cellulase on alkali-treated sugarcane bagasse, rice straw and water hyacinth as carbon sources. Enzymatic hydrolysis of sugarcane bagasse, which was regarded as the most effective carbon source for cellulase production (CMCase activity = 103.67 U/mL), followed by rice straw (74.70 U/mL) and water hyacinth (51.10 U/mL). This strain producing an efficient thermostable cellulose is a potential candidate for developing a more efficient and cost-effective process for converting lignocellulosic biomass into biofuel and other industrial process.

The effect of surfactant-assisted ultrasound-ionic liquid pretreatment on the structure and fermentable sugar production of a water hyacinth.

This study investigated the possibility of enhancing the disruption of water hyacinth (WH) in an ultrasound-ionic liquid (US-IL) pretreatment assisted by sodium dodecyl sulfate (SDS). 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was used to dissolve the WH. The optimum concentration of SDS for the highest production of reducing sugar was also determined. Compared to the US-IL pretreatment, the production of reducing sugars, cellulose conversion and delignification were increased by 72.23%, 58.74% and 21.01%, respectively, upon addition of 0.5% SDS. Moreover, the enhancement of SDS in the US-IL pretreatment was confirmed by the analysis of structural features, which demonstrated that the SDS increased the removal of lignin and decreased the cellulose crystallinity.

Impact of surfactant type for ionic liquid pretreatment on enhancing delignification of rice straw.

This work describes an environmentally friendly method for pretreating rice straw by using 1-Allyl-3-methylimidazolium chloride ([AMIM]Cl) as an ionic liquid (IL) assisted by surfactants. The impacts of surfactant type (including nonionic-, anionic-, cationic- and bio-surfactant) on the ionic liquid pretreatment were investigated. The bio-surfactant+IL-pretreated rice straw showed significant lignin removal (26.14%) and exhibited higher cellulose conversion (36.21%) than the untreated (16.16%) rice straw. The cellulose conversion of the rice straw pretreated with bio-surfactant+IL was the highest and the lowest was observed for pretreated with cationic-surfactant+IL. Untreated and pretreated rice straw was thoroughly characterized through SEM and AFM. In conclusion, the results provided an effective and environmental method for pretreating lignocellulosic substrates by using green solvent (ionic liquid) and biodegradable bio-surfactant.

Spent mushroom substrate biochar as a potential amendment in pig manure and rice straw composting processes.

Spent mushroom substrate (SMS) is a bulky waste byproduct of commercial mushroom production, which can cause serious environmental problems and, therefore, poses a significant barrier to future expansion of the mushroom industry. In the present study, we explored the use of SMS as a biochar to improve the quality of bio-fertilizer. Specifically, we performed a series of experiments using composting reactors to investigate the effects of SMS biochar on the physio-chemical properties of bio-fertilizer. Biochar was derived from dry SMS pyrolysed at 500°C and mixed with pig manure and rice straw. Results from this study demonstrate that the addition of biochar significantly reduced electrical conductivity and loss of organic matter in compost material. Nutrient analysis revealed that the SMS-derived biochar is rich in fertilizer nutrients such as P, K, Na, and N. All of these findings suggest that SMS biochar could be an excellent medium for compost.

Thermodynamic Equilibrium Calculations on Cd Transformation during Sewage Sludge Incineration.

Thermodynamic equilibrium calculations were performed to reveal the distribution of cadmium during the sewage sludge incineration process. During sludge incineration in the presence of major minerals, such as SiO2, Al2O3 and CaO, the strongest effect was exerted by SiO2 on the Cd transformation compared with the effect of others. The stable solid product of CdSiO3 was formed easily with the reaction between Cd and SiO2, which can restrain the emissions of gaseous Cd pollutants. CdCl2 was formed more easily in the presence of chloride during incineration, thus, the volatilization of Cd was advanced by increasing chlorine content. At low temperatures, the volatilization of Cd was restrained due to the formation of the refractory solid metal sulfate. At high temperatures, the speciation of Cd was not affected by the presence of sulfur, but sulfur could affect the formation temperature of gaseous metals.

Synergistic effects of surfactant-assisted ionic liquid pretreatment rice straw.

