Catalytic activity of mesoporous catalysts in Friedel–Crafts benzylation of benzene

Different samples of metal-incorporated MCM-41 were prepared and used as catalysts in Friedel–Craft’s benzylation of benzene. The catalytic performance was evaluated by off-line GC analysis. Fe-MCM-41 exhibited excellent activity, the sample with Si/Fe ratio = 10 showed 90% conversion with 95% selectivity towards diphenylmethane within a few minutes. Generally, the activity per Fe-site was an order of magnitude higher for the samples containing a combination of Fe₂O₃ nano-particles and isolated Fe³⁺ sites. A synergy of two catalytic centers (particles and isolated sites) is proposed to explain the high performance of the highly loaded samples. The catalytic performance of Fe-MCM-41 was superior to other metal-containing MCM-41 (e.g. Ga, Sn, and Ti) catalysts, or other Fe-containing mesoporous materials (e.g. Fe-HMS).     

煤系高岭土制备Fe-MCM-41介孔分子筛及其氨选择性催化还原NOx

以煤系高岭土、十六烷基三甲基溴化铵（CTAB）、硝酸铁等为原料,通过水热法合成不同Fe含量的六方介孔分子筛Fe-MCM-41。通过傅里叶变换红外光谱、N2吸附脱附、高分辨透射电子显微镜对催化剂进行表征,并以氨为还原剂研究其选择性催化还原NO活性以及反应条件（包括Fe掺量、反应温度、空速、氨氮比和O2浓度等）对催化性能的影响。结果表明,Fe成功进入MCM-41介孔材料的骨架内,Fe-MCM-41介孔分子筛BET比表面积为980.2～596.8 m2/g,孔容积为0.95～0.60 cm3/g,平均孔径在3.90～3.45 nm。随着铁掺杂量的增加,介孔结构的有序度下降。当n(Fe)/n(Si)=0.05、空速为5000 h?1,Fe-MCM-41催化剂在350 ℃反应时NO转化率最高,可达90.7%;且当氨氮比为1.1和O2含量为2.5%时,催化剂能保持较高的活性。     

5,6-二甲基苯并咪唑的合成工艺改进

以 3,4 二甲基苯胺为母体 ,合成了 5 ,6 二甲基苯并咪唑。产品收率达 41%。在乙酰化、硝化反应中引入了 1,2 二氯乙烷溶剂。用正交实验确定了最佳原料配比 :n(3,4 二甲基苯胺 )∶n(醋酐 )∶n(硫酸 ) =1 0 0∶1 30∶1 13。改进后 ,每mol母体的醋酐用量由 30 3 0g减少至 132 6g ,浓硫酸用量由 30 3 8g减少至 110 74g。     

Phenol hydroxylation using Fe-MCM-41 catalysts

Highly ordered iron-containing mesoporous material, Fe-MCM-41, with 0.5–4 Fe/Si mol% loading was prepared and characterization was performed using XRD, SEM/TEM, EDS, N₂-sorption, and FT-IR and UV–vis spectroscopies. Fe-MCM-41 exhibited high catalytic activity in phenol hydroxylation using H₂O₂ as oxidant, giving phenol conversion of ca. 60% at 50 °C [phenol:H₂O₂ = 1:1, water solvent]. Effects of Fe contents in Fe-MCM-41 and catalyst concentration, temperature, solvent used, phenol/H₂O₂ mole ratios and H₂O₂ feeding method, and catalyst calcination temperature on conversion profiles were examined. Catalyst recycling was performed to investigate the extent of potential metal leaching. Comparisons in performance were also made using nano-sized Fe₂O₃ particles and Fe-salt impregnated MCM-41 as catalyst. Catechol to hydroquinone in product ratio was close to 2:1 in accordance with a free radical reaction scheme involving Fe²⁺/Fe³⁺ redox pair and the larger amount of Fe species always achieved the given phenol conversion at a shorter reaction time. As the calcination temperature increases from 400 to 800 °C increasing amount of Fe species came out from the MCM-41 framework. Both tetrahedral Fe and extra-framework Fe species were found catalytically active, but high dispersion of Fe species achieved in Fe-MCM-41 was an advantage.     

