Corrosion resistance of Mg-Al-LDH steam coating on AZ80 Mg alloy:Effects of citric acid pretreatment and intermetallic compounds

In this study,the effects of intermetallic compounds(Mg_(17)Al_(12)and Al_(8)Mn_(5))on the Mg-Al layered double hydroxide(LDH)formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)_(2)steam coatings on AZ80 Mg alloy were investigated.Citric acid(CA)was used to activate the alloy surface during the pretreatment process.The alloy was first pretreated with CA and then subjected to a hydrothermal process using ultrapure water to produce Mg-Al-LDH/Mg(OH)_(2)steam coating.The effect of different time of acid pretreatment on the activation of the intermetallic compounds was investigated.The microstructure and elemental composition of the obtained coatings were analyzed using FE-SEM,EDS,XRD and FT-IR.The corrosion resistance of the coated samples was evaluated using different techniques,i.e.,potentiodynamic polarization(PDP),electrochemical impedance spectrum(EIS)and hydrogen evolution test.The results indicated that the CA pretreatment significantly influenced the activity of the alloy surface by exposing the intermetallic compounds.The surface area fraction of Mg_(17)Al_(12)and Al_(8)Mn_(5)phases on the surface of the alloy was significantly higher after the CA pretreatment,and thus promoted the growth of the subsequent Mg-Al-LDH coatings.The CA pretreatment for 30 s resulted in a denser and thicker LDH coating.Increase in the CA pretreatment time significantly led to the improvement in corrosion resistance of the coated AZ80 alloy.The corrosion current density of the coated alloy was lower by three orders of magnitude as compared to the uncoated alloy.

Co-Production of High-Grade Dissolving Pulp,Furfural,and Lignin from Eucalyptus via Extremely Low Acid Pretreatment and Pulping Technologies and Catalysis

Hemicellulose and lignin are not reasonably utilized during the dissolved pulp preparation process.This work aimed to propose a process for the co-production of dissolving pulp,furfural,and lignin from eucalyptus.High-grade dissolving pulp was prepared from eucalyptus using a combination of extremely low acid(ELA)pretreatment,Kraft cooking,and elementary chlorine-free(ECF)bleaching.The obtained pre-hydrolysate was catalytic conversion into furfural in a biphasic system,and lignin during Kraft cooking and ECF was recovered.The process condition was discussed as well as the mass flow direction.The results showed that ELA pretreatment could effectively remove 80.1%hemicellulose.Compared with traditional hydrothermal pretreatment,the ELA pretreatment significantly increased the xylose yield from 5.05 to 14.18 g/L at 170℃ for 2 h,which had practical significance for furfural production.The 82.7%furfural yield and 82.9%furfural selectivity were obtained from xylose-rich pre-hydrolysate using NaCl as a phase modifier in a biphasic system with 4-methyl-2-pentanone(MIBK)as an organic phase by ion exchange resin catalysts at 190℃ for 2 h.Subsequently,the pretreated eucalyptus was subjected to Kraft cooking,and the optimal alkali amount was 14%.Then,the Kraft pulp was bleached using the O-D1-EP-D_(2) sequence,and dissolving pulp was obtained with an ISO brightness of 86.0%,viscosity of 463 mL/g,andα-cellulose content of 95.4%.The Kraft lignin which has a potential application was investigated by 2D-HSQC NMR and 31P NMR.The results showed that the S/G ratio of Kraft lignin was 1.93,and the content of phenolic hydroxyl groups was 2.53 mmol/g.Moreover,based on the above proposed process,30.5 g dissolving pulp,5.5 g furfural,and 21.2 g lignin per 100 g eucalyptus chips(oven dry)were produced.This research will provide new catalysis and pulping technical routes for dissolving pulp,furfural,and Kraft lignin products,which are in great demand in the chemical industry.

Comparison of Dilute Organic Acid Pretreatment and a Comprehensive Exploration of Citric Acid Pretreatment on Corn Cob

As an important agricultural waste,corn cob is one of the most abundant lignocellulosic biomass.In this work,dilute acid pretreatment using seven different organic acids were compared for compositional analysis of corn cob.The first pKa of organic acids,influenced by the number and type of the side group and distance between two carboxylic groups,played a crucial role in the pretreatment effect.Citric acid was found to have better pretreatment performance than other tested dicarboxylic acids.Under the condition of 30 mM,160°C and 60 min,the level of xylose reached 22.64 g/L in pretreatment liquid,and the pretreated corn cob demonstrated the high enhancement of enzymatic hydrolysis up to 93.4%and the ethanol yield was 73.6%.