The aim of this work was to study an environmentally friendly method for pretreating rice straw by using 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as an ionic liquid (IL) assisted by surfactants. Different temperatures, reaction times, and surfactant concentrations were studied. Compared with [BMIM]Cl only pretreatment, the addition of 1% sodium dodecyl sulfate (SDS) and 1% cetyl trimethyl ammonium bromide (CTAB) increased lignin removal to 49.48% and 34.76%, respectively. Untreated and pretreated rice straw was thoroughly characterized through FTIR, XRD, and FE-SEM. Cellulose crystallinity and surface morphology of the rice straw were substantially altered after surfactant-assisted IL pretreatment. In conclusion, surfactant-assisted IL pretreatment is an effective method for producing fermentable sugars from lignocellulosic substrates.

Fate of volatile aromatic hydrocarbons in the wastewater from six textile dyeing wastewater treatment plants.

The occurrence and removal of benzene, toluene, ethylbenzene, xylenes, styrene and isopropylbenzene (BTEXSI) from 6 textile dyeing wastewater treatment plants (TDWTPs) were investigated in this study. The practical capacities of the 6 representative plants, which used the activated sludge process, ranged from 1200 to 26000 m(3) d(-1). The results indicated that BTEXSI were ubiquitous in the raw textile dyeing wastewater, except for isopropylbenzene, and that toluene and xylenes were predominant in raw wastewaters (RWs). TDWTP-E was selected to study the residual BTEXSI at different stages. The total BTEXSI reduction on the aerobic process of TDWTP-E accounted for 82.2% of the entire process. The total BTEXSI concentrations from the final effluents (FEs) were observed to be below 1 µg L(-1), except for TDWTP-F (2.12 µg L(-1)). Volatilization and biodegradation rather than sludge sorption contributed significantly to BTEXSI removal in the treatment system. BTEXSI were not found to be the main contaminants in textile dyeing wastewater.

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations.

Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na2S and Na2SO4) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na2SO4 and Na2S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO4(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO2, CaO, TiO2, and Al2O3 containing materials function as condensed phase solids in the temperature range of 800-1100 K as sorbents to stabilize Pb. However, in the presence of sulfur or chlorine or the co-existence of sulfur and chlorine, these sorbents were inactive. The effect of sulfur on Pb partitioning in the sludge incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the concentration of Si, Ca and Al-containing compounds in the sludge. These findings provide useful information for understanding the partitioning behavior of Pb, facilitating the development of strategies to control the volatilization of Pb during sludge incineration.

Effect of different sulfides on cadmium distribution during sludge combustion based on experimental and thermodynamic calculation approaches.

The effects of sulfur compounds on the migration of a semi-volatile heavy metal (cadmium) during sludge incineration were investigated with two methods, i.e., experiments in a tubular furnace reactor and thermodynamic equilibrium calculations. The representative typical sludge with and without the addition of sulfur compounds was incinerated at 850 °C. The partitioning of Cd among the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that sulfur compounds in the elemental form and a reduced state could stabilize Cd in the form of CdS, aluminosilicate minerals, and polymetallic sulfides, whereas sulfur in the oxidized forms slightly increases Cd volatilization during incineration. For Cd solidification points, the inhibition effect on the volatilization of Cd is as follows: S > Na2SO4 > Na2S. Chemical equilibrium calculations indicate that sulfur binds with Cd and alters Cd speciation at low temperatures (<950 K). Furthermore, SiO2- and Al2O3-containing minerals can function as sorbents stabilizing Cd as condensed phase solids (CdSiO4 and CdAl2O4) according to the results of equilibrium calculations. These findings provide useful information for understanding the partitioning of Cd and thus facilitate the development of strategies to control Cd volatilization during sludge incineration.

[Effects of chlorides on Cd transformation in a simulated grate incinerator during sludge incineration process ].

