Kinetic of Adsorption of Urea Nitrogen onto Chitosan Coated Dialdehyde Cellulose under Catalysis of Immobilized Urease

The adsorption of urea nitrogen onto chitosan coated dialdehyde cellulose (CDAC) under catalysis of immobilized urease in gelatin membrane (IE) was studied in batch system. The pseudo first-order and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model.

Deconvolution Method for Determination of the Nitrogen Content in Cellulose Carbamates

Cellulose carbamates (CC) were synthesized with microcrystalline cellulose as raw materials. The Fourier transform infrared spectra of CC with different nitrogen content were recorded. The accurate results of the nitrogen content for CC can be obtained by using the deconvolution method when the nitrogen content is less than 3.5%. The relationship between the nitrogen content and the absorption intensity ratio of the corresponding separated absorption peaks in FTIR spectra has been expressed bg an equation precisely.

Homogeneous Synthesis and Characterization of Quaternized Cellulose Derivatives in NaOH-urea Aqueous Solutions

Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.

Structure Elucidation of Hydroxypropyl Cellulose Homogenously Prepared from NaOH/Urea Aqueous Solution

Hydroxypropyl celluloses(HPC) were homogenously synthesized by the reaction of cellulose with propylene oxide in NaOH/urea aqueous solution.Water-soluble HPC with molar degree of substitution(MSNMR) in the range of 0.52~0.78 was prepared from microcrystalline cellulose,cotton linters,and spruce sulfite pulp.The structure of the HPC samples was characterized by means of FT-IR,NMR,gas chromatography(GC),and size exclusion chromatography(SEC) analyses.Three types of cellulose samples with different molecular weights were found to dissolve well in the NaOH/urea solvent with no obvious differences in reactivity and regioselectivity.The relative reactivity of hydroxyl groups in the glycosyl unit was in the following order:O-6>O-2>O-3.In addition,the results of the study indicated that the tandem reaction during hydroxypropylation could be ignored.

Effects of Coagulation Conditions on Tensile Properties of Regenerated Cellulose Fibers

The effects of coagulation conditions on tensile properties of the regenerated cellulose fibers prepared by wet-spinning from NaOH/thiourea/urea(8∶6.5∶8 by weight)aqueous solvent were investigated by tensile tester,X-ray diffraction(XRD),and scanning electron microscope(SEM).The results show that the tensile properties of the as-spun fibers change with the coagualtion concentration,temperature,and time.When the spinning solution is coagulated in 10% H2SO4/12.5% Na2SO4 aqueous solution,the as-spun fibers have a typical structure of cellulose II,a circular cross-section,and homogeneous morphological structure.

Preparative Optimization of Cellulose Microspheres Applied as Supports for High-Performance Liquid Chromatography

The aim of this work is optimizing the techniques to prepare pure cellulose microspheres, which are used as packing adsorbents for high-performance liquid chromatography. Thereupon, cellulose was dissolved in a pre-cooled NaOH/urea solution, from which various-size microspheres were prepared. The volume-average diameters were controlled approximately at 30 p,m, 8 ~tm and 4 pm grades when cyclohexane, liquid paraffin and pump oil were used as dispersants, respectively. The present investigations reveal that higher viscosity dispersant is suitable for the preparation of smaller-size microspheres, while larger size microspheres are prepared preferably using lower-viscosity dispersant. The chiral stationary phase derived from 8 μm grade microspheres can separate the enantiomers of efavirenz.

Optimal Method for Production of Amorphous Cellulose with Increased Enzymatic Digestibility

In this paper,a simple and cheap method for producing of amorphous cellulose was studied by treating the initial cellulosic material(MCC and waste paper)with a cold solvent,such as aqueous solution of 7%NaOH/12%Urea,at the various ratios of the solvent to cellulose(v/w)(R).If was found that after treatment of cellulose materials with the solvent at R≥5,a completely amorphous cellulose(AC)is formed.Due to high digestibility,the AC with concentration of 50 g/L is converted to glucose almost completely for 48 h under the action of cellulolytic enzyme CTec-3 with a dose of 30 mg/g solid sample.Such sample can be used as an amorphous standard in the study of crystallinity degree and enzymatic hydrolysis of various types of cellulose and lignocellulose.It was found that enzymatic saccharification is most advantageous to carry out at elevated concentrations of AC,150 g/L.Due to high cost of MCC,it is preferable to use a cheap cellulose raw material,such as mixed waste paper(MWP),for the commercial production of AC and glucose.The resulting glucose can find application in biotechnology as a promising nutrient for various microorganisms.