Fe2O3/TUD-1: an efficient catalysts for Friedel–Crafts alkylation of aromatics

Three-dimensional mesoporous (Fe-TUD-1) catalysts with different Si/Fe ratios (100, 50, 20 and 10) are prepared using triethanolamine as template. Physicochemical and textural measurements by XRD, elemental analysis, N₂ adsorption, UV–Vis spectroscopy and HR-TEM imaging indicate the formation of pure solid mesoporous materials and the presence of Fe₂O₃ nanoparticles in the prepared Fe-TUD-1 samples. The catalytic performance of Fe-TUD-1 catalysts is tested in Friedel–Crafts alkylations of single-ring aromatic compounds [e.g. toluene (T), ethyl benzene (EB) and cumene (C)] by benzyl alcohol (BnOH). Dispersion of Fe(III) in the mesoporous matrix of TUD-1 enhanced the catalytic activity of Fe-TUD-1 in the alkylation of aromatic compounds compared to pure Fe₂O₃ and TUD-1 catalysts. The catalytic activity further increases by the decreasing of Si/Fe ratio. Sample loaded with Si/Fe ratio = 10 (Fe-10) showed almost complete conversion of BnOH in a relatively very short reaction time (<30 min) with 95 % selectivity. The catalytic performance of Fe-TUD-1 was superior to other metal-containing TUD-1 (e.g. Ga, Sn, and Ti) catalysts, or other Fe-containing catalysts (e.g. Fe-MCM-41, ZSM-5 and Fe-HMS). Alkylation of C is the fastest among the three aromatic substrates investigated (at temperatures very close to their boiling points) due to the largest inductive effect by the isopropyl group compared to the methyl group of T and the ethyl group in EB. Dibenzyl ether is formed as a byproduct only in the early times of the reaction and proved to act as alkylating agent after being hydrolyzed backwards to reform BnOH. Leaching experiments show the Fe-TUD-1 materials are very stable and can be reused as alkylation catalyst.     

Highly active three-dimensional cage type mesoporous aluminosilicates and their catalytic performances in the acetylation of aromatics

Three-dimensional cage type mesoporous aluminosilicates (AlKIT-5) with different n_Si/n_Al ratios have been successfully synthesized hydrothermally using pluronic F127 as a template under highly acidic medium [P. Srinivasu, S. Alam, V.V. Balasubramanian, S. Velmathi, D.P. Sawant, W. Böhlmann, S.P. Mirajkar, K. Ariga, S.B. Halligudi, A. Vinu, Adv. Funct. Mater., in press]. The catalysts have been unambiguously characterized by XRD, N₂ adsorption, and TPD of NH₃, and utilized for the acetylation of veratrole, and other aromatic substrates such as anisole, isobutylbenzene, and 2-methoxynaphthalene, using acetic anhydride (AA) as an acylating agent under liquid phase conditions. The effect of various parameters such as the reaction temperature, reaction time, reactant mole ratios, and amount of aluminium, on the AA conversion in the acetylation of veratrole has been investigated in detail to discover the optimized reaction condition. The reaction conditions were optimized to get more conversion of acetic anhydride and the activity of these catalysts has been compared with zeolite catalysts namely HY, Hβ, H-mordenite, and HZSM-5 zeolites, and the results are discussed in detail. It has been found that the AlKIT-5 catalysts showed excellent performance in the acetylation of veratrole over zeolites and other mesoporous catalysts studied under the optimized reaction conditions. Among the catalysts studied, AlKIT-5(10) was found to be the best catalyst, showing high conversion of AA and very high selectivity to the desired products. The conversion of AA decreases in the following order: AlKIT-5(10) > AlKIT-5(28) > HY(13.5) > Hβ(30) > AlKIT-5(44) > AlMCM-41(22) > H-mordenite(20) > ZSM-5(60). Moreover, the kinetics of the AlKIT-5(10) catalyst in the acetylation of veratrole has been investigated in detail and the results are clearly discussed.     

Acetylation of phenol with Al-MCM-41

Mesoporous Al-MCM-41 molecular sieve materials with three different SiO₂/Al₂O₃ ratios were used as catalysts for the acetylation of phenol with acetic anhydride and acetic acid as the acetylating agents. The reactions gave 100% ortho-selectivity with acetic acid being the more effective acylating agent. The reactions were run under different conditions of temperature, feed flow rate, reactant mole ratio and SiO₂/Al₂O₃ ratio of the catalyst and all the variables were shown to have significant influence on the acetylation of phenol. A possible reaction mechanism is also suggested.     

