固体超强酸催化剂SO2-4/TiO2-MoO3的制备及其催化合成缩醛（酮）

SO4^2-/TiO2-MoO3, a novel solid superacid, has been prepared and its catalytic activity at different synthetic conditions was examined with esterification of n-butanoic acid and n-butyl alcohol as probing reaction.The optimum conditions were also found, that is, the mass ratio of MoO3 used in the compound is 25%, the calcination temperature 450℃, and the soaked consistency of H2SO4 is 0.5mol.L^-1. Then it was applied in the catalytic synthesis of six similar important ketals and acetals as catalyst and revealed high catalytic activity. Under the condition that the molar ratio of aldehyde/ketone to glycol was 1:1.5, the mass ratio of the catalyst to the reactants was 0.5% and the reaction time 1.0 h, the yield of ketals and acetals reached up to 63.2%. The catalyst can be easily recovered and reused.     

纳米N掺杂TiO2的制备及可见光催化活性研究

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.     

Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl?anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.     

单过氧丁二酸氧化环己酮合成ε-己内酯(英文)

In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid（PSA）. Then PSA was applied to synthesis of ε-caprolactone（ε-CL） by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR（infrared spectra） and1HNMR（1H nuclear magnetic resonance）. Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.     

福建无烟煤CO2气化过程纸浆黑液和钙混合物的催化活性

CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressure. When the coal was impregnated with an appropriate quantity of Ca and BL mixture, the catalytic activity of CO2 gasification was enhanced obviously. With a loading of 8%Na-BL＋2%Ca, the carbon conversion of three coal samples tested reaches up to 92.9%-99.3% at 950℃ within 30min. The continuous formation of alkali surface compounds such as （[-COM], [-CO2M]） and the presence of exchanged Ca, such as calcium phenolate and calcium carboxylates （COO）2Ca, contribute to the increase in catalytic efficiency, and using BL＋Ca is more efficient than that adding BL only, The homogeneous model and shrinking-core model were applied to correlate the data of conversion with time and to estimate the reaction rate constants under different temperature. The corresponding reaction activation energy （Ea） and pre-exponential factor of three anthracites were estimated. It is found that Ea is in the range from 73.6 to 121.4kJ·mol^-1 in the case of BL＋Ca, and 74.3 to 104.2kJ·mol^-1 when only BL was used as the catalyst, both of which are much less than that from 143.5 to 181.4kJ·mol^-1 if no catalyst used. It is clearly demonstrated that both of BL＋Ca mixture and BL could be the source of cheap and effective catalyst for coal gasification.     

Performance of Ni/Nano-ZrO2catalysts for CO preferential methanation简

Large surface areas nano-scale zirconia was prepared by the self-assembly route and was employed as support in nickel catalysts for the CO selective methanation. The effects of Ni loading and the catalyst calcination temperature on the performance of the catalyst for CO selective methanation reaction were investigated. The cata- lysts were characterized by Brunauer-Emmett-Teller （BET）, transmission electron microscope （TEM）, X-ray dif- fraction （XRD） and temperature-programmed reduction （TPR）. The results showed that the as-synthesized Ni/nano-ZrO2 catalysts presented high activity for CO methanation due to the interaction between Ni active particle and nano zir- conia support. The selectivity for the CO methanation influenced significantly by the particle size of the active Ni species. The exorbitant calcination resulted in the conglomeration of dispersive Ni particles and led to the decrease of CO methanation selectivity. Among the catalysts studied, the 7.5% （by mass） Ni/ZrO2 catalyst calcinated at 500℃ was the most effective for the CO selective methanation. It can preferentially catalyze the CO methanation with a higher 99% conversion in the CO/CO2 competitive methanation system over the temperature range of 260-280℃, while keeping the CO2 conversion relatively low.     

载体二氧化钛的晶型对对硝基苯酚加氢催化剂Ni/TiO2的影响

The catalytic hydrogenation ofp-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma （ICP）, X-ray powder diffraction （XRD）, transmission electron microscopy （TEM）, X-ray photoelectron spectra （XPS） and temperature-programmed reduction （TPR）. Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2（A） is higher than that of rutile titania supported nickel catalyst Ni/TiO2（R）, possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2（A） is easier than that for Ni/TiO2（R） at similar reaction conditions.     

