Synthesis of spherical nano-ZSM-5 zeolite with intergranular mesoporous for alkylation of ethylbenzene with ethanol to produce m-diethylbenzene

Catalytic synthesis of m-diethylbenzene(m-DEB)through alkylation of ethylbenzene(EB)may be a promising alternative route in comparison with traditional rectification of mixed DEB,for which the top priority is to develop efficient and stable heterogeneous catalysts.Here,the spherical nano-ZSM-5 zeolite with abundant intergranular mesoporous is synthesized by the seed-mediated growth method for alkylation of EB with ethanol to produce m-DEB.The results show that the spherical nano-ZSM-5 zeolite exhibits better stability and higher alkylation activity at a lower temperature than those of commercial micropore ZSM-5.And then,the spherical nano-ZSM-5 is further modified by La_(2)O_(3) through acid treatment followed by immersion method.The acid treatment causes nano-ZSM-5 to exhibit the increased pore size but decreased the acid sites,and subsequent La_(2)O_(3) loading reintroduces the weak acid sites.As a result,the HNO_(3)-La_(2)O_(3)-modified catalyst exhibits a slight increase in EB conversion and DEB yield in comparison with unmodified one,and meanwhile,it still maintains high m-DEB selectivity.The catalyst after acid treatment achieves higher catalytic stability besides maintaining the high alkylation activity of EB with ethanol.The present study on the spherical nano-HZSM-5 zeolite and its modification catalyst with excellent alkylation ability provides new insights into the production of mDEB.

季铵类离子液体催化熔融缩聚反应合成异山梨醇基聚碳酸酯（英文）

聚碳酸酯是一种性能优良的工程塑料,具有优异的透明性、绝缘性及无毒性等优点.目前实现大规模工业生产的是双酚A型聚碳酸酯,但是其生产原料双酚A具有毒性,限制了其应用.异山梨醇是一种生物基可再生单体,具有无毒、手性和刚性等特性,是双酚A的理想替代品.但是异山梨醇亲水性强,且羟基的活性低,导致碳酸二苯酯和异山梨醇通过熔融缩聚反应合成异山梨醇基聚碳酸酯(PIC)困难,因此选用合适的催化剂成为一个重要因素.目前报道的效果较好的催化剂是无机碱催化剂,这类催化剂催化活性差,容易引发副反应,在产品中残留影响产品质量.离子液体具有环境友好和阴阳离子可设计等优点,是无机碱催化剂的良好替代品.本文设计合成了六种季铵类的碱性离子液体(四乙铵二氰胺盐、四乙铵咪唑盐、四乙铵乳酸盐、四乙铵-1,2,4-三氮唑盐、四乙铵苯甲酸盐和四乙铵乙酸盐),用于催化熔融缩聚反应合成PIC.用核磁共振表征了PIC的结构,用凝胶色谱测定了PIC的分子量,通过对比PIC的重均分子量(Mw)和异山梨醇的转化率,研究了离子液体阴离子对催化剂活性的影响.发现催化活性不仅与离子液体的碱性强弱有关,还与离子液体阴离子的配位强度有关,催化效果最好的离子液体为四乙铵咪唑盐(TEAI).以TEAI为催化剂对合成PIC的条件进行了优化,得到的最优条件为:催化剂与异山梨醇的摩尔比为5×10^(-4),缩聚时间为5 h,缩聚温度为240 ℃.合成PIC的Mw为25600 g/mol,异山梨醇的转化率为92%.由于均聚物PIC分子链刚性大,导致PIC熔体粘度大,不利于聚合,为了降低PIC的刚性和提高分子量,在分子链中引入了柔性基团(脂肪族二醇)来合成共聚碳酸酯(PAIC).以TEAI为催化剂,异山梨醇和脂肪族二醇投料摩尔比为1:1,通过熔融缩聚反应合成了PAICs.利用~1H NMR和^(13)C NMR详细表征了PAICs化学组成和微观结构,发现不同脂肪族二醇的羟基活性不同,合成的PAICs分子链中异山梨醇和脂肪族二醇的比例与投料比有所差异,得到的共聚物为无规共聚物.此外,对PAICs进行了凝胶色谱测试,发现PAICs的Mw与PIC相比均有所提高.通过差示扫描量热仪和热重分析仪对PIC和PAICs进行了热稳定性测试.结果表明,对于不同直链二醇制备的PAICs,随着二醇链中亚甲基数量的增加,其玻璃化转变温度(T_g)逐渐降低,但热稳定性逐渐提高;而对于用1,4-环己烷二甲醇合成的PCIC,其Tg值和热稳定性明显高于直链脂肪族二醇共聚物.这些性能为共聚碳酸酯用作高性能聚合材料提供了可能性.