Synthesis, characterization, and unique catalytic performance of the mesoporous material Fe-TUD-1 in Friedel–Crafts benzylation of benzene

Iron (Fe)-containing mesoporous TUD-1 catalysts (denoted as Fe-TUD-1) with different Si/Fe ratios (100, 50, 20 and 10) were synthesized using triethanolamine as a template. They were characterized by XRD, elemental analysis, N₂ ad/desorption measurements, HR-TEM, UV–vis, ²⁹Si NMR, and ⁵⁷Fe Mössbauer spectroscopies. Catalytic performance was tested in the Friedel–Crafts benzylation of benzene. Fe-TUD-1 showed excellent activity, with 100% conversion and 100% selectivity towards diphenylmethane, superior to other metal-containing TUD-1 (e.g. Ga, Sn, and Ti) or other Fe-containing mesoporous materials (e.g. Fe-MCM-41 and Fe-HMS).     

助剂掺杂对Fe-MCM-41在环己烷氧化反应中催化性能的影响

以硅酸钠为硅源,十六烷基三甲基溴化铵为模板剂,硝酸铁为金属源,水热法直接合成Fe-MCM-41,再辅以助剂Co和Cr形成双金属掺杂的介孔材料,采用XRD、N2吸脱附、TG-DTA、FTIR、ICP对材料的结构和物化性质进行表征。以乙腈为溶剂,H2O2为氧化剂,考察所制备的材料对环己烷氧化的催化活性和选择性的影响。结果表明,与Fe-MCM-41的催化性能相比,FeCo-MCM-41会使环己烷的转化率下降,但环己醇的选择性增加;而FeCr-MCM-41会使环己烷的转化率和环己酮的收率增加。     

4,5-二甲基-1,2-二苯胺的合成工艺改进

以3,4-二甲基苯胺为原料,合成了4,5-二甲基-1,2-二苯胺,产品收率达69%以上。在乙酰化、硝化反应中引入了1,2-二氯乙烷溶剂。用正交实验确定了最佳原料配比:n(3,4-二甲基苯胺)∶n(醋酸酐)∶n(硫酸)=1.00∶1.15∶1.10,硝化反应温度为13°C,反应时间为3.5h,硝化产物收率为90.56%,溶剂回收率95%以上。改进后,每摩尔母体的醋酸酐用量由303g减少至118g,浓硫酸用量由304g减少至108g。     

助剂掺杂对Fe—MCM-41在环己烷氧化反应中催化性能的影响

z以硅酸钠为硅源，十六烷基三甲基溴化铵为模板剂，硝酸铁为金属源，水热法直接合成Fe—MCM-41，再辅以助剂co和cr形成双金属掺杂的介孔材料，采用XRD、N2吸脱附、TG—DTA、FTIR、ICP对材料的结构和物化性质进行表征。以乙腈为溶剂，H2O2为氧化剂，考察所制备的材料对环己烷氧化的催化活性和选择性的影响。结果表明，与Fe—MCM41的催化性能相比，FeCo—MCM41会使环己烷的转化率下降，但环己醇的选择性增加；而FeCr—MCM41会使环己烷的转化率和环己酮的收率增加。     

Novel Highly Acidic Nanoporous Cage Type Materials and Their Catalysis

Acylation of aromatic compounds such as veratrole (1,2-dimethoxybenzene), anisole, isobutyl benzene, and 2-methoxynaphthalene with acetic anhydride (Ac₂O) has been investigated over different solid acid catalysts such as MWW, BEA, FAU, MOR, and MFI. MWW catalysts have been characterized by X-ray diffraction, N₂ adsorption–desorption isotherm, and HR-FESEM characterization techniques. The reaction is studied in the temperature range 313–353 K under N₂ atmosphere. Among the catalysts tested, MWW was found to be more active than other zeolites. This is mainly due to its three dimensional porous structure with excellent textural characteristics. The effect of veratrole/Ac₂O molar ratio, catalyst concentration, and reaction temperature has been optimized to get higher conversion of Ac₂O. Under the optimized reaction conditions, MWW gave the Ac₂O conversion of 64.3% with a selectivity to acetoveratrone (3′,4′-dimethoxyacetophenone) (100%). It was also found that the structural features and acidity play an important role in the conversion and product distribution in the acylation of different aromatic substrates like anisole, isobutyl benzene, and 2-methoxy naphthalene. MWW catalyst has been reused in few cycles after regeneration by washing with ethyl acetate followed by calcination at 500 °C for 4 h without loss in its activity. The reaction kinetics of the catalyst was also studied and the results are discussed in detail.     