The effects of organic chloride-PVC and inorganic chloride-NaCl on Cd partitioning during sludge incineration with adding Cd(CH3COO)2 . 2H2O to the real sludge were investigated using a simulated tubular incineration furnace. And transformation and distribution of Cd were studied in different sludge incineration operation conditions. The results indicated that the partitioning of Cd tended to be enhanced in the fly ash and fule gas as the chloride content increasing. The migration and transformation of Cd-added sludge affected by different chloride were not obvious with the increasing of chloride content. With increasing temperature, organic chloride (PVC) and inorganic chloride (NaC1) can reduce the Cd distribution in the bottom ash. However, the effect of chlorides, the initial concentration and incineration time on Cd emissions had no significant differences. Using SEM-EDS and XRD technique, different Cd compounds including CdCl2, Na2CdCl4, K2CdCl6, K2CdSiO4 and NaCdO2 were formed in the bottom ash and fly ash after adding NaCl to the sludge. In contrast, after adding PVC to the sludge, the Na2CdCl4 and CdCl2 were the main forms of Cd compounds, at the same time, K4CdCI6 and K6CdO4 were also formed. The two different mechanisms of chlorides effects on Cd partitioning were affected by the products of Cd compound types and forms.

Levels, composition profiles and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sludge from ten textile dyeing plants.

As components of synthetic dyes, polycyclic aromatic hydrocarbons (PAHs) are present as contaminants in textile dyeing sludge due to the recalcitrance in wastewater treatment process, which may pose a threat to environment in the process of sludge disposal. In order to evaluate PAHs in textile dyeing sludge, comprehensive investigation comprising 10 textile dyeing plants was undertaken. Levels, composition profiles and risk assessment of 16 EPA-priority PAHs were analyzed in this study. The total concentrations of 16 PAHs (∑16 PAHs) varied from 1463 ± 177 ng g(-1) to 16,714 ± 1,507 ng g(-1) with a mean value of 6386 ng g(-1). The composition profiles of PAHs were characterized by 3- and 4-ring PAHs, among which phenanthrene, anthracene and fluoranthene were the most dominant components. The mean benzo[a]pyrene equivalent (BaPeq) concentration of ∑16 PAHs in textile dyeing sludge was 423 ng g(-1), which was 2-3 times higher than concentrations reported for urban soil. According to ecological risk assessment, the levels of PAHs in the textile dyeing sludge may cause a significant risk to soil ecosystem after landfill or dumping on soil.

[Effects of adsorbents on partitioning and fixation of heavy metals in the incineration process of sewage sludge].

Experiments were carried out on laboratory-scale electrically heated tube furnace sewage sludge combustion with different adsorbents. Four solid adsorbents (calcium oxide, Alumina, fly ash and kaolin) were used to control the emission of heavy metals (Pb, Cd, Cu, Cr, Ni, Zn) during the sewage sludge incineration. The results showed that the heavy metals tended to be fixed and left over in the incineration bottom ash with the addition of calcium oxide, Alumina, fly ash and kaolin. With the increase of the solid adsorbent ratio, the residual rate of heavy metals in the bottom ash also increased. Incineration temperature had a great influence on the heavy metal adsorption effect of the solid adsorbent. The forms, melting point and boiling point of the heavy metals were found to be important factors that determined its volatility. There was huge difference in the inhibitory effect of different adsorbents on heavy metals migration. From the view of controlling heavy metal evaporation, the adsorbents kaolin and CaO were superior to the other adsorbents. The interaction between the active center of the solid adsorbent and the molecules of the heavy metal compounds depended on the distribution of these active sites and the chemical properties of the heavy metals.

[Analysis of hydrolytic enzyme activities on sludge aerobic/anoxic digestion after ultrasonic pretreatment].

In order to evaluate the function of sludge aerobic/anoxic digestibility by ultrasonic pretreatment. The SS, VSS and hydrolytic enzyme activities (amylase, glucosidase, protease, phosphatase) were measured before and after ultrasonic pretreatment (28 kHz, 0.15 kW x L(-1), 10 min). The results showed that the performances of aerobic/anoxic were greatly improved after ultrasonic pretreatment, the removal efficiency of VSS went to 44.3%, 7.8% better than of traditional aerobic/anoxic digestion. The variational trend of sludge hydrolytic enzyme activities increased firstly and then fell off during 13d digestion, the maximum of amylase activity and glucosidase activity in ultrasonic sludge, appeared in the 5 d, amylase activity was 0.104 micromol x g(-1) and glucosidase activity was 0.637 (micromol x g(-1). The maximum of intracellular protease activity and extracellular proteases activity in ultrasonic sludge, appeared in the 7 d, intracellular protease activity was 23.68 micromol x g(-1), higher than extracellular proteases activity, and it was playing a leading role in sludge digestion. The acid phosphatase activity of ultrasonic sludge was higher than the control sludge, and the alkaline phosphatase was sensitive to environment. So the alkaline phosphatase activity reduced when the internal properties of sludge was changed.

