三乙胺催化合成2-羟丙基甲醚

以三乙胺为催化剂,环氧丙烷和甲醇为原料合成2 羟丙基甲醚。较适宜的工艺条件为反应初始压力0 1MPa;反应温度:80±5℃,CH3OH∶C3H6O=4∶1(mol);反应时间3h;三乙胺用量为环氧丙烷质量的4%,环氧丙烷的转化率可达95%,2 羟丙基甲醚的选择性可达91%以上。催化剂可回收循环使用。     

Selective oxidation of cyclohexane over TS-2, a titanium silicate molecular sieve

The selective oxidation of cyclohexane to cyclohexanol and cyclohexanone using hydrogen peroxide has been studied over TS-2, a titanium silicate molecular sieve with a MEL structure. The reaction is found to be catalyzed by the Ti present in the framework structure, the activity being proportional to the Ti content.     

Characterization and catalytic properties of titanium silicalite-1 catalyst

Titanium silicalite 1 (TS-1) catalyst was prepared by three different hydrothermal synthesis methods. XRD, elemental analysis, SEM, IR,²⁹Si MAS NMR, UV-vis DRS, physical adsorption of nitrogen, and EXAFS analysis were then performed to evaluate its physical properties. For a test of catalytic activity, liquid phase 2-butanol oxidation and 1-hexene epoxidation using hydrogen peroxide as an oxidant were conducted. The crystal size of the TS-1 catalyst was shown to have a considerable effect on the 1-hexene epoxidation, and smaller crystals resulted in higher activity.     

高选择性合成1-甲氧基-2-丙醇固体催化剂的筛选和催化作用

对碱土金属氧化物和两性氧化物等10种氧化物作为合成1 甲氧基 2 丙醇固体催化剂进行了催化性能筛选。发现在碱土金属氧化物MgO、CaO和BaO中,中强碱MgO具有较高的环氧丙烷(PO)转化率(71 07%)和1 甲氧基 2 丙醇(PPM)选择性(92 53%)。在两性氧化物中,ZnO具有较高的PO转化率(55 26%)和PPM选择性(92 37%)。系统考察了反应温度、催化剂用量、反应时间和原料摩尔配比对MgO、ZnO的催化作用特点的影响,发现MgO在催化性能和1 甲氧基 2 丙醇选择性方面表现出的综合性能优于其他催化剂。     

钛硅分子筛TS-1催化烯烃环氧化反应的研究进展

TS-1催化的烯烃环氧化反应具有条件温和、环境友好、符合绿色化学理念、应用前景广阔等优点.该文首先介绍了不同介质中TS-1催化过氧化氢(H2O2)氧化脂肪烯烃反应的进展,结果表明,在甲醇等质子溶剂中,溶剂可以和Ti—OOH(钛氧活性中心)通过氢键作用形成活性中间体,实现烯烃的环氧化;同时,TS-1的酸中心易引发环氧化物...     

Preliminary study on the TS-1 deactivation during styrene oxidation with H2O2

The deactivation of the TS-1 zeolite during styrene oxidation with H₂O₂ has been investigated by a series of kinetic experiments and further characterisation of the spent catalysts. A decline of the TS-1 activity with time has been observed, especially during the first hours of reaction. TG and TPD–MS analyses of the spent catalysts show that the main products occluded within the zeolite pores are styrene, phenylacetaldehyde and benzaldehyde. The presence of styrene oligomeric compounds has also been detected, although it is postulated they are formed mainly in the solution outside the zeolite pores. Diffusional hindrances due to the high degree of occupancy of the TS-1 pores, as well as, a strong adsorption of styrene, phenylacetaldehyde and benzaldehyde on the Ti sites are proposed as the main reasons for the TS-1 deactivation. These phenomena are enhanced at lower reaction temperatures, which cause a faster initial deactivation. Likewise, longer reaction times favour preferential chemisorption of aldehydes versus styrene.     

