Continuous,efficient and safe synthesis of 1-oxa-2-azaspiro[2.5]octane in a microreaction system

1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

Simultaneous removal of sulfur dioxide and nitrogen oxide from flue gas by phosphorus sludge:The performance and absorption mechanism

Developing low-cost and green simultaneous desulfurization and denitrification technologies is of great significance for sulfur dioxide(SO_(2))and nitrogen oxide(NO_(x))emission control at low temperatures,especially for small and medium-sized coal-fired boilers and furnaces.Herein,phosphorus sludge,an industrial waste from the production process of yellow phosphorus,has been developed to simultaneously eliminate SO_(2)and NO_(x)from coal-fired flue gas.The key factors affecting the experimental results indicate that desulfurization and denitrification efficiency of over 95%can be achieved at a low temperature of 55℃.Further,the absorption mechanism was investigated by characterizing the solid and liquid phases of the phosphorus sludge during the absorption process.The efficient removal of SO_(2)is attributed to the abundance of iron(Fe^(3+))and manganese(Mn^(2+))in the absorbent.SO_(2)can be rapidly catalyzed and converted to SO_(4)^(2-)by them.The key to NOx removal is the oxidation of NO toward watersoluble high-valent nitrogen oxides by oxidizing reactive substances induced via yellow phosphorus,which are then absorbed by water and converted to NO_(3)^(-).Meanwhile,yellow phosphorus is oxidized to phosphoric acid(H_(3)PO_(4)).The spent absorption slurry can be reused through wet process phosphoric acid production,as it contains sulfuric acid(H_(2)SO_(4)),nitric acid(HNO_(3)),and H_(3)PO_(4).Accordingly,this is a technology with broad application prospects.

Hollow ZIF-67-derived Co@N-doped carbon nanotubes boosting the hydrogenation of phenolic compounds to alcohols

The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.

Femtosecond laser-engineered 3D microfluidic chips: Synthesis system sprouting highly efficient multiphase organic reactions

Recent developments in the utilization of microfluidic chips(MFCs) have shown their potential utility in multiphase organic synthesis by enabling efficient organic reactions in flow chemistry. However, MFCs technology has been wandering in the laboratory of small dose synthetic routes, which is limited to the level of "tiny" fluid flux. To address this issue, we herein report the first case of the chips with highthroughput 3D channels produced by femtosecond laser being used to create a time-saving, cost-effective and risk-free approach suitable for large-scale flow synthesis. Several multiphase reactions have been successfully prepared on demand in our designed flow synthesis system containing 3D MFCs: 1) benzyl alcohol was converted to benzaldehyde in 3 min with a yield of 97.50% by liquid-liquid two-phase transfer catalytic oxidation;2) organozinc reagents and α-cyano carbonyl carbon compounds were synthesized by solid-liquid two-phase metal insertion reaction in 7 min, and the yield was up to 100%;3) benzoic acid was synthesized by gas-liquid two-phase carboxylation reaction in 2.8 s with a yield of 96%. Significant gains in production rate result from the effective scaling of flow reactors from microliters per hour in MFCs to intermediate milliliters per minute without affecting mass transport performance. Meanwhile,our 3D MFCs show excellent mass and heat transfer efficiency in large-scale industrial units, breaking through the bottleneck in this field. As a result, it is possible to imagine the creation of a new, streamlined flow synthetic technique via MFCs for green multiphase organic synthesis.

