毛竹在氢气中的催化热解研究

本文以分布广、产量大的速生生物质——毛竹为原料,研究其在H2氛围中、不同反应温度下热解所得产物的产率和分布,并与其在N2氛围中热解的结果进行了比较。结果表明,毛竹在H2气氛中热解,比在N2气氛中更有利于液体产物的生成。两种氛围中温度对液体产物影响的趋势不同,在本文条件下,H2气氛中升高温度始终有利于增加液体产率,使生物质有效转化率提高,在H2中毛竹热解生成甲醇、环丙基甲醇、呋喃甲醛等,这在N2中是不易得到的,但液体产物中含量最高的仍是乙酸。     

基于Fe负载的HZSM-5催化热解制备生物油实验研究

通过离子交换法制备含2%Fe(质量分数)的HZSM-5催化剂,采用X射线衍射仪(XRD)、激光粒度分析仪以及比表面积及孔径分析仪对催化剂进行表征,并在550℃下进行木屑的催化热解实验。对无催化剂和不同比例催化剂条件下得到的生物油进行GC-MS分析,结果表明,在Fe负载的HZSM-5作用下,生物油产率明显升高(最大增幅7%),轻质组分产率明显升高,重质组分产率略微升高。同时,轻质组分中的酮类、呋喃等含氧化合物含量降低,酚类、酸含量升高;重质组分中的酮类、呋喃类等含氧化合物含量明显降低,酚类、萘类含量明显增多。Fe负载的HZSM-5催化剂对木屑的热解反应有较好的催化效果,加强了对热解初始蒸汽的择形修饰,从而抑制了生物质三组分木质素初始热解产物中的醌类等容易一次或二次结焦物质的生成,孔道结构对蒸汽的二次反应被抑制,产物向较小分子的轻质产物上富集。     

CaZr1-xFexO3催化热解甘蔗渣木质素制备酚类化合物

采用固相反应法制备了一系列钙钛矿型混合离子电子导体CaZr_1-xFe_xO₃(CZFO-x, x=0, 0.2, 0.4, 0.6, 0.8, 1.0). 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)及X射线光电子能谱(XPS)对其晶型、 形貌和金属赋存价态进行了表征. 采用热重分析仪(TG)测试了其催化苷蔗渣木质素(BL)热解性能, 并采用固定床微型反应器对其催化热解BL制备酚类化合物性能进行了评价, 利用气相色谱/质谱(GC/MS)对BL催化热解的气相和液相产物进行分析. 研究结果表明, CZFO-x呈粒状或层状致密结构, 随着Fe掺杂量的增加, 其特征衍射峰强度增大, 且衍射峰位置向大角度偏移, 晶胞体积及晶粒尺寸减小. 固定床反应结果显示, 在CaZr_0.8Fe_0.2O₃(CZFO-0.2)催化下, BL热解液相产物收率可达23.71%, 其中酚类化合物主要包括苯酚类、 愈创木基类、 邻苯二酚类和紫丁香基类, 其选择性分别为35.19%, 6.18%, 10.68%和14.21%, 其余产物为苯类和甲氧基芳香化合物. 反应后催化剂经氧化再生后, 仍然具有较高的催化活性和结构稳定性. 对BL催化热解气体产物进行分析发现, CZFO-0.2促进了芳香烃烷基侧链的断裂, 致使气相产物组成中C_mH_n和CH₄含量增加.     

煤在合成气、氢气和氮气气氛下的热解研究

采用固定床反应器，在合成气气氛下对中国寻甸褐煤、蒙古Shiveeovoo褐煤和Khoot油页岩进行了热解研究。升温速率10 ℃/min，褐煤热解温度400 ℃～800 ℃，油页岩热解温度300 ℃~600 ℃，研究结果与氢气和氮气气氛下的热解进行了比较。结果表明,与加压热解不同，褐煤在不同气氛下常压热解半焦和焦油收率差别不大，但对油页岩，合成气和氢气气氛下热解焦油收率高于氮气，气体收率低于氮气。黄铁矿硫在不同气氛下热解均极易脱除，并部分转化为有机硫。油页岩的总硫脱除率远低于褐煤，与油页岩的高灰分含量有关。与氮气甚至氢气相比，合成气下寻甸褐煤的高总硫脱除率和低有机硫含量与合成气中的CO有关。但CO在油页岩热解脱硫中不起作用，也与油页岩高灰分含量有关。研究结果也表明合成气可代替氢气进行加氢热解。     