Nano⁃Silica Production by Rice Husk Combustion in a 0.7 MW Double⁃Circulating Fluidized Bed after Acid Pretreatment

Rice husk is an organic silicon source for amorphous nano⁃silica particles.This paper reports the experimental study on the industrial production of nano⁃silica by rice husk combustion in a specially⁃designed 0.7 MW double⁃circulating fluidized bed(DCFB)based on acid pretreatment process.The physicochemical properties of RHA were characterized by various testing instruments.Results showed that acid pretreatment removed a large amount of metal impurities in the rice husk and thus inhibited the formation of crystalline silica or the agglomeration during the fluidized bed combustion process.The combustion efficiencies were as high as 99.5%.The obtained RHA comprised white fine particles and exhibited an amorphous structure,but factors such as collection point and acid type had certain influences on the quality of RHA.The highest SiO2 purity was greater than 98.6 wt.%,the lowest content of unburned carbon was 0.2 wt.%,the specific surface area reached 178 m2/g,and the pore size reached 5 nm.The circulating fluidized bed combustion of rice husk based on acid pretreatment can prepare nano⁃silica while providing heat for industrial processes,which is a highly energy⁃rich process.

Effects of Ultrasonic and Acid Pretreatment on Food Waste Disintegration and Volatile Fatty Acid Production

This study aims at investigating the effects of ultrasonic and acid pretreatment on food waste( FW)disintegration and volatile fatty acid( VFA) production. Single-factor experiments are carried out to obtain optimal conditions of individual ultrasonic and acid pretreatment,and response surface method( RSM) is applied to optimize the conditions of the combination of ultrasonic and acid( UA) pretreatment. Results show that the optimal acid,ultrasonic and UA pretreatments conditions are individual pH 2,individual ultrasonic energy density of 1. 0 W / mL and the combination of ultrasonic energy density1. 11 W / mL and pH 1. 43,respectively. Correspondingly,the maximum disintegration degrees( DD) of 46. 90%,57. 38% and68. 83%are obtained by acid,ultrasonic and UA pretreatments,respectively. After optimizing pretreatment conditions,batch experiments are operated to produce VFA from raw and pretreated FW under anaerobic fermentation process. Both the maximum VFA production( 976. 17 mg COD / gV S) and VFA / SCOD( 72. 89%) are obtained with ultrasonic pretreatment, followed by UA pretreatment, non-pretreatment and acid pretreatment,respectively. This observation demonstrates that a higher acidity on acid and UA pretreatments inhibits the generation of VFA. Results suggest that ultrasonic pretreatment is preferable to promote the disintegration degree of FW and VFA production.

Kinetic features of xylan de-polymerization in production of xylose monomer and furfural during acid pretreatment for kenaf,forage sorghums and sunn hemp feedstocks

A kinetic study of acid pretreatment was conducted for sorghum non-brown mid rib(SNBMR)(Sorghum bicolor L Moench),sorghum-brown mid rib(SBMR),sunn hemp(Crotalaria juncea L)and kenaf(Gossypiumhirsutum L),focusing on rates of xylose monomer and furfural formation.The kinetics was investigated using two independent variables,reaction temperature(150°C and 160°C)and acid concentration(1 and 2 wt%),with a constant dry biomass loading of 10 wt%and a treatment time up to 20 min while sampling the mixture every 2 min.The experimental data were fitted using a two-step kinetic model based on irreversible pseudo first order kinetics at each step.Varied kinetic orders on the acid concentration,ranging from 0.2 to>3,were observed for both xylose and furfural formation,the values depending on the feedstock.The crystallinity index of raw biomass was shown to be a major factor influencing the rate of both xylose and furfural formation.A positive correlation was observed between the activation energy and biomass crystallinity index for xylose formation.

