Wet Oxidation Pretreatment of Poplar Waste for Enhancing Enzymatic Hydrolysis Efficiency

In this paper, we described the optimization of the wet oxidation pretreatment conditions to enhance enzymatic hydrolysis efficiency, using poplar waste from the stock section of a paper mill as the raw material. We showed that the optimal conditions of the pretreatment for poplar waste were an initial p H value of 10, a temperature of 195℃, a holding time of 15 min, and an oxygen pressure of 1.2 MPa. In this case, the yield of the obtained solid material produced by the process was 51.7% and the reducing sugar yield was 46.8%. The solid part obtained from the pretreatment process was hydrolyzed by cellulase L-10. The optimal enzymatic conditions were a temperature of 49℃, a duration time of 56 h, an enzyme dosage of 38 FPU/g at a p H value of 4.8, and a solid-to-liquor ratio of 1∶50. The resulting cellulose conversion rate reached 96.4% in terms of the pretreated substances. In addition, a chemical composition analysis of the poplar waste and pretreated material indicated that about 92% of the hemicelluloses and 43% of the lignin in the raw material were degraded and dissolved. In addition, the crystallization decreased from 57.5% to 54.8%. An obvious fibrillation of the fiber pretreated by the wet oxidization process was observed by SEM. Moreover, high-performance liquid chromatography(HPLC) results showed a high xylose content and monosaccharide degradation products in the pretreatment solution. In conclusion, the wet oxidation pretreatment process could efficiently degrade or remove the lignin and hemicellulose, as well as reduce the crystallinity of the lignocellulosic material, which resulted in animprovement of the enzymatic ability and an increase in the cellulose conversion rate.

Preparation of hexagonal and amorphous chromium oxyhydroxides by facile hydrolysis of K_xCrO_y

The hydrolysis process and mechanisms of unique as-prepared KCrO2 and K3 CrO4 were systematically investigated. The characterization results of XRD, IR and SEM show that the hydrolysis reaction can be realized at a low reaction temperature of 80 ℃ and a reaction time of 24 h. Moreover, the greyish-green α-CrOOH with a hexagonal plate-like morphology and a large size of 10 μm is formed via the hydrolysis of the single-phase hexagonal KCrO2, while the green sol-gel of amorphous Cr(OH)3 with a lumpy aggregate morphology is generated through the hydrolysis of a cubic K3 CrO4. It is a facile and rapid method to synthesize pure-phase chromium oxyhydroxide via the above hydrolysis.

Single Pt Atoms Supported on Oxidized Graphene as a Promising Catalyst for Hydrolysis of Ammonia Borane

Based on density functional theory calculations,the full hydrolysis of per NH3BH3 molecule to produce three hydrogen molecules on single Pt atoms supported on oxidized graphene(Pt1/Gr-O)is investigated.It is suggested that the first hydrogen molecule is produced by the combination of two hydrogen atoms from two successive B-H bonds breaking.Then one H2O molecule attacks the left*BHNH3 group(*represents adsorbed state)to form*BH(H2O)NH3 and the elongated O-H bond is easily broken to produce*BH(OH)NH3.The second H2O molecule attacks*BH(OH)NH3 to form*BH(OH)(H2O)NH3 and the breaking of O-H bond pointing to the plane of Pt1/Gr-O results in the desorption of BH(OH)2NH3.The second hydrogen molecule is produced from two hydrogen atoms coming from two H2O molecules and Pt1/Gr-O is recovered after the releasing of hydrogen molecule.The third hydrogen molecule is generated by the further hydrolysis of BH(OH)2NH3 in water solution.The rate-limiting step of the whole process is the combination of one H2O molecule and*BHNH3 with an energy barrier of 16.1 kcal/mol.Thus,Pt1/Gr-O is suggested to be a promising catalyst for hydrolysis of NH3BH3 at room temperature.