Ca1-xPrxFeO3催化热解甘蔗渣木质素制备酚类化合物

采用溶胶-凝胶法合成了一系列镨掺杂的铁酸钙氧化物(Ca_1-xPr_xFeO₃, 简称CPF-x), 优化了其焙烧机制, 研究了其对甘蔗渣木质素(BL)的催化热解作用, 考察了其再生性能. 研究结果表明, CPF-x适宜的合成及焙烧参数分别为: x=0.5, 焙烧温度为800 ℃, 焙烧时间为6 h, 在该条件下得到的CPF-0.5-800-6呈立方晶相, 为疏松多孔结构; 掺杂Pr后, 其比表面积提高了近3倍. CPF-0.5-800-6对BL催化热解最佳工艺参数为: m(CPF-0.5-800-6)∶m(BL)=1∶3, 热解温度为650 ℃, 液相收率最大可达20.73%, 其中主要产物为紫丁香酚类、 苯酚类及愈创木酚类, 其总选择性为63.21%. 以CPF-0.5-800-6为催化剂, 紫丁香酚类化合物选择性由20.60%增大到29.59%, 实现了提高BL催化热解中某种单酚化合物的选择性. CPF-0.5-800-6经5次催化热解-再生循环反应后, 仍具有良好的反应活性和结构稳定性.     

低密度聚乙烯丙烯酸气相光接枝体系反应机理的研究

研究了以二苯甲酮 (BP)为光敏剂 ,丙烯酸在低密度聚乙烯 (LDPE)膜上两步法气相光接枝聚合 ;从反应的基本要素出发 ,利用紫外光分光光度计跟踪测定了二苯甲酮在LDPE膜中的扩散情况 ,发现其扩散系数随BP浓度的升高而降低 ,约在 0 8～ 2 0× 10 -12 m2 ·s-1之间 .同样方法跟踪测定了BP在不同条件下的光还原反应 ,结果表明 :当远紫外光被滤掉后 ,其半衰期大大加长 ,氧气的存在更是加剧了这一效应 ;并且通过测定不同条件下气相光接枝聚合的一些基本规律 ,提出单体扩散为该气相光接枝聚合的控制步骤     

低密度聚乙烯-丙烯酸气相光接枝体系反应机理的研究

研究了以二苯甲酮(BP)为光敏剂,丙烯酸在低密度聚乙烯(LDPE)膜上两步法气相光接枝聚合;从反应的基本要素出发,利用紫外光分光光度计跟踪测定了二苯甲酮在LDPE膜中的扩散情况,发现其扩散系数随BP浓度的升高而降低,约在0.8～2.0×10-12m2.s-1之间.同样方法跟踪测定了BP在不同条件下的光还原反应,结果表明:当远紫外光被滤掉后,其半衰期大大加长,氧气的存在更是加剧了这一效应;并且通过测定不同条件下气相光接枝聚合的一些基本规律,提出单体扩散为该气相光接枝聚合的控制步骤.     

扎赉特旗油砂在氮气气氛下的热解制油研究

油砂是一种含有沥青或其他重质石油的沉积岩,主要用于提取油砂沥青,以生产合成原油。中国拥有相当数量的油砂资源,目前还未开采,仅处于初步研究阶段。加拿大在20世纪初期就展开了油砂的开采及制油研究工作,并于20世纪70年代由加拿大合成油公司实现了工业化生产。油砂生产的沥青和合成油已占其石油总产量的1／4以上。     

固体酸催化剂对LDPE与PS混合物催化裂解行为的研究

研究ZSM—G5和USY,及新型改性催化剂DeLaZSM-5对LDPE与PS混合聚烯烃的催化裂解行为,与热裂解相比,ZSM-5与DeLaZSM-5使裂解速率增加、残渣收率降低、产品分布变窄,而USY使裂解活性降低,其中De-LaZSM-5对LDPE／PS混合物具有最高的催化裂解活性。     

污泥微波高温热解条件下富氢气体生成特性研究

分别采用单模微波炉和电加热管式炉对污泥热解过程进行了实验研究,分析了污泥粒径、含水率、热解温度和微波吸收剂形态等参数对热解产物分布特性和气体组分浓度的影响规律和机理。结果表明,在粒径0~5.00 mm,污泥粒径大小对污泥微波热解产物分布无明显影响,但粒径减小可以提高H₂和CO浓度,当粒径从2.50~5.00 mm减小至小于0.45 mm,H₂和CO体积分数分别从31%和17%上升至34%和22%;污泥含水率和微波热解温度对热解产物分布和热解气组分浓度分布都有显著影响,提高污泥含水率或微波热解温度都可以显著提高H₂和CO浓度,当污泥含水率从0上升至83%,H₂和CO体积分数分别从32%和20%上升至42%和31%;相比粉末态吸波剂,固定形态的微波吸收器可以提高挥发分向热解气的转化,提高热解气产量,同时还能略微提高H₂和CO产率,但效果并不明显。     