Effects of imidazolium-based ionic liquids on the isobaric vapor–liquid equilibria of methanol+dimethyl carbonate azeotropic systems

The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems containing different imidazolium–based ionic liquids(ILs),i.e.MeOH+DMC+1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf2N]),MeOH+DMC+1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf2N]),and MeOH+DMC+1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])were measured at 101.3 kPa.The mole fraction of IL was varied from0.05 to 0.20.The experimental data were correlated with the NRTL and Wilson equations,respectively.The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and[Bmim][Tf2 N]showed a much more excellent performance on the activity coefficient of MeOH.The interaction energies of system components were calculated using Gaussian program,and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.

Glycerol carbonate synthesis from glycerol and dimethyl carbonate using guanidine ionic liquids

A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate. In this paper, a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate. The tunable basicity and the anion–cation cooperative effect were responsible for the obtained results. The [TMG][TFE] showed the best activity turnover frequency(TOF)of 1754.0 h^(-1), glycerol(GL) conversion of 91.8%, glycerol carbonate(GC) selectivity of 95.5%) at 80 °C with 0.1 mol% catalyst for 30 min. The reaction mechanism of the transesterification was also proposed.

酯交换法制备碳酸二甲酯过程模拟与系统?分析

针对酯交换制备过程中甲醇-碳酸二甲酯共沸体系难分离的问题,分别选择变压精馏、碳酸乙烯酯(EC)萃取精馏与乙二醇(EG)萃取精馏3种分离过程进行模拟与能量集成,对比了3种工艺流程的分离能耗,采用有效能([火用])分析方法分析了能耗最低的变压分离过程的有效能([火用])损失.结果表明,3种工艺流程的能耗EG萃取精馏>EC萃取精馏>变压精馏,碳酸二甲酯生产过程中内部循环物流能量是输入总能量的1.55倍,变压共沸分离过程的[火用]损失为7.9%。

Spatiotemporal characteristics of the expansion of an urban agglomeration and its effect on the eco-environment: Case study on the northern slope of the Tianshan Mountains