Coproduction of xylose and biobutanol from corn stover via recycling of sulfuric acid pretreatment solution

Sulfuric acid was used in the pretreatment of corn stover to obtain xylose as a value-added by-product,and the pretreated corn stover(Pre-CS)was hydrolyzed to produce glucose for butanol fermentation.The aim of this work is to achieve high xylose accumulation and reduced wastewater by recycling the pretreatment solution.The pretreatment conditions were optimized as follows:180°C,15 min,1:7 solid-liquid ratio(w/w),0.6%H_(2)SO_(4)(w/w,first batch)/0.9%H_(2)SO_(4)(w/w,second and third batches),in which pretreatment solution was recycled for three times.Under above conditions,pretreatment solution containing 56.3 g/L xylose and 4.5 g/L glucose was obtained.Pre-CS residue was further hydrolyzed by cellulase to achieve 35.7-39.9 g/L glucose.The condensed corn stover hydrolysate was subjected to simultaneous detoxification and sterilization using 1%(w/w)activated carbon and then applied in butanol fermentation.The highest butanol titer of 9.5 g/L was obtained in 72 h.The results provide a practical approach for coproducing xylose and biobutanol from corn stover.

Study on New Pretreatment Combining Dilute Acid Treatment and Organic Solvent Water / Ethanol for Biorefinery： Application to Switch Grass

Switch grass was developed as a pioneer energy crop in USA with great industrial prospect. It contains about 60% sugars and 18% lignin. The purpose of this research is to find pretreatment process to fractionate cellulose, hemicellulose and lignin from switch grass to obtain much more useful chemicals and enhance the residue solid to be hydrolyzed by enzymes. The six different pretreatment methods were studied, such as hot water pretreatment （HWP） alone, dilute acid pretreatment （DAP）, ammonia pretreatment （AP）, lime pretreatment （LP）, organosolv water / ehanol pretreatment （OWEP）, and organosolv water / acetone pretreatment （OWAP）. It was the best method combining DAP with OWEP because the hemicellulose sugars were recovered in the first residual liquid while a varied amount of cellulose was retained in the residual solid and the lignin fraction was obtained by simply adjusting the pH from the second liquid. The result shows the optimal two-stage process consisted of the first stage DAP at 428 K for 7 min with 0.8% sulfuric acid, resulting in 79.82% glucose recovery yield and 98.74% xylose removal and the second stage OWEP at 468K for 20 min in 45% （v / v） ethanol with 0.4% NaOH, resulting in 62% total glucose yield 99% xylose and 80% lignin removal. After enzymatic hydrolysis, the glucose yield was up to 92.6%, compared with 16% yield from untreated switch grass. Scanning electron microscopy （SEM） highlighted the differences in switch grass structure from the various pretreatment methods during biomass fractionation.

Conversion of Sugarcane Shoots and Leaves into Reducing Sugars by Pretreatment and Enzymatic Hydrolysis

Sugarcane shoots and leaves consist of 38% cellulose, 30.6% hemicellulose and 12.8% lignin on dry solid （DS） basis and have the potential to serve as low cost feedstocks for ethanol production. The pretreatment and enzymatic hydrolysis conditions include particle size, alkali （NaOH）/dilute acid （H2SO4） pretreatment, chemical and substrate concentrations, temperature, autoclaving time for pretreatment, enzyme concentration, pH and temperature for hydrolysis varied were evaluated for conversion of sugarcane shoots and leaves cellulose and hemicellulose to reducing sugar. The optimum conditions were accomplished by using 14% w/v DS of 0-10 mm sugarcane shoots and leaves in particle size, pretreated with 1.5% w/v of dilute sulfuric acid at 121℃, 15 lbs/in2 for 15 min and enzymatic saccharification using 40 FPU/g DS cellulose at 50℃ and pH 5, After incubating at 160 rpm for 12 hrs, 59 g/L or 386,38 mg/g DS of reducing sugar and 50.69% saccharification were obtained.

Influence of intermetallic Al-Mn particles on in-situ steam Mg-Al-LDH coating on AZ31 magnesium alloy

The influence of intermetallic Al-Mn particles on the corrosion behavior of in-situ formed Mg-Al layered double hydroxide(Mg-Al-CO32--LDH)steam coating on AZ31 Mg alloy was investigated.The alloy was pretreated with H3PO4,HCl,HNO3or citric acid(CA),followed by hydrothermal treatment,for the fabrication of Mg-Al-LDH coating.The microstructure,composition and corrosion resistance of the coated samples were investigated.The results showed that the surface area fraction of Al-Mn phase exposed on the surface of the alloy was significantly increased after CA pretreatment,which promotes the growth of the Mg-Al-LDH steam coating.Further,the LDH-coated alloy pretreated with CA possessed the most compact surface and the maximum coating thickness among all the coatings.The corrosion current density of the coated alloy was decreased by three orders of magnitude as compared to that of the bare alloy.