Compatibilizing effect of isocyanate functional group on polyethylene terephthalate/low density polyethylene blends

To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447–453, 1998     

Lamellar structure in melt crystallized low density polyethylene

The investigation of representative details in the lamellar microstructure of LDPE observed after controlled chlorosulfonation using both EM and SAXD is reported. For this purpose melt crystallized PE with two branch contents (=0.28 and 2.53 branches per 10²CH²) has been prepared using Kanig's technique over a range of temperatures and treatment times. During the first treatment hours the selective incorporation of electron-dense atoms at the lamellar surface produces a macroscopic weight increase, swelling of the sample and a concurrent decrease of the SAXS intensity. The main result, however, is that the thickness of the lamellar structure does not vary with treatment time. After long chlorosulfonation times a saturation of electron-dense atoms within the surface layer and a reduction in the lateral dimensions of the lamellae take place. Optimum conditions for revealing the representative morphology are such as to lead to a weight increase of 50% for PE with=0.28 of branches and only to an increase of 10% for material of branch content represented by an value of 2.53.On leave from Inst. Estructura de la Materia, Madrid-6. Spain     

Nonisothermal crystallization kinetics and melting behavior of bimodal medium density polyethylene/low density polyethylene blends

Nonisothermal crystallization kinetics and melting behavior of bimodal-medium-density- polyethylene (BMDPE) and the blends of BMDPE/LDPE were studied using differential scanning calorimetry (DSC) at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of BMDPE. The BMDPE DSC data were analyzed by the theory of Ozawa. Kinetic parameters such as the Avrami exponent (n), the kinetic crystallization rate constant (Z_c), the peak temperatures (T_p) and the half-time of crystallization (t_1/2) etc. were determined at various scanning rates. The appearance of double melting peaks and the double crystallization peaks in the heating and cooling DSC curves of BMDPE/LDPE blends indicated that the BMDPE and LDPE could crystallize respectively.     

Thermogravimetric characteristics and kinetic of co-pyrolysis of olive residue with high density polyethylene

The co-pyrolytic behaviour of olive residue/high-desity polyethylene mixture was examined with a thermogravimetric analyser. The experiments were done over the temperature range of room temperature to 1273 K at various heating rates (2, 10, 20 and 50 K min⁻¹) and in a nitrogen atmosphere. The results indicated that mass loss process of mixture consists of three distinct stages and the increase of the heating rate shifts in the maximum rate loss to higher temperature. The difference of mass loss (Δm) between experimental and theoretical, calculated as algebraic sums of the mixture for different heating rates of 2, 10, 20 and 50 K min⁻¹, is about 7–11% at 740–900 K. These experimental results indicate a significant synergistic effect during co-pyrolysis of olive residue with high-density polyethylene. In addition, a kinetic analysis was performed to fit thermogravimetric data, the mixture is considered as multi-stage process. A reasonable fit to the experimental data was obtained for all materials and their mixture by isoconversional Friedman method.     

Rheological investigation of the influence of molecular structure on natural and accelerated UV degradation of linear low density polyethylene

Metallocene and Ziegler-Natta (ZN) linear low density polyethylenes (LLDPEs) of different branch types and contents as well as linear high density polyethylene (HDPE) were exposed to natural and accelerated weather conditions. The degree of UV degradation of exposed samples was measured by rheological techniques and results were compared with unexposed polymers. Dynamic shear measurements were performed in an ARES rheometer in the linear viscoelastic range. The degree of enhancement or reduction in viscosity and elasticity was used as a measure of the degree of cross-linking or chain scission, respectively. The degradation results of LLDPE suggest that both cross-linking and chain scission are taking place. Chain scission dominated the degradation at high levels of short chain branching (SCB) and long exposure times. The degradation mechanism of m-LLDPE and ZN-LLDPE is similar; however, m-LLDPE showed a higher degradation rate than ZN-LLDPE of similar M_w and average SCB. ZN-LLDPE was found to be more stable than a similar m-LLDPE. Comonomer type had little influence on degradation. Dynamic shear rheology was very useful in revealing the influence of different molecular parameters and it exposed the degradation mechanism.     