Preparation of Fe_(3)O_(4) Film by in-situ Oxidative Hydrolysis on Chitosan

The Fe3O4 films were prepared by in-situ oxidative hydrolysis on chitosan. The structures and characteristics of the prepared Fe3O4 films were investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, atom force microscopy （AFM）, vibrating sample magnetometry （VSM） and thermogravimetric-differentia thermal analysis （TG-DTA）. The results show that, （1） the as-synthesized Fe3O4 films are pure Fe3O4 with cubic inverse spinel structure; （2） the network structured film can be obtained at lower temperature, and the compact particle film at higher temperature; （3） the prepared Fe3O4 films are super-paramagnetic, and the saturation magnetization is improved with increasing the reaction temperature, which is 49.03 emu/g at 80℃; （4） the temperature of phase transformation from Fe3O4 to a-Fe2O3 is about 495℃. Besides, the formation mechanism of Fe3O4 film was also proposed.

Study on Enzymatic Hydrolysis Technology and Antioxidant Activity of Glutinous Rice Glutinous Enzymatic Processes and Antioxidant Activity

[ Objective] This study aimed to investigate enzymatic hydrolysis technology of glutinous rice and the oxidation resistance activity of the enzymatic hydrolysis solution. [ Method ] White glutinous rice was hydrolyzed using four kinds of proteases including neutral protease, alkaline protease, papain and trypsin. Using the scavenging rate of hydroxyl radical （ ·OH） as an indicator and appropriate protease as hydrolytic enzyme, the effects of protein substrate concentration, enzyme dosage, enzymatic hydrolysis temperature and initial pH on the abilities of proteases to scavenge hydroxyl radical from enzymatic hydrolysis solution of glutinous rice were investigated. Based on single-factor test, L9 （34） orthogonal experimental design was adopted, to determine the optimal enzymatic hydrolysis condi- tions leading to the highest oxidation resistance activity of enzymatic hydrolysis solution. [ Result] The optimized process parameters for enzymatic hydrolysis of glu- tinous rice protein with neutral protease were： protein substrate concentration of 2%, enzyme dosage of 24 000 U/g protein （protein meter）, enzymatic hydrolysis temperature of 55 ℃, initial pH of 8.0, and enzymatic hydrolysis duration of 0.5 h; under these conditions, the hydroxyl radical scavenging rate could reach 56. 05% ; protein substrate concentration, enzyme dosage, enzymatic hydrolysis temperature and initial pH had extremely significant effects on the hydroxyl radical scavenging rate. In addition, the activities of antioxidant peptides in glutinous rice hydrolysates were well maintained within a temperature range of 60 - 100℃. [Condusion] The study produced theoretical feasibility reference for the production of functional base powder by spray drying.

Properties of TiO_2-SiO_2 Mixed Oxides and Photocatalytic Oxidation of Heptane and Sulfur Dioxide

A series of TiO 2-XSiO 2[X denotes the molar fraction(%) of silica in the mixed oxides] with different \{n(Ti)\}/n(Si) ratios was prepared with ammonia water as a hydrolysis catalyst. The photocatalysts prepared were characterized by XRD, thermal analysis, FTIR, UV-Vis and SPS. The characterization results of FTIR and UV-Vis spectra show that Ti atoms were gradually changed from octahedral coordination to tetrahedral coordination with the addition of silica, which is not beneficial for obtaining strong Brnsted acidity and higher photocatalytic activity. The photocatalytic activity experiments, which were conducted by using heptane(or SO 2) as the model reactant, showed that TiO 2-SiO 2 containing a suitable amount of silica can exhibit much higher photocatalytic activity than pure TiO 2. The enhanced photocatalytic activity can be attributed to three following factors: (1) smaller crystalline size; (2) higher thermal stability; (3) the new strong Brnsted acidity.

