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.     

硅烷处理N2O氧化苯生产苯酚催化剂抑制结碳失活研究

The main cause to the deactivation of ZSM-5 catalyst, used for oxidation of benzene to phenol (BTOP) by nitrous oxide, is that the carbon deposition on the catalyst surface blocks the mouth of pores of the catalyst.In the experiments, ZSM-5 catalyst was modified by chemical surface deposition of silicon, and then the effect of modification condition on the catalyst activation was studied. The catalyst samples were characterized by XRF,EPS, XRD, TEM, N2 adsorption at low temperature, pyridine adsorption-infrared technique and etc. All the above results show that the uniform SiO2 membrane can be formed on ZSM-5 crystal surface. The SiO2 membrane covers the acid centers on ZSM-5 surface to inhibit surface coking, to avoid or decrease the possibility of ZSM-5 pore blockage so that the catalyst activity and stability can be improved efficiently. The optimum siliconiting conditions determined by the experiments are as follows: 4% load of silanizing agent, volume (ml)/mass (g) ratio of hexane/ZSM-5=15/1, and 16 h of modification time. Compared with the samples without siliconiting treatment,the samples treated under the above optimum condition can increase the productivity of phenol by 14% for 3 h reaction time and by 41% for 6 h reaction time respectively.     

Ni-Na/Zr02-Mn02-Zn0催化合成甲基异丙基酮和二乙基酮（英文）

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.     

载体氧化铝的粒径对对硝基苯酚加氢催化剂Ni/Al2O3的影响

The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/Al2O3 catalyst on alumina support with different particle size. It is found that support particle size has significant influences on physiochemical properties and catalytic activity of the resulting Ni/Al2O3 catalyst, but little influence on the selec-tivity. At a comparable amount of Ni loading, the catalytic activity of Ni/Al2O3 prepared with alumina support of smaller particle size is lower. The reduction behavior of the catalyst is a key factor in determining the catalytic activity of Ni/Al2O3 catalyst. The supported nickel catalyst 10.3Ni/Al2O3-3 improves the life span of the membrane by reducing fouling on the membrane surface compared to nano-sized nickel.     

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.     

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.     

非均相羰基氧化一步合成碳酸二苯酯的研究(Ⅴ)筛选催化剂及优化合成条件

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the     

SO_3H-功能化离子液体催化4,4'-MDC合成反应

The synthesis of methylene diphenyl dimethylcarbamate (4,4′-MDC) from methyl N-phenyl carbonate (MPC) and formaldehyde (HCHO) was conducted in the presence of sulfonic acid-functionalized ionic liquids (ILs) as dual solvent-catalyst. The influences of the kind of anion in the ionic liquids, reaction conditions and the recycle of the ionic liquid on 4,4′-MDC synthesis reaction were investigated. In addition, the acid strength of ILs was determined by the Hammett method with UV-visible spectroscopy, and the acid strength-catalytic activity relationship was correlated. The activity estimation results showed that [HSO3-bmim]CF3SO3 was the optimal dual solvent-catalyst. Under the suitable reaction conditions of 70°C, 40 min, molar ratio of nMPC/nHCHO 10/1 and mass ratio of WILs/WMPC 4.5/1, the yield of 4,4′-MDC based on HCHO was 89.9 % and the selectivity of 4,4′-MDC with respect to MPC was 74.9%. Besides, [HSO3-bmim]CF3SO3 was reused four times after being purified and no significant loss in the catalytic activity was observed.     

采用CO2吸附剂吸附强化的甲烷水蒸汽反应制药厂氢过程特点

The objective of the present study is to characterize the production of hydrogen with a sorptionenhanced steam-methane reaction process using Ca(OH)2 as the CO2 adsorbent. Theoretical equilibrium compositions at different operation conditions were calculated using an iterative method. It was found that with Ca(OH)2 as the CO2 sorbent, the concentration of CO2 adsorption was reduced in the product stream, that gave rise to higher methane conversion and higher H2 concentration. An experimental setup was built to test the theoretical calculation. The effects of sorbents and the particle size of Ca(OH)2 on the concentration of CO2 and H2 were investigated in detail. Results showed that the reactor packed with catalyst and Ca(OH)2 particles produced H2 concentration of 94%. It was nearly 96% of the theoretical equilibrium limit, much higher than H2 equilibrium concentration of 67.5% without CO2 sorption under the same conditions of 500℃, 0.2 MPa pressure and a steam-to-methane ratio 6. In addition, the residual mole fraction of CO2 was less than 0.001.     

MoVPO型催化剂上氨氧化合成2-氰基吡嗪

The mechanism of 2-cyanopyrazine prepared from 2-methylpyrazine （2-MP） by catalytic ammoxidation has been explained by the theory of appropriate structure of group. A new catalyst of MoVPO was developed. The effects of catalyst promoter phosphorus and supports were investigated. The catalyst containing P, V and Mo in molar ratio of 1.4 ： 1 ： 0.02 and supported on activated alumina and prepared by impregnation method exhibits good activity and selectivity. Reaction factors such as reaction temperature, space velocity, feed composition and service life of catalyst were investigated. Optimum reaction conditions （the volume space velocity of 0.2h-1, the reaction temperature of 380 ~C and molar ratio of 1 ： 7.8 ： 8 ： 8 for 2-MP, water, oxygen and ammonia） were obtained. Selectivity of 93% and yield of 86% could be achieved under these conditions.     