PREPARATION OF UREA NITROGEN ADSORBENT OF COMPLEX TYPE AND ADSORPTION CAPACITY OF UREA NITROGEN ONTO THE ADSORBENT

The urea nitrogen adsorbent of complex type, which consists of chitosan coated dialdehyde cellulose （CDAC） and immobilized urease in gelatin membrane （IE）, was prepared. The cellulose, the dialdehyde cellulose （DAC） and the CDAC were characterized by scanning electronic microscope. The results indicate that the cellulose C2-C3 bond was broken under the oxidation of periodate and it was oxidated to DAC. The DAC was coated with chitosan and the CDAC was obtained. The adsorption of urea nitrogen onto the adsorbent in Na2HPO4-NaH2PO4 buffer solution was studied in batch system. The effects of the experiment parameters, including degree of oxidation of CDAC, initial urea nitrogen concentration, pH and temperature, on the adsorption capacity of urea nitrogen onto the adsorbent at CDAC/IE weight ratio 10：1 were investigated. The results indicate that these parameters affected significantly the adsorption capacity. The adsorption capacity of urea nitrogen onto the adsorbent was 36.7 mg/g at the degree of oxidation of CDAC 88%, initial urea nitrogen concentration 600 mg/L, pH 7.4 and temperature 37℃.

碱/尿素预处理的纤维素纤维塑化改性处理研究

本研究采用碱/尿素体系在不同温度下分别对阔叶木浆、针叶木浆和竹浆纤维进行润胀预处理,并通过四因素三水平正交实验,探究了甘油、甲酰胺和柠檬酸三乙酯3种塑化剂在不同塑化温度、塑化剂质量分数及塑化时间下对纤维的塑化改性效果。结果表明,在10℃下,碱/尿素体系预处理的针叶木浆纤维具有最高的润胀程度,有利于进一步塑化改性处理;本实验的最佳塑化改性处理条件为:甲酰胺质量分数30%,塑化温度25℃,塑化时间5 h。在该条件下制备的塑化纤维有望在特定领域作为塑料的替代材料。

基于NaOH-Urea预处理的微纤化纤维素制备研究

为开发高效制备微纤化纤维素的方法,探讨了基于氢氧化钠-尿素(NaOH-Urea)混合溶液对玉米芯微晶纤维素进行预处理后采用机械法处理的微纤化纤维素制备工艺。采用傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)、热重分析仪(TG)、场发射扫描电镜(FESEM)对制备的微纤化纤维素化学结构、结晶度、热稳定性及微观形貌进行表征。结果表明,制备的微纤化纤维素为纤维素Ⅰ型;微纤化纤维素的结晶度为60. 4%,得率高达78%;微纤化纤维素结晶度较玉米芯微晶纤维素有所提高;制备的微纤化纤维素表现出优良的热稳定性,热降解温度达238℃;微纤化纤维素呈棒状,直径为5～20 nm,长度大于200 nm。

深度共熔溶剂提取紫苏秸秆纤维素的研究

以紫苏秸秆为原料,研究深度共熔溶剂提取纤维素的工艺。以尿素和氯化胆碱作为氢键受体的深度共熔溶剂分离提取紫苏秸秆中的纤维素,在单因素的基础上,运用响应面法优化提取纤维素的条件。采用红外光谱、热重分析、X射线衍射、扫描电镜等对纤维素的形态和物理化学性质进行综合比较。最优工艺条件为:温度为121℃、时间为4 h、料液比为1∶21 g/mL,在此条件下,纤维素含量为73.82%。表征结果表明,纤维素的晶型没有发生改变;纤维素变得不均匀、松散、无序,有利于溶剂的渗透。本研究可为紫苏秸秆纤维素资源的利用提供一定的理论依据与技术支撑。