大庆常压催化裂解动力学研究

Catalytic pyrolysis of Daqing atmospheric residue on catalyst CEP-1 was investigated in a confined fluidized bed reactor. The results show that reaction temperature, the mass ratios of catalyst to oil and steam to oil have significant effects on product distribution and yields of light olefins. The yields of light olefins show the maxima with the increase of reaction temperature, the mass ratios of catalyst to oil and steam to oil, respectively. The optimized operating conditions were determined in the laboratory, and under that condition the yields of ethylene, propylene and total light olefins by mass were 15.9%, 20.7% and 44.3% respectively. The analysis of pyrolysis gas and pyrolysis liquid indicates that CEP-1 has good capacity of converting heavy oils into light olefins, and there is a large amount of aromatics in pyrolysis liquid.     

高岭土微球原位合成SAPO-34分子筛及其在流化床甲醇/二甲醚制烯烃过程中的应用(英文)

SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study, we developed the in situ synthesis technology to prepare SAPO-34 zeolite in kaolin microspheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods (micropore area, X-ray fluorescence and energy dispersive spectroscopy element analysis). Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst, SAPO/kaolin catalyst showed superior catalytic activities, better olefin selectivities (up to 94%, exclusive coke), and very good hydrothermal stability. The in situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO (methanol to olefins/dimethyl ether to olefins) process.     

Chemical dehydration coupling multi-effect evaporation to treat waste sulfuric acid in titanium dioxide production process

In order to concentrate the diluted sulfuric acid from the titanium dioxide(TiO_2) production of sulphate process,a new concentration process was proposed by coupling chemical dehydration and multi-effect evaporation. The ferrous sulfate monohydrate(FeSO_4·H_2O), as the dehydrant, was added to the diluted sulfuric acid to form ferrous sulfate heptahydrate(FeSO_4·7H_2O) according to the H_2SO_4-FeSO_4-H_2O phase diagrams, which partially removes the water. This process was named as Chemical Dehydration Process. The residual water was further removed by two-effect evaporation and finally 70 wt% sulfuric acid was obtained. The FeSO_4·H_2O can be regenerated through drying and dehydration of FeSO_4·7H_2O. The results show that FeSO_4·H_2O is the most suitable dehydrant, the optimal reaction time of chemical dehydration process is 30 min, and low temperature is favorable for the dehydration reaction. 45.17% of the entire removed water can be removed by chemical dehydration from the diluted sulfuric acid. This chemical dehydration process is also energy efficient with 24.76% saving compared with the direct evaporation process. Furthermore, 51.21% of the FeSO_4 dissolved originally in the diluted sulfuric acid are precipitated out during the chemical dehydration, which greatly reduces the solid precipitation and effectively alleviates the scaling in the subsequent multi-effect evaporation process.     

Investigation of N-(Hydroxylethyl)pyrrolidone Dehydration over REO_x-doped Nano-ZrO_2 Catalyst

1 INTRODUCTION Poly-N-vinyl-pyrrolidone (PVP) is a non-ionic water-soluble chemical, which is widely used in many industrial fields such as pharmaceutical, cosmetic, foodstuff, electronics, printing, paper-making, deter- gent and adhesive etc.[1]. Traditional acetylene process is dangerous because of using acetylene under high temperature and pressure[2] Nowadays, it is usually produced by polymerization of N-vinyl-pyrrolidone (NVP), which is produced by cata- lytic dehydration of N-(h…     

REOx和MOX掺杂的ZrO2催化剂催化羟乙基吡咯烷酮脱水反应研究

研究了REOx掺杂量及掺杂方式(共沉淀法和固相分散法)以及MOx的掺杂对ZrO2催化剂在羟乙基吡咯烷酮脱水反应中的催化性能影响,结果表明利用固相分散法合成的掺杂1%REOx的ZrO2催化剂具有优异的催化脱水性能。初步研究显示,该催化剂以单斜相为主,催化NHP脱水转化率达到97.0%,NVP选择性82.3%,总收率79.8%。而MOs(M=Na,K,Ca)使催化剂晶相以四方相为主,对羟乙基吡咯烷酮脱水反应有不利影响。     

