高岭土微球上无胺法ZSM-5的原位合成

无胺体系中,采用水热法在焙烧高岭土微球上原位晶化合成了ZSM-5分子筛。考察了晶化温度、晶化时间、晶种加入量以及合成体系硅铝比等主要因素对分子筛合成的影响,得出了较佳的原位晶化合成条件。采用XRD、SEM、N2吸附脱附等手段对合成样品进行了表征。结果表明:在高岭土微球上合成出了颗粒尺寸小于1μm的小晶粒原位ZSM-5分子筛;晶化产物的比表面积、总孔容、微孔表面积和微孔孔容均明显增大,微孔分布集中于0.54nm。

含有乙醚的无胺无氟反应物体系中高硅丝光沸石的合成

研究含有乙醚的Na2O-Al2O3-SiO2-H2O反应物中高硅丝光沸石在413～453K下的水热合成.乙醚的存在能有效促进丝光沸石的结晶过程,且有助于提高产物结晶度和硅铝比.反应物胶体中硅铝比与碱度对产物的生成有关键作用.合成原料使用不同铝源,体系结晶规律相近,但产物的形貌和硅铝比有差异.在优化的反应条件下合成的高硅丝光沸石硅铝比达30左右.低温氮吸附与27Al魔角旋转核磁谱表征证实该沸石骨架结构完美,孔道开放畅通,其水热稳定性优于低硅丝光沸石.

无胺合成[Fe]ZSM-5分子筛的结构鉴定及其催化性能的研究

不用有机胺为模板剂,在碱性介质中采用水热合成法成功地合成了[Fe]ZSM-5分子筛.用X射线衍射、透射电镜、红外光谱、顺磁共振谱、X射线光电子能谱和穆斯堡尔谱等对其结构进行了表征,结果表明,Fe原子进入了分子筛骨架,并处于四面体的配位环境.在由甲醇转化为汽油的过程中,以本文合成的[Fe]ZSM-5与用有机胺为模板剂合成的[Fe]ZSM-5分子筛为催化剂相比,其活性和选择性几乎相同,且都比通常的H[Al]ZSM-5好,C_5组分以上的选择性大于80％,且芳烃(包括脂环烃)和异构烃的含量达75％以上.

无胺体系高硅ZSM-5分子筛合成工艺的正交试验探索

在160℃水热条件下,选取硅铝比、碱硅比、水硅比、醇硅比(均为物质的量之比)和晶化时间5个合成参数作变量,通过设计5因素4水平的正交试验L_(16)(4^(5)),采用silicalite-1作为晶种,经无胺法制备了一系列ZSM-5分子筛。通过XRD表征考察了不同合成条件下产物的结构和相对结晶度,并结合产物产率筛选了无胺体系高结晶高硅ZSM-5分子筛的合成相区,最后通过SEM、NH-TPD和Py-IR等对其微观形貌和酸性进行了表征。结果表明,在160℃和较低水硅比(10~30)条件下,当投料硅铝比为50和100时,可在碱硅比0.050~0.125和醇硅比0.5~3.5较宽的合成相区制得高结晶度(>100.0%)、高产率(>74.0%)的纯相ZSM-5分子筛,但投料硅铝比为150和200时,合成相区较窄,不易制得高纯、高结晶ZSM-5分子筛。硅铝比为100的高结晶ZSM-5分子筛呈六棱柱状,具有典型的强酸性和B酸、L酸分布。