Wood preservation by a mixed anhydride treatment: A 13C‐NMR investigation of simple models of polymeric wood constituents

The treatment of wood by a mixed aceto/oleic (or other fatty acid residue) anhydride promoted as a safe and environmentally friendly wood preservation system was examined quantitatively by liquid‐phase ¹³C‐NMR and solid‐phase magic angle spinning–DEC (proton decoupling) ¹³C‐NMR through of all its different stages to determine which reactions occurred with simple model compounds of the polymeric constituents of wood. The preparation of the mixed aceto/oleic anhydride under different conditions was also undertaken. The anhydride formed, but its percentage yield was only 30%. The mix composed of unreacted acetic anhydride, the mixed aceto/oleic anhydride, and a large proportion of free acetic and oleic acid, which are used for wood preservation, yielded the acetylation of the lignin model compound (1) by the reaction of the acetic anhydride with it and (2) by the reaction of the acetic part of the mixed anhydride. In this reaction, all of the mixed anhydride was consumed. The oleic part of the mixed anhydride was unable to form esters with either lignin or wood holocellulose as it was far less reactive than the acetic part. Some acetylation of holocellulose occurred, and some traces of its oleic acid ester also occurred under some conditions. This system of treatment through a mixed anhydride appeared to consist of just an acetylation with acetic anhydride mixed with some oleic acid as a water repellent, both of which are already known processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A Novel Synthetic Route to Hexanitrohexaazaisowurtzitane

A new, non‐hydrogenolytic synthesis of hexanitrohexaazaisowurtzitane (HNIW, 1 ) has been investigated. The treatment of hexabenzylhexaazaisowurtzitane (HBIW, 2 ) with potassium permanganate in acetic anhydride resulted in oxidative debenzylation and acetylation to give tetraacetyldibenzylhexaazaisowurtzitane (TADB, 3a ) and other intermediates from the oxidation. Subsequent nitrosolysis and nitrolysis of these intermediates with 65% HNO₃/NaNO₂ and 70% HNO₃/AN produced HNIW in fair yield.     

Removal of citric acid from aqueous solution by catalytic wet peroxidation using effective mesoporous Fe‐MCM‐41 molecular sieves

The presence of citric acid in decontamination waste can cause complexation of radioactive cations, resulting in interferences in their removal by various treatment processes such as chemical precipitation and ion exchange, and may pose a potential danger to the environment. Mesoporous Fe‐MCM‐41 molecular sieves (Si/Fe = 25, 50, 75 and 100) were synthesized hydrothermally and characterized by X‐ray diffraction, N₂ adsorption studies, diffuse reflectance UV‐visible spectroscopy, electron paramagnetic resonance and transmission electron microscopy to evaluate the removal of citric acid from aqueous solution by the wet peroxidation method. The effect of time, pH, Si/Fe ratios of Fe‐MCM‐41 and temperature has been studied to achieve efficient removal of citric acid from the aqueous solution. Unlike homogeneous Fe³⁺ catalysis, more mineralization of citric acid was achieved by heterogeneous catalysis with Fe‐MCM‐41 with the percentage removal of total organic carbon of citric acid following the order Fe‐MCM‐41 (Si/Fe = 25) > Fe‐MCM‐41 (Si/Fe = 50) > Fe‐MCM‐41 (Si/Fe = 75) > Fe‐MCM‐41 (Si/Al = 100). Moreover, it was also observed that during the reaction only a minimum amount of iron is leaching from Fe‐MCM‐41. Copyright © 2007 Society of Chemical Industry     

Reaction of Hydrogen Bromide with Long Chain 1,2-Diols

The reactions of 1,2-hexadecanediol and 1,2-octadecanediol with hydrogen bromide in the presence of acetic anhydride have been investigated. The treatment of hydrogen bromide (48%) in acetic anhydride with 1,2-hexadecanediol gives mainly 1-bromo-2-acetoxy hexadecane (66%), 2-acetoxy hexadecanol (26%), and 1,3-hexadecanediol (8%). Similar products result from 1,2-octadecanediol. The structures of the products are based on combustion data, spectroscopic, and chemical evidences. The mechanism of the reaction has been discussed.     