Recent development of catalytic strategies for sustainable ammonia production

Presently,ammonia is an ideal candidate for future clean energy.The Haber-Bosch process has been an essential ammonia production process,and it is one of the most important technological advancements since its invention,sustaining the explosive growth of military munitions industry and fertilizers in the first half of the 20th century.However,the process is facing great challenges:the growing need for ammonia and the demands of environmental protection.High energy consumption and high CO_(2) emissions greatly limit the application of the Haber-Bosch method,and increasing research efforts are devoted to"green"ammonia synthesis.Thermocatalytic,electrocatalytic,and photocatalytic ammonia production under mild conditions and the derived chemical looping and plasma ammonia production methods,have been widely developed.Electrocatalytic and photocatalytic methods,which use low fossil fuels,are naturally being considered as future directions for the development of ammonia production.Although their catalytic efficiency of ammonia generation is not yet sufficient to satisfy the actual demands,considerable progress has been made in terms of regulating structure and morphology of catalyst and improving preparation efficiency.The chemical looping approach of ammonia production differs from the thermocatalytic,electrocatalytic,and photocatalytic methods,and is the method of reusing raw materials.The plasma treatment approach alters the overall ammonia production approach and builds up a new avenue of development in combination with thermal,photocatalytic,and electrocatalytic methods as well.This review discusses several recent effective catalysts for different ammonia production methods and explores mechanisms as well as efficiency of these catalysts for catalytic N2fixation of ammonia.

Enhanced selective hydrogenation of glycolaldehyde to ethylene glycol over Cu^(0)-Cu^(+)sites

Selective hydrogenation of hydroxyaldehydes to polyalcohols is challenging due to the competitive hydrogenation of C=O and CAO.This study develops heterogeneous Cu catalysts for the selective synthesis of ethylene glycol via batch liquid-phase hydrogenation of glycolaldehyde.SiO_(2)supported Cu,fabricated by ammonia evaporation,enables to catalyze the C=O bond hydrogenation with retaining the CAO bond intact,yielding higher selective hydrogenation activity with ethylene glycol selectivity up to 99.8%relative to MgO,Al_(2)O_(3),CeO_(2),and TiO_(2)supports and Cu/SiO_(2)synthesized by deposition–precipitation and impregnation.Characterizations confirm that highly efficient 20Cu/SiO_(2)-AE-623 K catalyst fabricated by ammonia evaporation is featured with larger Cu^(0)and Cu^(+)surface areas,of which the Cu^(+)species created from reducing copper phyllosilicate exhibit higher reactivity.A synergistic effect between Cu^(+)and Cu^(0)facilitates the selective adsorption/activation of glycolaldehyde on Cu^(+)sites and the dissociation of H_(2)on Cu^(0)sites,bringing a remarkable improvement in the selective hydrogenation performance.

Multiphase surfactant-assisted reaction-separation system in a microchannel reactor

The Lewis acid-catalyzed addition of tri-methylsilyl cyanide to p-chlorobenzaldehyde in a micro-channel reactor was investigated.The microchannel was integrated to promote both reaction and separation of the biphase system.FeF3 and Cu(triflate)2 were used as water-stable Lewis acid catalysts.Sodium dodecyl sulfate was incorporated in the organic-aqueous system to enhance the reactivity and to manipulate the multiphaseflow inside the microchannel.It was found that the dynamics and the kinetics of the multiphase reaction were affected by the new micellar system.Parallel multiphaseflow inside the microchannel was obtained,allowing for continuous and acceptable phase separation.Enhanced selectivity was achieved by operating at lower conversion values.

CFD modeling using heterogeneous reaction kinetics for catalytic dehydrogenation syngas reactions in a fixed-bed reactor

A comprehensive 2D computational fluid dynamics （CFD） model was developed to simulate the flow behavior and catalytic dehydrogenation reaction of syngas in a heterogenous fixed-bed reactor （FBR）. The model combined the porous medium CFD model with a reaction kinetics model. To acquire an accu- rate reaction kinetics model, a comprehensive reaction mechanism was studied for the heterogeneous catalytic dehydrogenation reaction ofsyngas over a supported metal catalyst. Based on the reaction mech- anism and a statistical test, a reliable kinetics model was proposed. The CFD model combined with the above kinetics model was validated with one set of experimental data. The CFD model was also used to predict key reaction variable distributions such as the temperature and the component concentrations in the reactor.