Catalytic hydrolysis of carbonyl sulfide over modified coal-based activated carbons by loading metal

A novel type of metal oxide/activated carbon catalyst was prepared by sol-gel method for the hydrolysis of carbonyl sulfide （COS）. The influences of the calcination temperature, additive content （2.5%-10.0% Fe2O3, mass fraction） and the basic density of the activation process were thoroughly investigated. The surface of catalysts was characterized by Boehm titration. The products were characterized by scanning electron microscopy （SEM）, X-ray diffractometry （XRD） and X-ray photoelectron spectroscopy （XPS）. The results show that catalysts with 2.5%-5.0% Fe2O3 after calcining at 500 ℃ have superior activity. The conversion rate of COS increases with increasing the relative density of basic capacity loaded onto activated carbon（AC）, and the activity follows the order： KOH〉Na2CO3 〉NaHCO3. Boehm titration data clearly show that the total acidity increases （from 0.06 to 0.48 mmol/g） and the basic groups decrease （from 0.78 to 0.56 mmol/g） after COS hydrolysis and H2S adsorption. The XPS results show that the product of HzS may be absorbed by the interaction with metal compounds and 02 to form sulfate （171.28 eV） and element sulfur （164.44 eV）, which lead to catalysts poisoning.

Effect of Ultra-Turrax on Nanocellulose Produced by Acid Hydrolysis and Modified by Nano ZnO by Sol-Gel Method

Cellulose nanocrystals (NCC) and cellulose nanofibrils (CNF) were obtained by a single step process, with synergy between 64% sulfuric acid hydrolysis and high shear from ultra-turrax stirring, which is an advantageous process for disintegrating cellulose microcrystalline and also may improve the hydrolysis process. The surface modification on the cellulose was performed by the sol-gel process, in which the sulfate groups from hydrolysis were replaced by nanoparticles of zinc oxide, which led to the increase of up to 54°C Tonset, according to thermogravimetric analysis (TGA) results. The morphology and crystallinity degree were characterized by Helium Ion Microscopy (HIM), atomic force microscopy (AFM) and X-ray diffraction. In addition, the ZnO band was observed in Fourier transform infrared spectroscopy, furthermore, the change in the zeta potential confirmed the cellulose modification. The changes in the values of proton spin-spin relaxation time for the systems showing the confined hydrogen in the rigid domains, confirmed the results observed with the aforementioned techniques, for both cellulose after hydrolysis and ZnO modified cellulose, suggesting that ZnO disrupted crystal formation in cellulose.

Dehydration, hydrolysis and oxidation of cerium chloride heptahydrate in air atmosphere

The thermal decomposition of CeCl3·7 H2O was studied from room temperature to 800 ℃. Analysis was performed by applying TG-DTA, XRD, FESEM, EDXS, and TG-MS technologies to investigate the thermal decomposition mechanism of CeCl3·7 H2O in air atmosphere. Multiple forms of hydrated cerium chloride compound were observed in the dehydration products. The CeCl3hydrolysis product was separated by a continuous centrifugation method and the phase composition was identified as CeO2,Ce(OH)3,and CeCl3·4 H2O by XRD analysis. The evolved gas composition was identified as CI2and HCI by TG-MS system. Based on the analysis of the experimental results, the mechanism of thermal decomposition of CeCl3·7 H2O was proposed with completion of the dehydration reaction at 224 ℃,the hydrolysis reaction at 170-480 ℃,and the oxidation reaction of CeCl3above 480 ℃.

Synthesis of Y_2O_3 phosphor by a hydrolysis and oxidation method

A novel and convenient hydrolysis and oxidation method was first used in preparation of carbon contained Y2O3 phosphor powders. The alloy was hydrolyzed in deionized water and the obtained Y（OH）3 powders were heat treated in air atmosphere. The final products - Y2O3 powders were micron clusters which were aggregated by hundreds of nanoparticles with the size of about 5 nm. The chemical composition, structural and morphological features of the samples were characterized by means of X-ray powder diffraction （XRD） analysis, transmission electron microscopy （TEM）, Fourier-transform infrared （FT-IR） spectra, X-ray photoelectron spectra （XPS） and carbon sulfur analyzer. The obtained powders showed good bluish-white photoluminescence （PL） emissions （ranging from 430 to 600 nm, peaking at 468 nm and 578 nm） under the xenon light excitation. The luminescent mechanism was ascribed to the carbon impurities in the Y2O3 host.