γ-丁内酯催化合成聚乙烯吡咯烷酮(PVP)单体的研究

以 γ-丁内酯为原料 ,经过乙醇胺的胺解得到羟乙基吡咯烷酮 (NHP) ,研制筛选出 NHP脱水反应较理想的催化剂 ,其组成为 K1Si50 B0 .4 ,由 NHP的脱水反应合成了 PVP单体。通过实验得到最佳 NHP脱水反应最佳条件为 :催化剂用量 9～ 1 1 m L,反应温度 380～ 390°C,真空度 90～ 95k Pa进料空速 1 0 0～ 1 50 m L/g·h。使 NHP脱水反应转化率达 70 %以上 ,选择性达 90 %以上。     

MaSibLacCed多元氧化物催化NHP脱水反应合成NVP

合成了一系列组成为M_aSi_bLa_cCe_d（M代表碱金属，a=0～1，b=0～50，c=0～1，d=0～1）的多元氧化物催化剂，在常压条件下评价了其对N-羟乙基吡咯烷酮（NHP）脱水反应活性的影响。研究发现，M_aSi_bLa_cCe_d对目标反应的活性随组成而变化，含有稀土的多元氧化物活性较高，双稀土具有相互促进的协同效果。以K₁Si₅₀La_0.1Ce_0.1为催化剂，探讨了反应温度和NHP分压等主要因素对反应的影响，重点研究了低压与N₂稀释至常压反应两种方法的效果。结果显示，采用N2稀释至常压反应的方法在技术上更具优势。     

二次纳米自组装制备纳米氧化锆体相催化剂

以二次纳米自组装法制备纳米氧化铝和纳米氧化锆粉体,采取混捏挤条法和压片法分别制备纳米氧化锆体相催化剂。采用BET、SEM等技术对催化剂进行了表征,考察了2种制备方法对催化剂结构与性质的影响。     

N-乙烯基吡咯烷酮的合成研究进展

N-乙烯基吡咯烷酮(NVP)是一种重要的精细化工产品。简要叙述NVP的国内外市场情况,分析了乙炔法、催化脱水法及吡咯烷酮法等NVP合成技术,对比分析反应历程、催化剂种类、产品的选择性及原料的转化率,提出了国内研究发展的建议。     

Modified iron-molybdate catalysts with various metal oxides by a mechanochemical method: enhanced formaldehyde yield in methanol partial oxidation

A mechanochemical method was employed to prepare modified iron molybdate catalysts with various metal salts as precursors. The physicochemical properties of the iron molybdate catalysts were characterized, and their performances in catalyzing the reaction from methanol to formaldehyde (HCHO) were evaluated. Iron molybdate catalysts doped with Co(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O resulted in high HCHO yields. Compared with a commercial catalyst, the HCHO yields in the reaction with the modified catalyst at an optimal Co/Mo molar ratio reached 97.37%. According to chemical state analysis, the formation of CoO and the efficient decrease in the MoO₃ sublimation rate could be important factors enhancing the HCHO yield in reactions catalyzed with iron molybdate doped with different Co/Mo mole ratios.     

火焰喷涂PA1010/nano-ZrO2复合涂层的非等温结晶动力学

利用火焰喷涂法制备了聚酰胺1010 (PA1010)/纳米氧化锆（nano-ZrO₂）复合涂层。采用示差扫描量热法（DSC）研究其非等温结晶行为,对所得的数据分别用Jeziorny法、Ozawa法和Mo法进行处理。结果表明,用Jeziorny法和Mo法处理非等温结晶过程比较理想,而Ozawa法不适用。用Jeziorny法求出的参数Z_c(结晶速率常数）和n（Avrami指数)均随降温速率的增加而增加;nano-ZrO₂的加入使复合涂层的Z_c和n略大于纯PA1010涂层;并使复合涂层结晶半衰期降低、结晶速率及结晶度增大。表明nano-ZrO₂具有明显的成核剂作用,加快PA1010的结晶速率,提高涂层的结晶度。     

HZSM-5分子筛催化剂上乙醇脱水制乙烯的工艺分析

对商品化的HZSM-5分子筛催化剂的乙醇脱水性能进行了考察,结果表明：使用HZSM-5分子筛催化剂时,随着反应温度的升高,气态产物中正丁烯的含量增加,乙烯的含量下降,说明分子筛的表面酸性过强,不能有效的抑制乙烯的二聚反应,脱水反应条件是：反应温度240~260℃,空速范围0.7~1.0h-1,乙烯的收率在98%以上,适用于低浓度乙醇的脱水反应。