卤醇脱卤酶催化合成(R)-1-氯-3-苯氧基-2-丙醇的工艺优化

以卤醇脱卤酶重组湿菌体E. coli BL21（pET28a-HHDH）为催化剂,催化外消旋的1-氯-3-苯氧基-2-丙醇的动力学拆分可以获得光学纯的(R)-1-氯-3-苯氧基-2-丙醇。本文系统地研究了卤醇脱卤酶催化合成光学纯(R)-1-氯-3-苯氧基-2-丙醇的影响因素,对反应pH、反应温度、菌体浓度、亲核试剂 {\mathrm{N}}_{\mathrm{3}}^{-} 浓度和底物浓度进行了探究。结果表明,卤醇脱卤酶催化合成(R)-1-氯-3-苯氧基-2-丙醇的最佳工艺条件为：pH为7.0,反应温度为28℃,菌体浓度为22.5g/L,亲核试剂NaN₃的浓度为50mmol/L,底物外消旋1-氯-3-苯氧基-2-丙醇的浓度为10mmol/L。在此工艺条件下,(R)-1-氯-3-苯氧基-2-丙醇的ee值和收率分别为100%和16.97%。     

(S)-(+)-2-氨基丙醇合成工艺改进

对硼氢化钾还原法制取(S) (+) 2 氨基丙醇(AP)工艺进行了改进,采用氯化四甲基铵与硼氢化钾反应制备硼氢化四甲基铵来提高硼氢离子的还原性,还原L 2 氨基丙酸乙酯盐酸盐制取AP。比较了不同链长的硼氢化季铵盐对还原反应的影响,筛选出最优还原剂硼氢化四甲基铵。考察了物质的量比对反应的影响,获得了最优工艺条件:n(硼氢化四甲基铵)∶n(L 2 氨基丙酸乙酯盐酸盐)=(1 52～1 55)∶1,45℃反应3～4h,AP收率89%。w(C3H9NO)=98 6%(高氯酸滴定法测定)。同原工艺直接使用硼氢化钾还原剂比较,生产1tAP少用硼氢化钾1 1～1 2t。     

Selective catalytic oxidation of aniline to azoxybenzene over titanium silicate molecular sieves

The oxidation of aniline using aqueous H₂O₂ and titanium silicates, TS-1 and TS-2 as catalysts was carried out in a batch reactor in the temperature range 333–353 K. TS-1 catalyzes aniline selectively to azoxybenzene and is superior to TS-2. The influence of different solvents, concentration of H₂O₂ and the catalyst in the reaction mixture on the conversion and product distribution has been studied. Acetonitrile is a suitable solvent in this reaction, while acetone is not. For the TS-1 catalyzed oxidation reaction,t-butyl hydroperoxide is not a suitable oxidant. At optimum conditions, a H₂O₂ efficiency of about 100% for aniline conversion is obtained with a selectivity of 97% to azoxybenzene in the product.     

TS-1合成时晶种与模板剂的协同导向作用

在无机钛硅原料体系合成TS - 1时 ,加入晶种 ,模板剂TPABr (orTPAOH)的用量大量减少甚至可以低于极限用量。实验发现晶种和模板剂具有协同导向作用 ,并对产生这种协同作用进行了讨论。     

超声辐射合成1-甲氧基-4-(2-乙基)己氧基苯

以对甲氧基苯酚和CH2BrCH(CH2CH3)(CH2)3CH3为原料,乙醇钠和乙醇为溶剂,在Ar气保护下,用超声辐射催化合成1-甲氧基-4-(2-乙基)己氧基苯,反应5~6h,收率可达86%~88.5%。反应的适宜条件为:MOPh和CH2BrCH(CH2CH3)(CH2)3CH3物质的量比为1∶1.5,乙醇钠的浓度2.5mol/L(溶剂CH3CH2OH),超声频率40kHz。     