无胺ZSM—5型辛烷值助剂的研究

本文介绍金陵石化公司炼油厂研究所开发研究试制的无胺型辛烷值助剂，在小型固定床和小型流化床上的评价结果。

焙烧温度对HZSM-5催化剂催化环己烯水合反应性能的影响

采用水热法在无胺体系中制备了NaZSM-5分子筛,用硝酸铵进行离子交换,并在300～ 550℃下焙烧制得HZSM-5催化剂.考察了焙烧温度对HZSM-5催化剂催化环己烯水合制环己醇反应性能的影响;采用XRD、FTIR、NH3-TPD和低温N2吸附-脱附等技术,对不同焙烧温度下制备的HZSM-5催化剂进行了结构表征.实验结果表明,焙烧温度对HZSM-5催化剂的性能影响显著,在最佳温度400℃下焙烧时,HZSM-5催化剂的微孔比表面积高达265m2/g,强酸酸量为4.46 mmol/g,环己烯的转化率达14.0％,环己醇的选择性为83.3％.随焙烧温度的升高,HZSM-5催化剂的酸量逐渐减少,尤其是强酸量减少较明显,这是其催化环己烯水合反应活性降低的主要原因.

无溶剂复合PE膜摩擦系数性能分析及应用

以无添加的低密度聚乙烯作为载体树脂,加入无胺爽滑剂、开口剂和抗氧化剂制成爽滑母料,然后添加一定比例的爽滑母料吹塑成 PE 热封膜,并对其进行无溶剂复合,研究了 PE 膜在复合及熟化后摩擦系数的变化。结果表明,在无溶剂复合过程中 PE 热封膜的摩擦系数始终保持在 0. 15 ~ 0. 25,并且在 40 ℃以内的熟化温度下,摩擦系数几乎保持不变,同时复合膜的热封强度保持在 63 N/15 mm 以上,剥离强度保持在 2. 2 N/15 mm 以上,60 μm PE 热封膜的透光率和雾度分别为 90. 8 和 0. 23,与相同厚度的普通 PE 膜的差距较小,完全符合 GB/T 10004—2008 中薄膜性能的要求,解决了采用胺类爽滑剂母料导致无溶剂复合产品摩擦系数变大的现象。

晶种导向合成MOR分子筛及其催化应用

具有8元环与12元环孔道结构的丝光沸石(MOR)分子筛因其独特的孔道结构和酸性被广泛应用到烷基化、异构化和羰基化等反应过程,通过晶种辅助无胺绿色合成MOR分子筛一直是人们关注的热点,但添加的晶种类型对产物的影响鲜有研究。借助XRD、IR和SEM在内的多种表征手段详细考察了同晶MOR晶种及异晶(FER)晶种在MOR无胺绿色合成路线中的导向作用。实验结果表明,因合成体系碱度过高,添加MOR分子筛晶种并未显著加速晶化。当MOR分子筛作晶种合成得到纺锤形的MOR纳米团聚体,尺寸在1μm左右,样品性质与无晶种添加路线相似。以FER为晶种可导向合成棒束状形貌的MOR分子筛,跟踪晶化过程发现,FER晶种首先诱导形成了FER晶相,随后薄片状FER晶体溶解转晶生成了MOR晶相。上述结果为分子筛无胺转晶路线制备棒束状MOR沸石提供了新的合成思路。在异丁烯齐聚反应中,通过添加MOR晶种制得的纺锤形MOR纳米团聚体因其丰富的晶间介孔呈现较佳的反应稳定性。

均匀设计法应用于NaZSM-5分子筛无机酸交换条件的优化

采用无胺法水热合成NaZSM-5分子筛,分别用盐酸和硝酸将Na ZSM-5分子筛交换为HZSM-5,考察酸浓度、交换时间及温度、液固比(V(交换液)∶m(催化剂))等对其催化环己烯水合制环己醇性能的影响。采用XRD、XRF、NH3-TPD、SEM和N2吸附-脱附等技术对试样进行表征。运用均匀设计法对分子筛无机酸交换条件进行优化。实验结果表明,无机酸交换方法较传统铵盐交换方法简便、节能和高效。最优盐酸交换条件为:盐酸浓度1.2 mol/L、交换温度80℃、交换时间3 h、液固比11 mL/g,环己醇理论收率为9.29%,实际收率为8.71%。最优硝酸交换条件为:硝酸浓度1.2 mol/L、交换温度63℃、交换时间3 h、液固比为11 mL/g,环己醇理论收率为8.92%,实际收率为8.90%。理论收率与实际收率较吻合,说明均匀设计法在分子筛无机酸交换条件优化上具有较高的实用价值。