Urban agglomerations, which are highly integrated urban groups, form during the advanced stages of industrialization and urban development. The urban agglomeration on the northern slope of the Tianshan Mountains is one of the 19 urban agglomerations promoted by China’s 13th Five-Year Plan and a key area of urbanization in Xinjiang. Based on remote sensing data, we analyzed the expansion of construction land in the urban agglomeration on the northern slope of the Tianshan Mountains and its effect on ecological value in 1980–2015. The results show that the expansion of construction land significantly affected ecological value in the study area over the past 35 years. Among land use types, grassland was the dominant contributor to changes in ecological value;its contribution rate reached 66.27% with an interannual variation of only 5%. The contribution rate of urban and rural residential land along with industrial and mining lands was very low(0.82%), while the interannual variation was large(86%). The area of construction land in the urban agglomeration expanded from 1,067 to 2,586 km^2, and the conversions of different land use types had different effects on ecological value. Among land use types, the conversions of lowcoverage grassland and dry land made the largest contributions to changes in ecological value. During the study period, a total of 1,685 km^2 of ecological land, 69.91% of which belonged to cultivated land and grassland, was converted into construction land.A total area of 1,082 km^2 of dry land and low-coverage grassland was converted into construction land, accounting for 64.21% of the total ecological land that was converted into construction land. In 2000–2015, the area of urban construction land increased significantly along with the proportion of unused land, including gobi(172 km^2), bare land(65 km^2), and salt-affected land(65 km^2), being converted into construction land. In contrast, the area of construction land that was converted into ecological land was less than 166 km^2. The areas with the largest expansions of construction land were concentrated in Urumqi, Karamay,and Changji, where the areas of construction land increased by 399, 186, and 126 km^2, respectively. The areas with the most rapid expansions in construction land were concentrated in Kuytun, Toksun, and Usu. The environmental effects of construction land expansion and land use change were more positive in the late stage of urban agglomeration(2000–2015) compared to in the early stage(1980–2000). Kuytun City, Shihezi City, and Wujiaqu City showed large changes in ecological value caused by the expansion of construction land, whereas the changes in ecological value in the 14 other cities were relatively small, and the expansion of construction land slowed in 2000–2015 compared to in 1980–2000. In the future, further development of the urban agglomeration on the northern slope of the Tianshan Mountains should fully consider the sensitivity and carrying capacity of the vulnerable ecological environment in this area. Population growth and industrial development in the urban agglomeration should be controlled based on the available water resources and ecological capacity to reduce the pressure on the environment and ensure sustainable development.

Synthesis of Cyclic Carbonate Catalyzed by DBU Derived Basic Ionic Liquids

In this work, 1,8-diazabicyclo[5.4.0]undec-7-ene （DBU）, 1,5-diazabicyclo[4.3.0]-5-nonene （DBN）, and imidazole （MIM）-derived bromide ionic liquids （ILs） were synthesized and used to catalyze the cycloaddition reactions of carbon dioxide （CO_2） with several kinds of epoxides to form cyclic car- bonates. The DBU derived bromide ionic liquid system was found to have the best catalytic activity among all the tested ILs. The influences of reaction conditions （including temperature, pressure and reaction time） on the reaction of CO_2 to propylene oxide （PO） were studied to show the best conditions of 120℃, 1 MPa, 2.5 h catalyzed by 2 mol% DBU-derived bromide ionic liquid, with the conversion of PO and the selectivity of propylene carbonate （PC） reaching 99% and 99%, respectively. Under the optimum reaction conditions, the ionic liquid system could be reused at least five times without decrease in selectivity and conversion. NMR spectroscopy and DFT calculations were used to reveal the hydrogen-bond interaction between ionic liquids and rea- gent, based on which the reaction mechanism was proposed.

Poultry litter biochar application in combination with chemical fertilizer and Azolla green manure improves rice grain yield and nitrogen use efficiency in paddy soil

Poultry litter biochar is known to improve crop productivity.However,its beneficial interactions with chemical fertilizer and/or organic manure on rice yield and nitrogen(N)use efficiency(NUE)are not well studied.The objective of this study was to co-apply poultry litter biochar(hereinafter biochar)and chemical fertilizer and/or Azolla as organic manure(herein N fertilizer sources)to improve the productivity of rice and NUE.Eight treatments-no amendments(control),chemical fertilizer(NPK),Azolla as green manure(Azolla),and NPK+Azolla without and with biochar amendment-were evalu-ated in a pot trial.Selected rice plant growth components,yield,and NUE were determined.Compared to the treatments without biochar,co-application of biochar and N fertilizer sources significantly improved grain N uptake by 23.9%and NUE by 34.3-246.9%.These treatments also significantly improved rice growth components(5.6-18.2%)and grain yield(32.4%).Significant changes in soil properties including increases in pH,electrical conductivity(EC),total N,organic car-bon,and available phosphorus were observed following biochar application.Except for the soil pH and EC parameters,no significant synergistic interactions between biochar and N fertilizer sources were observed for any parameters in the present study.Notably,compared to other treatments,the co-application of biochar and Azolla offers a feasible approach to improve rice productivity and NUE and reduce chemical fertilizer use,thereby reducing agricultural pollution and production costs.