1-[3-（三氟甲基）苯基]-2-丙酮合成的研究

以间-溴三氟甲苯为原料,经格氏反应和氧化反应合成1-[3-（三氟甲基）苯基]-2-丙酮。反应优化条件为：溴化亚铜为催化剂,反应时间3h,反应温度5℃,氧化时n（重铬酸钠）：n（浓硫酸）=1：4。在此优化条件下。总收率82．3％。产物结构经IR和^1H NMR确证。     

3-甲硫基-2-羟基-丙基肼生产中废水处理方法的改进

文章使用电解氯化钠酸性水溶液法处理3-甲硫基-2-羟基-丙基肼生产中甲硫醇污水的工艺,取得了良好的治理效果,去除了污水中甲硫醇一类的恶臭物质,处理后的废水无色无臭。而目前国内生产厂家普遍采用氯氧化法去除工艺生产废水中恶臭的甲硫醇,虽然效果良好,但氯气价昂且有毒,在储存、运输、装卸、及使用过程中风险大,操作不易控制,且可能导致环境的二次污染。而使用电解氯化钠水溶液法改变了目前国内生产厂家氯氧化法处理工艺的一系列弊病,更适于投入工业生产。     

Simultaneous Absorption of Carbon Dioxide and Nitrogen Dioxide into Aqueous 2-amino-2-methy-1-propanol

Carbon dioxide and nitrogen dioxide were simultaneously absorbed into aqueous 2-amino-2-methyl-1-propanol (AMP) in a stirred semi-batch tank with a planar gas-liquid interface within a range of 0–4.0 kmol/m³ of AMP, 0.03–0.3 atm of CO₂, 0.005–0.2 atm of NO₂, and 298–318 K. Absorption data of each gas in the CO₂-AMP and NO₂-AMP systems were obtained to verify their reaction regimes, based on film theory, respectively, which were then used to analyze the simultaneous absorption mechanisms of CO₂ and NO₂ in the CO₂-NO₂-AMP systems. The measured absorption rates of CO₂ and NO₂ were compared to those formulated by an approximate solution of the mass balances with simultaneous reactions.     

Mn含量对Cu-Mn-Al催化丙二醇单甲醚脱氢的影响

以硝酸铜、硝酸锰、硝酸铝和碳酸钠为原料,通过共沉淀法制备了不同Mn含量的Cu-Mn-Al催化剂。采用BET,XRD,SEM,TEM,H2-TPR和NH3-TPD等对催化剂进行了表征,在固定床反应器上考察了催化剂对丙二醇单甲醚直接脱氢制备甲氧基丙酮反应活性的影响。结果表明:Mn含量对Cu-Mn-Al催化剂理化性质有较大影响。适量添加Mn能够促进Cu的分散,改变催化剂还原性能,降低催化剂表面酸性。当n(Cu):n(Mn):n(Al)=2.0:3.5:1.0时,Cu-Mn-Al催化剂表面酸量低,具有较低还原温度。在反应温度260℃、常压、进料组成为含5%(质量分数)水的丙二醇单甲醚溶液、液时空速为2.5h-1的条件下,该催化剂上丙二醇单甲醚转化率可达61.57%,甲氧基丙酮选择性可达96.83%,且副产物丙酮选择性低,为1.20%。     

Absorption of carbon dioxide into aqueous blends of 2-amino-2-methyl-1-propanol and diethanolamine

This work presents an experimental and theoretical investigation of CO₂ absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and diethanolamine (DEA). The CO₂ absorption into the amine blends is described by a combined mass transfer-reaction kinetics-equilibrium model, developed according to Higbie's penetration theory. The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (AMP+DEA+H₂O). The good agreement between the model predicted rates and enhancement factors and the experimental results indicate that the combined mass transfer-reaction kinetics-equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer for the aqueous amine blends AMP/DEA.     