生产乙炔对电石的要求及乙炔清净

目前国内外乙炔大部分仍是由电石制得。然而由于工业电石除CaC2 外还含有很多杂质 ,所以生产乙炔不仅要求电石的纯度、粒度 ,还要求水温。一般电石的块度采用 8～ 2 5mm ,发生器温度控制在 85± 5℃ ,乙炔气体中含H2 S、H3 P、NH3 等气体会使氯乙烯合成氯化催化剂活性下降。因此 ,必须对乙炔气体进行清洁。采用次氯酸钠液体的氧化性将乙炔中的杂质氧化成酸性物质而除去。     

Al2O3-SiO2-ZrO2-TiO2陶瓷复合膜的烧成及表征

将制备好的Al2O3-SiO2-ZrO2-TiO2复合溶胶在担载体上涂膜、干燥、烧成，制成了有担载体的复合膜。应用SEM，XRD等测试手段对Al2O3-SiO2-ZrO2-TiO2复合膜的结构、表面形貌和孔径进行了表征，并研究了溶胶性能和烧成制度对膜性能的影响。进行了对污水处理实验，并取得了很好的效果。     

Al2O3-SiO2-ZrO2-TiO2复合溶胶的制备与研究

以硝酸铝、正硅酸乙酯、氧氯化锆、钛酸丁酯为前驱体,水和无水乙醇为溶剂,用溶胶-凝胶法制备适合涂膜的复合溶胶.     

TiO2／SiO2复合物与H2O2对有机染料的协同光催化降解作用研究

采用溶胶凝胶法制锯了SiO2含量较高的TiO2/SiO2复合氧化物,并采用SEM,XRD、FTIR等手段进行了表征。测试结果表明,制备得到的复合物是由TiO2和SiO2纳米颗粒所组成的具有多孔网络结构的聚集体,钛氧基强通过Ti-O-Si键固定于SiO2基体中,TiO2主要以无定型态存在。实验发现,在紫外光作用下,TiO2／SiO2复合物与H2O2协同作用,对有机染料曙红B溶液具有较高的催化降解效率。复合物对曙红B的光催化降解符合一级反应动力学方程。     

SiO_2-TiO_2薄膜的制备及光致超亲水性能研究

为了制备具有良好的光致超亲水性的SiO2-TiO2薄膜,实验用溶胶凝胶法结合超声技术以正硅酸乙酯(TEOS)和钛酸丁酯(TBOT)为前驱体制备SiO2-TiO2溶胶;采用浸渍提拉法在普通载玻片上涂膜;然后分别运用微波炉和马弗炉2种不同的烧结方式进行热处理制得产品。将所得产品分别进行接触角、紫外-可见分光光度计、FT-IR、AFM测试。结果表明:马弗炉烧结得到的SiO2-TiO2薄膜亲水性要好于微波炉烧结,并且在V(TEOS)∶V(TBOT)=0.75∶1时,接触角最小,可达到4.3°,满足防污自清洁的要求;红外谱图说明有Ti—O—Si键的生成,证明SiO2和TiO2之间生成了复合氧化物。     

二氯甲烷和有机氟141b在冰机清洗上的应用

由于冰机油发生变质、发黑、发臭且炭渣类杂质较多，使冰机不能正常运行。为了保障冰机正常运行，采用CH2CI2和141b清洗冰机。冰机房外侧冷媒系统采用CH2CI2清洗；冰机房内油路部分(除压缩机机头外)，采用CH2CI2和热空气相结合的清洗方法；压缩机机头部分用有机氟141b清洗。     

TiO2和ZrO2对MgO-Cr2O3合成耐火材料性能和显微结构的影响

镁铬耐火材料具有耐火度高、高温稳定性好、热膨胀率低、抗冶金渣好的特点,广泛应用在钢铁、水泥和铜工业上。在本研究中,加入TiO2和ZrO2,以伊朗铬矿和活性高的苛性MgO为原料,开发了镁铬合成料。结果发现苛性MgO的活性和添加剂对改善镁铬合成耐火原料的物理性能和显微结构具有重要作用。由于形成的合成尖晶石对致密化特性有影响,阐明了添加TiO2和ZrO2有利于提高晶界活性和最终形成直接结合,从而使合成试样致密化,改善了其高温力学性能和抗侵蚀性。     

Al2O3-SiO2-ZrO2-TiO2溶胶的制备与研究复合

以硝酸铝、正硅酸乙酯、氧氯化锆、钛酸丁酯为前驱体，水和无水乙醇为溶剂，用溶胶-凝胶法制备适合涂膜的复合溶胶。     

CuSO_4-CeO_2/TS催化氧化NO及其抗H_2O和SO_2毒化性能

采用共沉淀法制备了载体TiO2-SiO2(TS),用浸渍法制备了催化剂CuSO4-CeO2/TS,考察了组分配比、焙烧温度等制备条件和反应温度、NO进口浓度、O2含量、空速等操作条件对其催化氧化NO活性的影响及其抗H2O和SO2毒化的能力,对载体和催化剂分别进行了分析.结果表明,在最佳条件下制备的催化剂,在反应温度350℃、进口NO浓度500×10-6(φ)及O2浓度8%(φ)、空速10000h-1条件下,NO转化率可达67.5%,能满足NOx高效吸收的要求.但因NO催化氧化过程的反应温度和O2含量均较高,其抗SO2和H2O毒化能力低于NO催化还原过程.     

溶胶-凝胶法制备不锈钢表面SiO2-ZrO2-Al2O3-Cr2O3涂层的研究

用溶胶-凝胶法在不锈钢表面制备了SiO2-ZrO2-Al2O3-Cr2O3，涂层，并用XRD、SEM等手段对其相结构、界面形貌进行了表征，且完成了900℃高温下的抗氧化性实验及FeCl3腐蚀实验。结果表明：预涂Al2O3-Cr2O3过渡层可使基体与涂层结合较好；涂有薄膜的不锈钢抗氧化性、耐腐蚀性均有显著提高。