Characterization of value-added chemicals derived from the thermal hydrolysis and wet oxidation of sewage sludge

We evaluated the effect of hydrothermal pretreatments,i.e.,thermal hydrolysis(TH)and wet oxidation(WO)on sewage sludge to promote resource recovery.The hydrothermal processes were performed under mild temperature conditions(140°C–180°C)in a high pressure reactor.The reaction in acidic environment(pH=3.3)suppressed the formation of the color imparting undesirable Maillard’s compounds.The oxidative conditions resulted in higher volatile suspended solids(VSS)reduction(~90%)and chemical oxygen demand(COD)removal(~55%)whereas TH caused VSS and COD removals of~65%and~27%,respectively at a temperature of 180°C.During TH,the concentrations of carbohydrates and proteins in treated sludge were 400–1000 mg/L and 1500–2500 mg/L,respectively.Whereas,WO resulted in solids solubilization followed by oxidative degradation of organics into smaller molecular weight carboxylic acids such as acetic acid(~400–500 mg/L).Based on sludge transformation products generated during the hydrothermal pretreatments,simplified reaction pathways are predicted.Finally,the application of macromolecules(such as proteins),VFAs and nutrients present in the treated sludge are also discussed.The future study should focus on the development of economic recovery methods for various value-added compounds.

Design and optimization of an integrated process for the purification of propylene oxide and the separation of propylene glycol by-product

It is difficult to separate the methanol and hydrocarbons in the propylene oxide(PO)purification process due to their forming azeotrope.As for this,a novel PO separation process,in that the deionized water is employed as extractant and 1,2-propylene glycol(MPG)that is formed from the PO hydrolysis reaction is recovered,is presented in this work.The salient feature of this process is that both the non-catalyzed reactions of PO hydrolysis to form MPG and dipropylene glycol(DPG)are simultaneously considered and MPG by-product with high purity is obtained in virtue of the deionized water as reflux liquid and side take-off in MPG column.In addition,the ionic liquid(IL)extractant is screened through the conductorlike screening model for segment activity coefficient(COSMO-SAC)and the comparisons of separation efficiency between the IL and normal octane(nC_(8))extractant for the separation of PO and 2-methylpentane are made.With the non-random two-liquid(NRTL)thermodynamic model,the simulation and optimization design for the full flow sheet are performed and the effects of the key operation parameters such as solvent ratio,theoretical stages,feeding stage etc.on separation efficiency are detailedly discussed.The results show that the mass purity and the mass yield of PO can be up to 99.99%and 99.0%,and the condenser duty,reboiler duty and PO loss in the process with IL extractant can be decreased by 69.66%,30.21%and 78.86%compared to ones with nC_(8).The total annual cost(TAC)calculation also suggests that the TAC would be significantly reduced if using IL in replace of nC_(8) for the investigated process.The presented results would provide a useful guide for improving the quality of PO product and the economic efficiency of industrial plant.

A New Method for Preparing Ti-Si Mixed Oxides

Ti-Si mixed oxides with different TiO2 content were prepared by sol-gel one step hydrolysis, using TiCl4 as the precursor. The samples were characterized by BET, FT-IR and XRD. The results indicated that titanium is in fourfold coordination with oxygen in the SiO44- in mixed oxides, form the bond of Ti-O-Si, and the low titania materials are mixed on an atomic scale. The phase of anatase appeared when TiO2 content is up to 80%. The mixed oxides had high specific surface areas up to 681.5 m2/g. 10TiSi is a better support than SiO2 in the reaction of CO oxidation.