Liquid heat capacity of aqueous sulfolane + 2-amino-2-methyl-1-propanol solutions

Heat capacities of aqueous solutions of sulfolane with 2-amino-2-methyl-1-propanol (AMP) were measured over the temperature range from 303.15 to 353.15 K with a differential scanning calorimeter. Twelve solutions of sulfolane + AMP + water that cover the mole fractions of water from 0.6 to 0.8 were studied. The liquid heat capacities of sulfolane alone and of binary mixtures such as sulfolane + water and sulfolane + AMP were also studied. The heat capacities of sulfolane and sulfolane + water were found to be in good agreement with those values reported in the literature. A Redlich-Kister type equation was applied to represent the composition dependence of the heat capacities of binary and ternary systems. For 132 data points of sulfolane + AMP + water, the fitted results of heat capacity calculations (overall average absolute percentage deviation (AAD%)) were 0.3 and 7.7% for the molar heat capacity and the excess molar heat capacity, respectively. The heat capacities of aqueous mixtures of sulfolane with AMP presented in this study can be used to estimate the head load of absorbents in acid gas capture process when using sulfolane + AMP + water as the absorbent.     

1-甲氧基-9,10-二苯基蒽的制备及在农业上的应用

以蒽醌、溴苯等为主要起始原料,通过蒽的1位及9、10位取代,合成了1-甲氧基-9,10-二苯基蒽(MDPA)。改进和优化了各步合成工艺条件:在汞盐催化下,当反应温度为130℃,发烟硫酸浓度为20%~25%,反应时间为1.5 h时,中间体蒽醌-1-硫酸钾收率为53.7%;采用苯基锂与1-甲氧基蒽醌加成后,直接用SnC l2的乙酸水溶液还原,产品收率为68.9%。测试了MDPA在PE农膜中的转光性质。结果表明,将MDPA掺入PE树脂中而形成的蓝光膜能在波长438 nm处光致发光,该波长与植物光合作用所需的蓝光区相吻合;与普通农膜相比,蓝光膜可促进作物生长,使白菜、茼蒿、莴笋等蔬菜产量增加20%左右。     

Absorption of carbon dioxide by the absorbent composed of piperazine and 2-amino-2-methyl-1-propanol in PVDF membrane contactor

This paper tests the performance of microporous polyvinylidinefluoride (PVDF) hollow fiber in a gas absorption membrane process (GAM) using the aqueous solutions of piperazine (PZ) and 2-amino-2-methyl-1-propanol (AMP). Experiments were conducted at various gas flow rates, liquid flow rates and absorbent concentrations. Experimental results showed that wetting ratio was about 0.036% when used with the aqueous alkanolamine solutions, while that was 0.39% with aqueous piperazine solutions. The CO₂ absorption rates increased with increasing both liquid and gas flow rates at N_Re < 20. The increase of the PZ concentration showed an increase of absorption rate of CO₂. The CO₂ absorption rate was much enhanced by the addition of PZ promoter. The resistance of membrane was predominated as using a low reactivity absorbent and can be neglected as using absorbent of AMP aqueous solution. The resistance of gas-film diffusion was dominated as using the mixed absorbents of AMP and PZ. An increase of PZ concentration, the resistance of liquid-film diffusion decreased but resistance of gas-film increased. Overall, GAM systems were shown to be an effective technology for absorbing CO₂ from simulated flue gas streams, but the viscosity and solvent-membrane relationship were critical factors that can significantly affect system performance.     

TS-1分子筛在过氧化氢氧化苯制苯酚反应中的催化性能研究

以TS-1分子筛为催化剂,在淤浆反应器中对过氧化氢氧化苯制苯酚反应的催化性能进行了研究,考察了不同溶剂、过氧化氢进料方式、原料配比和反应条件等对催化性能的影响,优化了反应工艺条件,苯的转化率约达12.5%,苯酚的选择性约达92%,为进一步开展研究奠定了基础。