Effects of thermal ageing on mechanical and thermal behaviors of linear low density polyethylene pipe

The mechanical and thermal behaviors of linear low density polyethylene (LLDPE) pipe with variation in thermal exposure time were studied. The prolongation of thermal exposure time leads to a progressive increase, until 6000 h, in tensile strength and a slight increase in hardness, while a proportional decrease in elongation at break. These results can be explained by the increase of crystallinity, followed by the increase of crosslinking density and the decrease in chain mobility due to thermal oxidation as the exposure time increases. The additional ageing to the antioxidant-depleted LLDPE pipe induces the formation of T2 endotherm, which leads to a negative effect in mechanical properties. Long-term hydrostatic pressure test result implies the existence of transition point from ductile to brittle fracture in terms of the thermal exposure time. Chemiluminescence (CL) and oxidation induction time (OIT) tests are employed to monitor the thermo-oxidative degradation of LLDPE pipe. The CL emission intensity increases with increasing with thermal exposure time. Furthermore, the OIT result suggests that after 6000 h of the thermal ageing, the depletion of antioxidant originally added in LLDPE pipe occurs. Fourier transform-infrared spectroscopy results show the increase of carbonyl (-CO) and hydroxyl (O-H) function groups on the surface of thermally exposed LLDPE pipe. This result suggests that the hydrocarbon groups locally undergo the oxidation on the LLDPE surface due to thermal degradation.     

高密度聚乙烯与两种典型生物质在Y型分子筛上的催化共热解研究

采用固定床反应器,在氢气气氛下研究了高密度聚乙烯(HDPE)与两种典型生物质(杉木、毛竹)(8:2wt%)的共热解及在Y型分子筛上的催化共热解。结果表明,与HDPE单独热解相比,共热解生成的油相液体的碳数分布变窄,使C5-C11汽油馏分的含量显著增加,而C12-C20以及C20 组分相应降低。共热解最高的总液体收率出现在NaY催化剂上,毛竹与HDPE共热解中达到58·9%。在Y型分子筛加入后,共热解水相产物中乙酸含量明显增加,苯酚类产物含量则显著下降。乙酸生成量最多的是USY催化剂,其次是HY、NaY。在USY催化剂作用下,毛竹与HDPE共热解水相液体所含有机物中,乙酸含量达到38·3%。     

Morphology and mechanical properties of blown films of a low‐density polyethylene/linear low‐density polyethylene blend

The morphologies of films blown from a low‐density polyethylene (LDPE), a linear low‐density polyethylene (LLDPE), and their blend have been characterized and compared using transmission electron microscopy, small‐angle X‐ray scattering, infrared dichroism, and thermal shrinkage techniques. The blending has a significant effect on film morphology. Under similar processing conditions, the LLDPE film has a relatively random crystal orientation. The film made from the LDPE/LLDPE blend possesses the highest degree of crystal orientation. However, the LDPE film has the greatest amorphous phase orientation. A mechanism is proposed to account for this unusual phenomenon. Cocrystallization between LDPE and LLDPE occurs in the blowing process of the LDPE and LLDPE blend. The structure–property relationship is also discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 507–518, 2002; DOI 10.1002/polb.10115     

Morphology and crystallization of blends of linear low density polyethylene with a semiflexible liquid crystalline polymer

The morphology and the crystallization behavior of blends of linear low density polyethylene (LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 112 by Eniricerche, Italy) have been studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The blends possess a two-phase morphology, due to immiscibility of the two components. SEM observations show that dispersion of the minor SBH phase is favored at low (相似文献   

Reactive compatibilization of recycled low density polyethylene/butadiene rubber blends during dynamic vulcanization

For reactive compatibilization of the recycled LDPE with butadiene rubber (BR) an equal quantity of few couples of reactive polyethylene copolymer/reactive polybutadiene (1/1) were introduced into the corresponding phases before the dynamic vulcanization. The LDPE/BR thermoplastic dynamic vulcanizates (TDVs) produced using the poly(ethylene-co-acrylic acid), PE-AA/polybutadiene terminated with isocyanate groups, PB-NCO compatibilizing couple with different ratio of functional groups have demonstrated the best mechanical properties and have been characterized by X-Ray analysis and DMTA measurements. For all of systems studied the increasing components compatibility due to the formation of the essential interface layer have been observed. The PB-NCO modifier participates in two processes: it is co-vulcanised with BR in rubber phase and reacts in the interface with the PE-AA dissolved in LDPE. The amorphous phase of LDPE is dissolved by rubber phase, i.e. the morphology with dual phase continuity is formed that provides an improvement of mechanical characteristics of material obtained. The best combination of mechanical characteristics was obtained for LDPE(PE-AA)/BR(PB-NCO), PB-NCO=7.5 wt.% per PB, COOH/NCO=1/1. The tensile strength and an elongation at break for these blends were 3.9 MPa and 353% and for the basic non-compatibilized blend 3.2 MPa and 217%, relatively.