Kinetic study on hydrolysis and oxidation of formamidine disulfide in acidic solutions

Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography （HPLC） and mass spectrometry （MS） at 25 ~C. By controlling the slow reaction rate and choosing appropriate mobile phase, HPLC provides the unique advantages over other methods （UV-Vis, chemical separation） in species tracking and kinetic study. In addition to thiourea and formamidine sulfinic acid, two unreported products were also detected in the hy- drolysis reaction. Mass spectrometry measurement indicates these two products to be formamidine sulfenic acid and thiocyan- ogen with mass weights of 92.28 and 116,36, respectively. In the oxidation of formamidine disulfide by hydrogen peroxide, besides thiourea, formamidine sulfenic acid, formamidine sulfinic acid, thiocyanogen and urea, formamidine sulfonic acid and sulfate could be detected. The oxidation reaction was found to be first order in both forrnamidine disulfide and hydrogen per- oxide. The rate constants of hydrolysis and oxidation reactions were determined in the pH range of 1.5-3.0. It was found both rate constants are increased with the increasing of pH. Experimental curves of different species can be effectively simulated via a mechanism scheme for formamidine disulfide oxidation, including hydrolysis equilibrium of formamidine disulfide and irre- versible hydrolysis of formamidine sulfenic acid.

一种能温和产氢且具有高活性保持能力的Al-Bi-Zn基复合粉体

通过相图计算和气体雾化的方法,设计并制备Al-10Bi-7Zn和Al-10Bi-7Zn-1.5X (X:Cu, Fe, Ni)(质量分数,%)复合粉体。研究Cu、Fe和Ni对Al-Bi-Zn基复合粉体水解制氢性能的影响。通过X射线衍射(XRD)和扫描电子显微镜(SEM)以及能量色散谱(EDS)分析对粉体的组成和形貌进行表征。水解制氢性能测试结果表明,添加Cu、Fe或Ni可以改变Al-10Bi-7Zn三元合金复合粉体的制氢速率,并且提高其抗氧化性能。在四元复合粉体体系中,Al-10Bi-7Zn-1.5Ni表现出最佳的制氢性能,在60℃下与蒸馏水反应时,500 min内的产氢率为75.3%(954.1 m L/g),在储存7 d后(30℃,相对湿度60%),1500 min内保持57.9%(733.7 m L/g)的产氢率。此外,机理研究表明,在Al-Bi-Zn基复合粉体中添加Cu、Fe或Ni可以稳定Al基体,抑制复合粉体在空气中的开裂,保持粉体的高活性。

基于氧化钙-加热法的剩余污泥蛋白质提取率及嗅味值的影响因素研究

目的 研究温度、pH、反应时间和含水率对剩余污泥蛋白质提取率及嗅味值的影响。方法 以污水厂剩余污泥为原料、氧化钙为药剂,采用联合加热的方法处置剩余污泥,采用单因素和正交试验的方法来分析蛋白质提取率、嗅味值与各个反应条件之间的关系。结果 氧化钙-加热法提取剩余污泥蛋白质的最优工艺条件:pH为13,反应时间为4 h,温度为100℃,含水率为90%,蛋白质提取率为63.47%,嗅味值为6;氧化钙-加热法提取剩余污泥蛋白质各因素作用大小依次为:pH、反应时间、温度、含水率;各因素对嗅味值影响大小依次为:温度、pH、含水率、反应时间。结论 氧化钙-加热法有利于污泥水解反应的进行,但在碱性条件下温度过高会加剧美拉德反应,释放更多的恶臭物质而提高嗅味值,不利于提取剩余污泥中蛋白质。

面向工业气源中COS水解转化的催化剂研究进展

综述了COS水解催化剂载体与活性组分对其催化性能的调控作用、水解机理以及工业气氛中影响催化剂催化活性因素的研究现状。研究发现:氧化铝基复合载体负载碱金属活性组分所制备的COS水解催化剂能更好的提高催化剂的活性与稳定性,COS水解反应具有明显的碱催化特征,工业气氛中的CO_(2)与O_(2)气氛浓度对水解催化剂的抗氧耐酸性能有较大的影响,单质硫的生成和/或催化剂表面的硫酸盐化是催化剂失活的主要原因。通过对催化剂失活因素分析,定向调控催化剂的组成与结构制备高活性及高抗氧耐酸性能的新型COS水解催化剂与基于工业气源及水解热力学动力学条件优选下的水解催化反应工艺参数相结合来延长催化剂的寿命是未来的发展趋势。