Preliminary evaluation of five elephant grass cultivars harvested at different time for sugar production

Five elephant grass cultivars, Pennisetum purpureum, cv. Huanan （Huanan）, P. purpureum, cv. N51 （N51）, P. purpureum, cv. Sumu No. 2 （Sumu-2）, （ Penniseturn americanum x P. purpureum ） x P. purpureum cv. Guimu No. 1 （Guimu-1） and P. americanum cv. Tift23A x P. purpureum cv. Tilt NS1 （Hybrid Pennisetum）, at three harvest stages were studied. With dilute sulfuric acid pretreatment followed by enzymatic hydrolysis, it is found that cel- lulose conversion of the five elephant grass cultivars harvested in August and September is higher than that har- vested in October. The cellulose conversion for elephant grass cultivars harvested in August and September follows an order of Hybrid Pennisetum 〉 Sumu-2 〉 Huanan 〉 Guimu-1 〉 N51. This may be explained by the fact that lignification is gradually strengthened with time, inhibiting degradation of cellulose and hemicellulose. Moreover, cellulose conversions of Hybrid Pennisetum, Sumu-2 and Huanan harvested in August and September are higher based on hierarchical clustering results.

Sorghum as Dry Land Feedstock for Fuel Ethanol Production

Dry land crops such as sorghums （grain sorghum, promising feedstocks for fuel ethanol production. The major issue sweet sorghum and forage sorghum） have been identified as for using the sweet sorghum as feedstock is its stability at room temperature. At room temperature, the sweet sorghum juice could lose from 40% to 50% of its fermentable sugars from 7 to 14 days No significant sugar content and profile changes were observed in juice stored at refrigerator temperature in two weeks. Ethanol fermentation efficiencies of fresh and frozen juice were high （-93%）. Concentrated juice （≥25% sugar） had significantly lower efficiencies and large amounts of fructose left in finished beer; however, winery yeast strains and novel fermentation techniques may solve these problems. The ethanol yield from sorghum grain increased as starch content increased. No linear relationship between starch content and fermentation efficiency was found. Key factors affecting the ethanol fermentation efficiency of sorghum include starches and protein digestibility, amylose-lipid complexes, tannin content, and mash viscosity. Life cycle analysis showed a positive net energy value （NEV） = 25 500 Btu/gal ethanol. Fourier transform infrared （FTIR） spectroscopy and X-ray diffraction （XRD） were used to determine changes in the structure and chemical composition of sorghum biomasses. Dilute sulfuric acid pretreatment was effective in removing the hemicellulose from biomasses and exposing the cellulose for enzymatic hydrolysis. Forage sorghum lignin had a lower syringyl/guaiacyl ratio and its pretreated biomass was easier to hydrolyze. Up to 72% hexose yield and 94% pentose yield were obtained by using a modified steam explosion with 2% sulfuric acid at 140℃ for 30 min and enzymatic hydrolysis with cellulase.

Structural Changes of Poplar Wood Lignin in Hydrothermal pretreatment in Acetic Acid-Sodium Acetate system

Hydrothermal pretreatment of poplar wood chips was performed in an acetic acid/sodium acetate buffer medium.To characterize the structural changes of lignin in the pretreatment process,milled wood lignin(MWL)was isolated from both the un-treated and treated poplar wood chips,and analyzed by ^(1)H-NMR,^(13)C-NMR,^(31)P-NMR,FT-IR,and GPC-MALLS.Results showed that the lignin in the pretreated wood chips had more phenolic OH groups,less aliphatic OH groups,higher molecular weight,and narrower polydispersity,in comparison with the lignin in the un-treated wood.The acetic acid-sodium acetate buffer pretreatment facilitated the removal of-OCH_(3) groups and the cleavage of the inter-unit linkages ofβ-O-4 bond in the lignin.Furthermore,the re-polymerization of lignin in the acetic acid-sodium acetate buffer pretreatment was found to be less than that in autohydrolysis.