[Chlorination transformation and volatilization of heavy metals in fly ash from the incineration during the disposal process with higher temperature].

The volatilization of heavy metals Pb, Cd, Cu and Zn were studied at 900 degrees C and 1 000 degrees C with different residence time, meanwhile the influence of chlorination agents CaCl2, MgCl2, NaCl, FeCl3 and AlCl3 on heavy metals volatilization was studied. The results showed that the volatilization of heavy metals had great differences with the volatilization rate followed the order Pb > Cd > Zn > Cu, in which the volatilization rate of Pb was more than 80% and that of Cu was less than 30%. In the thermal disposal process, the volatilization rate influenced by temperature was greater than that by the residence time, and the volatile elements Pb and Cd were particularly evident in the volatilization. After adding chlorides in fly ash, the volatilization of heavy metals changed significantly, and the volatilization rate of the low volatile elements Cu and Zn increased significantly compared with Pb and Cd. With the content of chloride increasing, the volatilization rate of heavy metals increased, but different types of chloride compounds on heavy metal transformation were quite different, in which the promotion effect of NaCl on heavy metals Cd, Zn and Cu was less than that of other chlorinating agents. The results can provide strategies for the harmless disposal and maximize resource utilization and recycling of fly ash.

[Effects of sulphur compounds on the volatile characteristics of heavy metals in fly ash from the MSW and sewage sludge co-combustion plant during the disposal process with higher temperature].

Fly ash sample was collected from a MSW co-combustion with sewage sludge plant and the volatilization of heavy metals Pb, Cd, Cu and Zn was investigated before and after the water washing of fly ash, meanwhile, the influence of adding different sulphur compounds (S, NaS, Na2 SO3, Na2 SO4) on the volatilization of heavy metals was studied. The results showed that the contents of Zn, Pb and Mn were high, the Ni content was low and the Cd content reached 29.4 mg x kg(1). The contents of Pb, Cu, Zn increased, while that of Cd reduced in the fly ash after water washing. TG-DTG curves of fly ash showed highest weight loss in ranges of 579-732 degrees C and 949-1 200 degrees C, with 690 degrees C and 1 154 degrees C as the inflection point temperatures. The volatilization of different heavy metals showed great difference in the volatilization rate, following the order of Pb > Cd > Zn > Cu, in which the volatilization rate of Pb was more than 80% and that of Cu was less than 30%. After water washing, the volatilization of different heavy metals showed great difference in the volatilization rate, with the order of Zn > Pb > Cd > Cu, in which the volatilization rate of Zn was more than 20%. With the pretreatment of adding Na2 SO3 and Na2 SO4, the evaporation rates of heavy metals (Cu, Pb, Zn, Cd) were significantly decreased. After adding S, the evaporation rate of Zn was reduced, whereas the addition of Na2S reduced the evaporation rates of Cd and Zn. The evaporation rates of the four heavy metals were all reduced after adding Na2S in the washed fly ash. The evaporation rates of Cu and Zn were reduced with addition of S and Na2SO3 and the evaporation rate of Cd was reduced by adding the four sulfides. The results can provide a basis for the harmless disposal and maximized resource utilization and recycling of fly ash.

[Determination of metals in waste bag filter of steel works by microwave digestion-flame atomic absorption spectrometry].

A method of microwave digestion technique-flame atomic absorption spectrometry was proposed to determine the total contents of Cu, Zn, Pb, Cd, Cr and Ni in five different kinds of waste bag filters from a steel plant. The digestion effects of the six acid systems on the heavy metals digestion were studied for the first time. The relative standard deviation (RSD) of the method was between 1.02% and 9.35%, and the recovery rates obtained by standard addition method ranged from 87.7% to 105.6%. The results indicated that the proposed method exhibited the advantages of simplicity, speediness, accuracy and repeatability, and it was suitable for determining the metal elements of the waste bag filter. The results also showed that different digestion systems should be used according to different waste bag filters. The waste bag filter samples from different production processes had different metal elements content. The Pb and Zn were the highest in the waste bag filters, while the Cu, Ni, Cd and Cr were relatively lower. These determination results provided the scientific data for further treatment and disposal of the waste bag filter.