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1.
本文研究了在氢气氛围及HZSM-5、H-Beta、NaY和TiO2催化剂作用下玉米芯与LDPE混合物(重量比2∶8)的共热解情况。通过催化热解所得油相液体的烃族分析及碳数分布发现:在催化剂作用下,油相液体的碳数分布变窄,共同热解所得气体产率最高的是H-Beta催化体系,液体产率最高的是NaY,残渣量最多的是TiO2催化体系。催化共热解所得油相液体的碳数分布主要集中在C4~C19之间,使用NaY可获得高品位的油相液体,其研究法辛烷值(RON)为97.5;水相液体中的主要物质是醋酸,加入催化剂后其含量明显增加。四种催化剂中,醋酸生成量最多的是NaY催化剂,其次是HZSM-5,最后是H-Beta和TiO2。其中在NaY催化体系作用下生成的水相液体组分中,醋酸含量为57.8%。  相似文献   

2.
聚丙烯和毛竹共热解的研究   总被引:2,自引:1,他引:1  
在自制固定床反应器中,对聚丙烯和毛竹共热解进行研究,得到了反应气氛、热解温度、反应物配比、反应时间对共热解的影响规律。实验结果表明,由于毛竹与聚丙烯在热解过程中的相互影响,两者共热解时的液体收率和产物分布均与两者单独热解时不同,油相液体产物的辛烷值随毛竹加入量的增加而增大,在聚丙烯和毛竹的最佳配比下,两者共热解的协同作用最明显,不仅原料的转化率最大,而且所得液体产物的收率最高,H2气氛较之N2气氛更有利于油相产物的生成和毛竹中木质素成分的热解。本文条件下,获得最佳油相液体收率的条件为,聚丙烯/毛竹配比8∶2,热解温度520℃,反应时间4h,H2气氛,油相液体收率达53.9wt.%,辛烷值为77.3。  相似文献   

3.
应用TG-FTIR技术研究黄土庙煤催化热解特性   总被引:1,自引:0,他引:1  
用浸渍法制备过渡金属氧化物担载型催化剂MOx/USY(M=Co、Mo、Co-Mo),用热重红外联用技术考察了MOx/USY催化剂对黄土庙(HTM)煤热解失重特性和热解产物生成规律的影响。热重实验结果表明,MOx/USY催化剂可使HTM煤热解的二次脱气条件更为温和,热解峰温分别提前14、23和9℃。动力学分析结果表明,MOx/USY催化剂可降低HTM煤样热解的活化能。FT-IR研究表明,MOx/USY催化剂可有效改善HTM煤热解产物的组成和分布,CoOx/USY催化剂能显著提高HTM煤热解产物中高热值气体(CO、CH4)和轻质芳烃以及脂肪烃类化合物的含量;MoOx/USY催化剂没有明显改善HTM煤热解产物组成和分布;MoOx-CoOx/USY催化剂可促进CO、CH4、轻质芳烃和脂肪烃类化合物的生成,却使热解产物的生成向高温区移动,说明USY负载的不同过渡金属氧化物对煤样热解行为和热解产物有较大影响。  相似文献   

4.
采用液相离子交换法制备了不同稀土含量的Y型分子筛(HY、USY和NaY),研究了稀土铈(Ce)阳离子在Y型分子筛上吸附-脱附烃类分子(苯)过程中的作用机理与影响。通过X射线荧光光谱仪(XRF)、智能质量分析仪(IGA)、脱附指数的计算和巨正则蒙特卡罗模拟计算等多种表征计算方法,对引入稀土物种后,Y型分子筛对苯的饱和吸附量、吸附作用力、脱附热力学参数、苯在Y分子筛上的吸附势能分布及扩散行为等方面进行了研究。结果表明,Ce离子对苯在Y分子筛上脱附活化能的降低、吸附作用力的减弱以及吸附态由团聚态向分散态转变等方面具有显著影响,该作用构成了CeY分子筛催化剂在流化催化裂化(FCC)过程中能够优化轻质产品选择性的重要因素。  相似文献   

5.
Y型分子筛结构破坏的动力学分析(英文)   总被引:1,自引:0,他引:1  
Y型分子筛是催化裂化(FCC)的速率控制组分.FCC过程中,催化剂在反应器和再生器中往往面临高温水蒸气存在的苛刻环境.因此,分子筛的热稳定性和水热稳定性是催化剂最为关注的性能之一.由于FCC原料中通常含有V、Ni、Na、Fe等不同数量的金属污染物,会对催化剂造成污染及钝化.进料中存在的卟啉类有机复合物持续不断的沉积在催化剂表面,由于含钒的有机金属卟啉化合物在反应中转化形成V_2O_5,V_2O_5在水热条件下形成H_3VO_4组分,在高温水热气氛下加速分子筛骨架结构水解,破坏了Y型分子筛的晶体结构,从而降低了催化剂活性,影响产品选择性.稀土Y型分子筛在FCC中扮演重要的角色,稀土交换分子筛可以提高催化酸性、裂化活性和热与水热稳定性.此外,Na在高温水蒸气条件下也会对分子筛结构造成破坏.一方面,钠能够中和Y型分子筛B酸中心,降低催化裂化活性;另一方面,水热条件下钠的存在会加速破坏Y型分子筛的结构.有关Y型分子筛结构破坏的机理解释较多,然而该过程的动力学研究鲜有报道.反应动力学不能提供一个直接的反应机理,但是任何反应机理的提出必须符合反应动力学的数据.本文采用离子交换法分别制备了一系列不同Na含量USY,不同稀土含量USY,以及含钠和稀土的USY分子筛,通过固相动力学模型考察了上述Y型分子筛水热结构破坏活化能的变化及钒对其活化能的影响.结果表明,Y型分子筛的结构破坏存在三种路径,分别是脱铝、脱硅和La-O键的断裂.钒加速了分子筛骨架水解速率;钒钠具有协同作用,同时存在时对分子筛破坏作用更加显著;NaOH的形成是速率控制步骤;稀土稳定了分子筛的结构,降低了分子筛的水热脱铝速率;钒与定位于分子筛小笼里稀土作用,破坏分子筛的[RE-OH-RE]~(5+)的RE-O键夺取分子筛的骨架氧,导致骨架结构崩塌.由于稀土本身稳定了分子筛的结构,同时钒稀土作用时形成稳定的REVO_4固定了钒的流动性,因此钒对REY结构的影响是几种因素相互叠加和抵消的结果.  相似文献   