UN_(x)与O_(2)、H_(2)O、H_(2)的相容性

U金属化学性质活泼,在环境中容易发生氧化、水解、氢蚀等反应,严重影响其物理化学性能。有很多方法被用于U表面的防腐蚀研究,其中最常用的方法之一是在表面形成一层能够有效隔断金属表面与外部气氛关联的UN_(x)(U_(2)N_(3+x)或UN)表面改性层。该表面层与外部环境直接接触,其与环境气氛,特别是气氛中的O2、H_(2)O、H_(2)等分子的相容性是决定改性层是否能够长期稳定存在并保持良好防腐蚀特性的关键因素。本文综述了UNx与O2、H_(2)O、H_(2)等的相容性,认为改性层的均匀性与完整性是长期防腐蚀的关键要素,氧化及水解过程中的N富集是一个值得关注的问题,水解过程中气相成分变化显著,需要深入研究。

煤矸石富镓母液中低浓度硫酸镓水解沉淀制备氧化镓

我国煤矸石中蕴藏大量镓资源,镓的伴生回收利用逐渐成为研究热点。伴生镓经酸法提取与富镓母液电解造液制备金属镓,镓综合回收率仅60%。随着氧化镓需求量增加,研究富镓母液直接水解沉淀制备氧化镓新工艺,通过缩减金属镓制备流程,显著提高镓产品综合回收率。然而富镓母液中镓离子浓度低、且与硫酸根共同作用水解转化机制尚不明确,为实现低浓度硫酸镓母液中氧化镓的高效制备,开展水解过程工艺和转化机理研究。通过正交试验考察硫酸体系下镓水解过程的反应温度、反应时间、搅拌转速、体系pH、初始镓浓度等因素对镓沉淀率和水解产物的影响,结合理论计算不同pH下镓的羟基配离子形态变化,明确低浓度硫酸镓溶液水解过程镓的转化机理,进一步通过单因素试验优化得到最优镓水解参数,水解产物经过煅烧制备得到氧化镓。结果表明,镓水解过程影响因素排序依次为体系pH、反应时间、初始镓浓度、搅拌速率、反应温度。硫酸体系不同沉淀pH下镓羟基配离子形态转变与沉淀物相对应规律为pH<3.5时,溶液中Ga^(3+)和Ga(OH)^(2+)占据主要优势,在硫酸根与镓离子的亲和作用下沉淀物相为镓明矾石;3.56.5时,溶液中以Ga(OH)_(4)^(-)为主,沉淀物相由无定形氢氧化镓氧化缩合为羟基氧化镓。根据正交和单因素试验优化得到硫酸镓溶液沉淀工艺参数为pH=5.0、初始镓质量浓度1 000 mg/L、反应时间20 min、搅拌速率150 r/min、反应温度20~25℃,镓回收率达99.5%以上,沉淀物相为无定形氢氧化镓。

核桃仁原位水解工艺优化及氧化稳定性研究

为延长核桃仁货架期,提高核桃仁储藏品质。以去皮核桃仁为原料,利用复配蛋白酶(胰酶)酶解核桃仁实现原位富集抗氧化肽,采用单因素实验分别研究了底物质量分数、酶质量分数、水解温度、水解时间对水解液抗氧化活性的影响。在此基础上,采用正交实验确定最优水解工艺为:酶质量分数12%、底物质量分数40%、水解温度45℃、水解时间20 min。萃取酶解处理的核桃仁(样品组)和未处理的核桃仁(空白对照组)油脂测定其氧化诱导时间,将样品组和空白对照组用铝袋分装在60℃烘箱内加速氧化。结果表明,样品组具有更长的氧化诱导时间及Q10指数,其氧化自由能从59.896 kJ/mol上升到78.103 kJ/mol;加速氧化过程对照组过氧化值始终高于样品组,以过氧化值为指标结合油脂氧化规律得到在20℃下样品组货架期相对于对照组延长了68 d。