Isolation and Identification of Eleven Tertiary Alkaloidsin Corydalis decumbens

Eleven tertiarv alkaloids were isolated from Corvdalis decumbens rhizome Their structures were identified as protopine(Ⅶ),allocryptopine(Ⅷ),cryptopine (Ⅸ),muramine(ⅩⅦ);(+)-tetrahydropalmatine(Ⅲ),(+)-kikemanine (Ⅳ),(一)-scoulerine (ⅩⅧ),(十)-bulbo- capnine (ⅩⅨ),and(一)一capnoidine(Ⅰ),(一)一bicuculline(Ⅴ),(+) coriumidine(ⅩⅣ), respecti vely。 Among these,cryptopine,muramine,(+)-kikemanine,(-)-scoulerine,(一)capnoidine,(一)一bicuculline were isolated for the first time from this plant

一种低泡的中性喷淋式水基链条润滑剂的研制

为了满足目前食品行业对自动输送设备使用的水基链条润滑剂所提出的既要润滑性好又要泡沫低的新要求,研制了一种由脂肪酸、非离子表面活性剂、防锈剂、螯合剂、消泡剂及抑菌剂组成的低泡中性喷淋式水基链条润滑剂。该水基链条润滑剂的润滑度可达到目前市售主流的含脂肪胺组分的水基链条润滑剂产品的性能指标,而且因其不含脂肪胺,具有泡沫性极低的特性,并具有去污、抗腐蚀和抑菌的特点。

高硅丝光沸石的合成及其在C5／C6异构化工艺中的应用

采用无胺法高硅丝光沸石合成了产率，降低了生产成本并解决了环保及生产问题。结果表明，采用本高硅载体工艺，直接合成出合格的C5／C6异构化催化剂载体，免去盐酸处理，提高制成的异构化催化剂活性达到了工业要求。

Application of Tertiary Amine Cationic Polyacrylamide with High Cationic Degree in Salt-free Dyeing of Reactive Dyes

Tertiary amine cationic polyacrylamide with high cationization degree was used as a new cationic agent to pretreat cotton with dip-pad-bake method. The obtained cationic cotton was dyed with reactive dyes in the ab-sence of electrolyte. The effects of the characteristics of the cationic agent and the pretreatment conditions on dye-ability of reactive dye were investigated. The results showed that the fixation and K/S values of the reactive dyes on the cationic cotton were improved compared with those on the untreated one in the presence of salt. Tests on fast-ness properties of the dyed cotton and fabric quality of the pretreated cotton were carried out and the results showed that wash and rub fastness of the salt-free dyeing were both satisfactory. And anti-crease property,tensile and tear strength,and handling of the cationic cotton were also good compared with that of the untreated one.

A shaped binderless ZSM-11 zeolite catalyst for direct amination of isobutene to tert-butylamine

A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The binderless catalyst was synthesized using a dry‐gel conversion technique, inwhich 1,6‐hexanediamine and tetrabutylammonium bromide were used as structure‐directingagents and no other alkaline materials were added. The catalytic performance of the zeolites in the direct amination of isobutene to tert‐butylamine was evaluated in a fixed‐bed reactor. By virtue of its high crystallinity as well as its good mechanical strength, the shaped binderless ZSM‐11 catalyst showed a higher rate of formation of tert‐butylamine than did the binder‐containing catalysts.