6.
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。  相似文献   

7.
碱溶液处理NaY分子筛形成的介孔有利于反应物及产物分子的扩散,调节碱溶液浓度可控制Y分子筛中的介孔结构,通过溶液离子交换法制备CuY催化剂,研究了NaY分子筛介孔结构调变对CuY催化剂催化甲醇氧化羰基化反应活性的影响。通过BET、~(29)Si-NMR、XRD、NH_3/CO-TPD、H_2-TPR和TEM等表征及催化活性分析表明,在碱溶液处理过程中,NaY分子筛骨架中的Si(0Al)和Si(1Al)原子被优先脱除,且笼结构坍塌使得临近超笼连接,逐步形成直径为3.47~3.66 nm,孔容介于0.142~0.226cm~3·g~(-1)的介孔,在提高反应物分子和产物分子扩散性能的同时,提高了活性物种的可接近性。随着碱液浓度的增加,CuY催化剂的催化活性先升高后降低。当碱液浓度为0.2 mol·L~(-1)时,NaY分子筛介孔直径为3.47 nm,孔容达到最大(0.226 cm~3·g~(-1)),相应CuY催化剂DMC的时空收率、选择性和甲醇转化率分别达到204.0 mg·g~(-1)·h~(-1)、67.8%和14.0%,活性最佳。  相似文献   

8.
微波辐射促进ZnCl_2与Y分子筛固相反应的研究   总被引:6,自引:0,他引:6  
采用XRD、IR和原子吸收光谱等手段对微波固相法制备的ZnCl2/Y催化剂进行了表征·微波辐射促进了ZnCl2在分子筛表面分散和固态离子交换,分散的ZnCl2可与分子筛表面氧原子发生较强的配住键合作用.当ZnCl2的负载量达到37.5%时,ZnCl2仍可完全分散于NaY分子筛表面,此时的固态离子交换度为84%.随着分子筛表面酸菌和区强度的增加,ZnCl2与分子筛的固态离子交换量减少.  相似文献   

9.
采用浸渍法与化学还原法相结合制备了一系列USY型分子筛负载非晶态合金硼化钴(Co B/USY)催化剂,并系统探究了该催化剂在催化硼氢化钠水解制氢中的催化活性。XRD表征表明,USY分子筛载体上负载的活性组分Co B属于非晶态结构。通过扫描电子显微镜,对比了负载型Co B/USY催化剂和粉末状Co B催化剂的微观形貌,发现非晶态合金活性组分Co B能够很好的分布在USY分子筛载体表面,较粉末状Co B有更高的分散度。催化硼氢化钠水解制氢实验结果表明,相对于粉末状Co B催化剂,负载型Co B/USY催化剂在硼氢化钠水解制氢中具有更高的催化活性,30℃时Na BH4水解产氢速率约为1.5 L/(min·g)。反应动力学的计算结果显示,负载型Co B/USY催化剂在催化Na BH4水解制氢反应中表观活化能约为65.9 k J/mol,大大低于粉末状Co B催化剂的活化能(72.1 k J/mol)。  相似文献   

10.
针对催化裂化(FCC)废催化剂的回收利用问题,提出了一种废催化剂再利用的方法,即以FCC废催化剂为铝源,合成时只补充部分硅源,采用自制的高效NaY沸石导向剂,水热合成NaY分子筛。同时,以普通的化工原料合成了对比试样Y型分子筛。讨论了不同的FCC废催化剂预处理方式对合成产物性能的影响,发现以经过碱熔活化处理的废催化剂为原料合成的Y分子筛拥有更高的结晶度和纯度。采用X射线衍射、热分析、程序升温脱附法(NH3-TPD)和N2静态容量吸附法对结晶产物和对比样品的晶体结构,热稳定性、酸性质、比表面积以及孔分布进行了表征。结果显示,以FCC废催化剂为原料完全可以合成出与普通原料性能接近的NaY分子筛。其BET比表面积可以达到615 m2·g-1,孔体积可达0.38 cm3·g-1,孔径集中在0.51 nm左右。  相似文献   

11.
The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.  相似文献   

12.
非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。  相似文献   

13.
翟宗玺  刘树深  夏树屏 《化学学报》1990,48(10):946-950
用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。  相似文献   

14.
Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.  相似文献   

15.

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

  相似文献   

16.
Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.  相似文献   

17.
In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.  相似文献   

18.
Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, Mo, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

19.
20.
The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe2O3. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

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