基于三元DES体系制备硫酸化改性CNF及其性能研究

以漂白硫酸盐浆为原料,采用氨基磺酸/尿素/氯化胆碱三元低共熔溶剂(DES)体系预处理结合机械处理的方法制备硫酸化改性的纤维素纳米纤丝(CNF),并采用纤维图像分析仪、元素分析仪、场发射扫描电子显微镜、原子力显微镜、傅里叶变换红外光谱仪、Zeta电位分析仪、热重分析仪和多重光散射分析仪对制得的CNF性能进行表征。结果表明,三元DES预处理既可改性纤维原料又可对其产生润胀效果,从而促进其在纳米均质化过程中的纤丝化。与未经DES预处理的纤维原料在均质化处理过程中能耗(9.49×10^(7) kJ/kg)相比,DES预处理(1.61×10^(7)~2.11×10^(7) kJ/kg)可节省77.8%~83.0%的能耗。DES预处理提高了所得CNF悬浮液的稳定性但导致其热稳定性下降;此外,延长DES预处理时间可促进纤维的纤丝化并降低纤维聚合度。

大麻落麻纤维素膜制备及性能

将大麻长麻纺过程中产生的落麻溶解在氢氧化钠/硫脲/尿素水溶液中得到再生纤维素纺丝原液,通过相转化法制备出大麻落麻再生纤维素膜,并对大麻落麻纤维素的提取、溶解性能、成膜效果及再生纤维素膜的结构和性能进行研究。根据各项研究结果得出:4%浓度碱液处理后的大麻落麻纤维的纤维纯度较高,一定条件下能很好的溶解于氢氧化钠/硫脲/尿素溶剂中;当纤维素浓度达到6%时,可得到形貌较好的纤维素薄膜;纤维素经溶解制膜后,纤维素膜在较大程度上仍保留着纤维素的特征,纤维素晶型从纤维素Ⅰ转变为纤维素Ⅱ,纤维素薄膜的表面呈波纹状,并具有不均匀的多层结构。

不同温度条件粪秆结构配比及尿素、纤维素酶对沼气产量的影响

提高农村户用沼气的产气量和秸秆等农业废弃物利用效率,是当前循环农业领域面临的主要问题。通过利用自行设计的可控性厌氧发酵装置,在室内模拟农村户用沼气发酵过程,研究在不同温度条件下作物秸秆和禽畜粪便配比以及添加尿素和纤维酶对沼气产量的影响。结果表明,20～35℃范围内,粪秆配比的产气量随温度升高而升高。35℃条件下,2.5 kg料液发酵50 d,鸡粪和秸秆配比(干物质量比)以2︰1的产气量高于其它粪秆比例,其中鸡粪与玉米秆2︰1(干物质量比)总产气量最高,达51120 mL。在发酵中期(发酵后28 d),向2.5 kg发酵料液中添加2.5 g尿素和2.0 g纤维素酶, 均显著提高沼气产量,平均增加99.8%和40.8%,且鸡粪与麦秆2︰1配比产气量增幅最大,分别为261.2%,117.3%。研究 20℃粪秆厌氧发酵环境pH值动态变化,表明其呈动态变化,发酵初期pH值平均为6.8,发酵中期平均为6.4,随后缓慢回升至6.6。因此,适宜的温度,合理的秸秆配比、添加一定量酶和尿素是提高产气量的有效措施。

氧化纤维素的制备及吸附性能的研究

比较了碱处理纤维素与未处理纤维素制备氧化纤维素(DAC)的过程.当氧化剂NaIO4的质量分数为6.78%,介质的pH值为2,反应温度为35℃,反应时间为3h时,以纤维素为原料,DAC的醛基质量分数可达68.20%.若以碱纤维素为原料时,其醛基质量分数可提高到84.25%.氧化纤维素醛基质量分数为50%时对尿素氮的吸附性能最高.

