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Investigation of the reaction mechanism of chloromethane on ZSM5 is a new topic. In this work an in situ FTIR technique was employed to study the conversion processes of chloromethane, the active sites on HZSM5, and the desorption state of surface species. The catalytic conversion of chloromethane to higher hydrocarbons was also studied. It is demonstrated that chloromethane can be reversibly adsorbed on acidic sites of HZSM5 at room temperature. At 100°C chloromethane is irreversibly and dissociatively adsorbed on the strong acidic sites of HZSM5, on which surface methoxyl is formed as proved by infrared characteristic C-H stretchings of-CH3 at 2960 and 2870 cm–1. Alkoxyls are produced and adsorbed on the catalyst surface as characterized by the infrared absorption bands of -CH2-groups at 1460 and 2930 cm–1. At 100°C the adsorbed methoxyl and alkoxyls are the main surface species, and a small amount of aromatics might exist as detected by a characteristic absorption band at 1510 cm–1. Between 100 and 200°C the adsorbed surface methoxyl and alkoxyls are converted to aromatics, and the occupied OH groups partially appear. At temperature higher than 300°C the adsorbed aromatics are thermally desorbed into the gas phase. Aromatics and alkanes are the main products in catalytic conversion. These results reveal that the formation of aromatics from methoxyl and alkoxyls is easier than the desorption of aromatics from HZSM5 catalyst. An alkoxyl mechanism is proposed for the conversion of chloromethane on HZSM5 based upon the experimental results and the three assumptions: (a) The primary C-C bond is formed from surface methoxyl groups via the methoxyl group polarization and C-H bond weakening, (b) The adsorbed alkoxyls are converted to aromatics via hydrogen transfer and bond rearrangement similar to the conventional carbenium ion mechanism for the aromatization of olefins and alkanes on HZSM5. The hydrogen atoms from the aromatization stimulate the desorption of alkoxyls to alkanes. (c) At temperature higher than 300°C surface reactions and desorption of adsorbed species take place simultaneously, determining the product distribution in the catalytic conversion. 相似文献
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Manoj Parameswaran Xia Zhao Andrew B. Whinston Fang Fang 《Computer》2007,40(1):40-44
The growing proliferation of malware is raising doubts about the Internet's future. Security measures primarily target inbound traffic, but service providers have no incentive to stop attacks and spam at the source. A proposed certification scheme motivates providers to control outgoing traffic, efficiently increasing overall security while preserving the Internet's open, decentralized structure 相似文献
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Lorenz Frederick O.; Melby Janet N.; Conger Rand D.; Xu Xia 《Canadian Metallurgical Quarterly》2007,21(3):498
Scholars who study close relationships often measure the same concept with both observational ratings and questionnaire items. In studies where this has been done, the correlations between the two measures have often been low, and one reason may be a "context by measurement" confound. Observational ratings are usually based on behaviors during a specific task, whereas most questionnaire responses are based on a broader context such as "during the past month." In 2001, a total of 292 young couples were videotaped during a discussion task and asked to report on their own behavior and that of their partner during the discussion task and during the past month. The data were configured as a multitrait, multimethod matrix, and the magnitudes of the correlations were estimated with confirmatory factor analysis. The resulting correlations between observer ratings and questionnaire reports of hostile behavior during the videotaped discussion were roughly twice the magnitude of the correlations between observer rating and questionnaire reports during the past month. This suggests that the correspondence between behavioral categories and the content of questionnaire items is greater than previous studies have indicated. (PsycINFO Database Record (c) 2010 APA, all rights reserved) 相似文献
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高瑞霞 《消防技术与产品信息》2005,(3):59-60
设想某一个城镇生产木材调色板的流水线车间里 ,由于电器原因引发了一场火灾 ,致使建筑物坍塌。没有人能够确切地说出有多少工人被埋压在里面 ,更糟的是 ,当毗邻墙体坍塌时 ,隔壁的旧轮胎储藏室也被埋压在下面。于是市消防局派遣一批机器人去现场救援。第一个到达的机器人进入现场调查情况 ,该机器人能忍耐80 0℃的高温炙烤 ,身上安装了摄像机 ,可以给 90 m外的控制室发送图片 ,控制室的指挥人员就可以根据图片决定是否派消防队员冒险进入现场。第二个机器人是无人驾驶卡车 ,进入后便从 75 m远的地方以2 6 gal/ s的速度往火场喷水 ,并用它所… 相似文献
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带中置锅炉的氨合成塔和带后置式锅炉的氨合成塔,在结构和节能方面有许多异同之处.本文经过计算,定量地对这两种塔进行比较. 相似文献