A method to refine crude cottonseed oil using non-toxic polyamine-based cationic polymers

The traditional method to refine crude cottonseed oil is time-consuming and expensive.This study evaluates the effectiveness of coagulation–flocculation–sedimentation process using quaternary polyamine-based polymers in refining crude cottonseed oil.Flocculated by four commercial polyamine-based cationic polymers(SL2700,SL3000,SL4500 and SL5000)with varied molecular weight(MW)and charge density(CD)and followed by coagulation with sodium hydroxide,crude cottonseed oil can be effectively purified.Free fatty acids,gossypol,pigments and trace elements are all effectively and sufficiently removed by the four polymers in a MW-and CDdependent manner.Our results suggest that the use of polyamine-based cationic polymers may offer an effective and feasible alternative to the traditional method for crude cottonseed oil refining.

An open add-on study on cyclophosphamide in patients with refractory myasthenic crisis

Objective: To assess the efficacy and side effects of cyclophosphamide on refractory myasthenic crisis. Methods: Five patients of myasthenic crisis refractory to usual comprehensive treatment, entered an open additional study with cyclophosphamide 200 mg VD q. d or 400 mg VD q. o. d with 6-10 g of total dosage. The patients were followed up for 1-8 years. Results: All the 5 patients were effectively treated with obvious remission in 3 and improvement in 2. Two patients have returned to partial work. The side effects were tolerable. Conclusion: The present clinical trial showed that cyclophosphamide was effective, particularly in a long term as an additional therapy for treating MG patients with refractory crisis of myasthenia gravis.

Selection of extractive agent for mixture chlorobenzene and measurement of VLE data for m-dichlorobenzene-p-dichlorobenzene -o-dichlorobenzene -diphenylamine

Extractive agents of extractive distillation separation for mixtures of dichlorobenzene were analyzed and compared, gas-liquid equilibrium data （VLE data） was measured for dichlorobenzene and diphenylamine, the appropriate extractive agent was selected by relatively volatility, the temperature was studied on the effect of extractive separation. VLE data was measured for dichlorobenzene, the parameters were simulated in Wilson equation. The infinite dilute activity coefficient of dichlorobenzene in diphenylamine were measured by chromatogram apparatus, the model parameters were correlated by the single parameter method for dichlorobenzene and diphenyl -amine, VLE data of m-dichlorobenzene-p- dichlorobenzene -o-dichlorobenzene-diphenylamine system was measured and calculated by six part model parameters. The results of correlation and experiment were provided a basis for study of extractive distillation simulation and experiment in this work.

Aromatic bromination with hydrogen production on organic‐inorganic hybrid perovskite‐based photocatalysts under visible light irradiation

Aromatic bromides are important chemicals in nature and chemical industries.However,their tra‐ditional synthesis routes suffer from low atomic economy and pollutant formation.Herein,we show that organic-inorganic hybrid perovskite methylammonium lead bromide(MAPbBr_(3))nanocrystals stabilized in aqueous HBr solution can achieve simultaneous aromatic bromination and hydrogen evolution using HBr as the bromine source under visible light irradiation.By hybridizing MAPbBr_(3) with Pt/Ta_(2)O_(5) and poly(3,4‐ethylenedioxythiophene)polystyrene sulfonate as electron‐and hole‐transporting motifs,aromatic bromides were achieved from aromatic compounds with high yield(up to 99%)and selectivity(up to 99%)with the addition of N,N‐dimethylformamide or its analogs.The mechanistic studies revealed that the bromination proceeds via an electrophilic attack pathway and that HOBr may be the key intermediate in the bromination reaction.

沸石分子筛的绿色合成路线

沸石分子筛因具有独特的孔道结构、较强的酸性和高的水热稳定性,在吸附分离、催化和离子交换等领域得到了广泛的应用。沸石分子筛的合成方法大多采用水热法,需要使用大量含硅铝的化工产品和有机模板剂,导致沸石分子筛的合成成本较高、效率较低,且环境污染较为严重,因此沸石分子筛高效绿色合成路线的研究具有重大意义。本文主要从沸石分子筛的合成原料绿色化、合成条件绿色化以及合成方法绿色化等三个方面综述了国内外沸石分子筛绿色合成路线的研究新进展,并提出现有沸石分子筛绿色合成路线存在的问题以及将来的发展方向。