纤维素氨基甲酸酯的合成及表征

系统地研究了纤维素氨基甲酸酯的合成方法、原料聚合度、合成温度及其时间、载体及其用量、尿素用量等对产物含氮量的影响.结果表明：载体的加入可提高反应试剂的可及度;纤维素浆粕的聚合度在320～390时反应性能较好;反应体系呈碱性时,有利于酯化反应的进行;产物含氮量随尿素用量的增大及预处理时间的延长而增加.最终确定最佳合成工艺条件为尿素用量40%,预处理2 h,酯化反应温度150℃,酯化反应时间3 h.产物的FT-IR谱图证实了酰胺键的存在.X-射线衍射表明产物的晶型与活化后纤维素的晶型类似,结晶度变化不大.

尿素氨化预处理改善稻秸干法厌氧发酵特性

为了提高稻秸的可生物降解性,利用尿素氨化预处理方式,研究不同尿素质量分数（2%、4%、6%、8%、10%）和不同预处理温度（25、30、35、40、45、50℃）对稻秸预处理前后木质纤维素含量变化及干发酵产气特性的影响。结果表明：1）不同尿素质量分数对稻秸预处理效果影响显著,尿素预处理能够破坏稻秸木质纤维素的结构,预处理后稻秸的碳氮比降低,预处理后稻秸的累计产气量比未经处理组高20.67%~38.20%（P〈0.05）,尿素质量分数为4%时效果较好;2）不同预处理温度对稻秸预处理效果影响不显著,尿素预处理效果主要受尿素质量分数的影响。研究结果为秸秆的预处理工艺提供参考,并为秸秆厌氧干发酵技术提供数据支持。

纤维素氨基甲酸酯的合成研究

以微晶纤维素和尿素为原料 ,二甲苯为溶剂合成了纤维素氨基甲酸酯。考察各种影响因素 ,得到优化的反应条件为 :微晶纤维素在质量分数为 2 0 %的氢氧化钠水溶液中预处理 4～ 6h ,尿素与微晶纤维素质量比为 ( 3～ 4)∶1,反应温度为 137℃ ,反应时间为 4h。元素分析测得产品氮的质量分数约为 8%

低温碱尿素法制备纤维素纤维的研究进展

纤维素是最有可能大规模替代石油的资源,但是纤维素的特殊结构导致其难以溶解在普通溶剂中,也不能熔融纺丝,极大地限制了这类强极性高分子的工业发展,因此纤维素纤维的高效绿色制备新方法成为国际研究热点。在我国已发明的低温碱尿素水溶液直接溶解纤维素新方法的基础上,对这一新技术进行了纺丝工程研究,分别包括间歇式、连续式以及连续式原位化学改性。结果证明将双螺杆应用于纤维素的溶解,利用双螺杆挤出机的强剪切力可以明显提高纤维素的溶解效率,提高纤维素的溶解度,提高溶液均匀性并延长纺丝液凝胶时间,从而实现纤维素纺丝液的高浓度连续稳定纺丝。

尿素和纤维素酶对厌氧发酵的影响

【目的】研究尿素和纤维素酶对厌氧发酵产气效果的影响,为解决沼气发酵原料利用率低、实际沼气转化率和沼气产气量低等问题提供科学依据。【方法】以鸡粪和玉米秸秆(干物质(TS)质量比为2∶1)为原料,采用自行设计的可控性恒温厌氧发酵装置,控制TS质量分数为8%,温度为(30±1)℃,在厌氧发酵的前期(装料时)、中期(正常发酵15 d时)和末期(正常发酵30 d时),分别添加尿素和纤维素酶,添加水平均设5,10,15,20 g/kg 4个水平,进行为期46 d的厌氧发酵,研究尿素和纤维素酶不同添加时期及不同添加水平对厌氧发酵产气特性的影响。【结果】尿素和纤维素酶的3个不同添加时期对产气量均没有显著影响,各个时期添加均可促进厌氧发酵的进行,提高累积产气量。尿素的最佳添加量为20 g/kg,前期、中期、末期添加20 g/kg尿素可使产气量较未加尿素的对照分别提高23.3%,18.3%和12.4%。纤维素酶的添加量对产气量没有显著影响,较好的添加方法为末期添加10 g/kg,该法可使累积产气量较未加纤维素酶的对照提高16.8%。【结论】添加尿素和纤维素酶均可促进厌氧发酵的进行,提高产气速率,添加尿素的效果更明显。