Catalytic performance of metal ion doped MCM-41 for methanol dehydration to dimethyl ether

Metal ion doped MCM-41 mesoporous molecular sieves (M-MCM-41, M = Al, Ga, Sn, Zr and Fe) were prepared using a hydrothermal synthesis method, with metal chlorides serving as the dopant sources. The M-MCM-41 structures were characterized by Fourier transform infrared spectroscopic (FTIR) analysis, X-ray diffraction, energy dispersive spectroscopy and N₂ adsorption–desorption measurement. The surface of M-MCM-41 acidities were determined by NH₃ temperature-programmed desorption and pyridine-adsorption FTIR analysis, and their catalytic performance for methanol dehydration to dimethyl ether (DME) was evaluated. The results showed that the prepared M-MCM-41, which exhibited a structure similar to that of MCM-41 with long-range ordered mesoporous structure, contained weak acidic sites. The number of weak acid sites in Al-MCM-41 increased as the Al content increased. The Al content in Al-MCM-41 had an important effect on its catalytic performance, where the highest catalytic activity was 80 and 100 % DME selectivity was achieved at a Si/Al molar ratio of 10. For MCM-41 doped with various types of metal ions, M-MCM-41 (M = Al, Ga, Sn and Zr) also presented a similar wide distribution of acidity, and their catalytic activities were ranked in the following order: Al-MCM-41 > Ga-MCM-41 > Zr-MCM-41 > Fe-MCM-41 > Sn-MCM-41, which were related to the coordination of the metal ions.     

Effective acetylation of alcohols,phenols and amines over mesoporous aluminophosphate solid acids under solvent free conditions

Solid acids such as amorphous aluminophosphates (AlP) and iron aluminophosphates (FeAlP) were synthesized by either precipitation or co-precipitation methods. These solid acids were characterized by BET, NH₃-TPD, PXRD, FT-IR and NMR techniques for their surface area, surface acidity, crystallinity and functionality. AlPs and FeAlPs were found to be mesoporous in nature. The catalytic activity of these solid acids was determined in acetylation of various alcohols, phenols and amines with acetic anhydride under solvent free conditions. The reaction conditions were optimized by varying the parameters such as molar ratio of the reactants, reaction temperature and amount of the solid acid catalyst. Among the solid acids, FeAlP consisting of 0.025 mol% Fe showed good catalytic activity in the acetylation reaction. These solid acid catalysts can also be reused for acetylation at least for five reaction cycles without any appreciable loss of catalytic activity.     

缓蚀阻垢剂HEDP的制备及性能分析

以三氯化磷和乙酸酐为原料,经三步合成羟基乙叉二膦酸（HEDP）并考察其缓蚀阻垢性能;考察了乙酰化反应的条件。结果表明,最佳乙酰化反应合成工艺条件为：反应温度100℃,乙酸酐滴加速率为先快后慢,（CH3CO）2O∶PCl3摩尔比为1∶3;HEDP的最佳使用条件：浓度为10 mg/L,温度为60℃,实验时间为24 h,缓蚀率和阻垢率分别高达86.6%,93.8%。     

Study of the influence factors on the synthesis of Fe-MCM-48 with binary mixed cationic and anionic surfactants

Highly ordered Fe-MCM-48 was synthesized by a mixed template method under low molar ratio (0.17:1) of mixed surfactants to silica. The effect of various factors, such as Fe sources, the amount of Fe salt, Si sources, surfactant/SiO₂, crystallization temperature and crystallization time on the synthesis were discussed in detail. The Debye-Huckel theory, the theory of salts formation, the local effective surfactant packing parameter theory and the charge balance theory were used to explain the reason that various factors can affect the product structure reasonably. The optimum synthesis conditions for Fe-MCM-48 were obtained.