络合沉淀法制备Al2 O3 -ZrO2复合粉

以工业纯ZrOCl2.8H2O,分析纯AlCl3.6H2O,分析纯Y2O3等为原料,将AlCl3.6H2O和ZrOCl2.8H2O分别配制成0.5mol.L-1和1mol.L-1的水溶液,按ZrO2和Al2O3的质量比为44:56配成混合溶液;将混合溶液与用盐酸溶解稳定剂Y2O3后配制成一定浓度的YCl3溶液混合并搅拌均匀,再向均匀溶液中加入2%PEG分散剂制成母液;然后向母液中滴加过量的0.5mol.L-1的草酸溶液形成络合母液,滴加氨水调节其pH值。研究了pH值在4~10之间,直接沉淀法和络合沉淀法对Al2O3-ZrO2复合粉前驱体溶胶团聚及粉体粒度分布的影响。利用透射电镜(TEM)和激光粒度分析仪对溶胶和复合粉粒度组成进行了分析。结果表明:采用草酸为络合剂,氨水为沉淀剂的络合沉淀法可以明显的改善Al2O3-ZrO2复合粉前驱体溶胶的团聚,干燥后得到的复合粉体没有明显的硬团聚;反应溶液的pH值为9时效果最佳;络合沉淀法制备的Al2O3-ZrO2复合粉的平均粒径为3.704μm,直接法制得的粉体的平均粒径为7.052μm。     

攀钢密地选钛厂4万吨微细粒级选钛工程浮选尾矿治理

简要介绍了攀钢密地选钛厂微细粒级 4万 t选钛工程的基本工艺流程 ,较详细地分析了所设计的尾矿处理设备不能达到生产要求的原因 ,并从理论和实践上提出了解决问题的具体措施     

沉淀剂的不同对固体超强酸SO_4~(2-)/TiO_2-NiO性能的影响

通过对固体超强酸的比表面测定,差热分析及催化酯化性能考察, 研究了不同沉淀剂对固体超强酸ＳＯ４２－ ／ＴｉＯ２ － ＮｉＯ 催化剂在物性和催化性能的影响,认为尿素作沉淀剂可增强ＴｉＯ２ 与ＮｉＯ之间相互作用,抑制Ｎｉ 离子和ＳＯ４２ － 生成盐,氨水作为沉淀剂则不能促使ＴｉＯ２ 与ＮｉＯ 的强相互作用,用尿素作沉淀剂得到的催化剂比表面、稳定性要比氨水作沉淀剂时的比表面大,稳定性要高。     

原油正构烷烃沥青质聚沉机理研究及沉淀量测定

用IP 143标准方法测定了我国孤岛和草桥原油正构烷沥青质沉淀量。结果表明两种原油的沥青质沉淀量均随沉淀剂分子量增大而减小、随剂油比增大而增大。在原油沥青质 胶质胶束模型的基础上提出了一种新的沥青质聚沉机理 ,该机理的基本假设是原油中沥青质分子以胶束形式存在 ,其中胶核为沥青质缔合物 ,溶剂化层为胶质和溶剂分子。通过分析沉淀剂性质、剂油比、体系温度和压力等对沥青质 胶质胶束稳定性的影响得出了沥青质沉淀点、沉淀量、沉淀物平均分子量以及沉淀物平均颗粒大小随沉淀剂性质和剂油比等因素变化的规律。经比较说明 ,这些规律与本文及文献实验结果相符     

Water-gas shift reaction over CuO/CeO2 catalysts: Effect of CeO2 supports previously prepared by precipitation with different precipitants

A series of CeO₂ supports were firstly prepared by precipitation method with NH₃⋅H₂O (NH), (NH₄)₂CO₃ (NC) and K₂CO₃ (KC) as precipitant, respectively, and then CuO/CeO₂ catalysts were fabricated by depositing CuO on the as-obtained CeO₂ supports by deposition-precipitation method. The effect of CeO₂ supports prepared from different precipitants on the catalytic performance, physical and chemical properties of CuO/CeO₂ catalysts was investigated with the aid of XRD, N₂-physisorption, N₂O chemisorption, FT-IR, TG, H₂-TPR, CO₂-TPD and cyclic voltammetry (CV) characterizations. The CuO/CeO₂ catalysts were examined with respect to their catalytic performance for the water-gas shift reaction, and their catalytic activities and stabilities are ranked as: CuO/CeO₂-NH > CuO/CeO₂-NC > CuO/CeO₂-KC. Correlating to the characteristic results, it is found that the CeO₂ support prepared by precipitation with NH₃⋅H₂O as precipitant (i.e., CeO₂-NH-300) has the best thermal stability and least surface “carbonate-like” species, which make the corresponding CuO/CeO₂-NH catalyst presents the highest Cu-dispersion, the highest microstrain (i.e., the highest surface energy) of CuO, the strongest reducibility and the weakest basicity. While, the precipitants that contain CO₃^2- (e.g. (NH₄)₂CO₃ and K₂CO₃) result in more surface “carbonate-like” species of CeO₂ supports and CuO/CeO₂ catalysts. As a result, CuO/CeO₂-NC and CuO/CeO₂-KC catalysts present poor catalytic performance.     

The influence of different precipitants on the copper-based catalysts for hydrogenation of ethyl acetate to ethanol

Ethanol fuel has become a hot topic in the economic, political, environmental, and scientific areas. In this work, a new way for the synthesis of ethanol by hydrogenolysis of ethyl acetate is introduced and the impact of different precipitants on the ethyl acetate hydrogenolysis catalysts is systematically investigated by several considerations, including dispersion effects, the texture of the catalysts, and the copper phases in the surface layer of the reduced catalysts, etc. These precursors and catalysts are characterized by inductively coupled plasma-atomic emission spectroscopy, N₂-adsoption, X-ray diffraction, transmission electronic microscope, H₂ temperature-programmed reduction and X-ray photoelectron spectroscopy. It is confirmed that the choice of precipitant is of great importance. The samples are classified into two types, depending on the anion of precipitant. Except the catalyst prepared by (NH₄)₂CO₃, in which low copper loading is observed, type B catalysts (–CO₃²⁻) possess smaller copper particles and larger BET surface than that of type A catalysts (–OH), while the difference of catalysts in the same type is not obvious. Moreover, the coexistence of Cu⁺ and Cu⁰ is only detected in reduced type B catalysts. In general, ethyl acetate hydrogenolysis activity varies considerably with the precipitant, in the following order: Na₂CO₃ ≥ NaHCO₃ > NaOH ≥ KOH > (NH₄)₂CO₃.     

Study on α-alumina precursors prepared using different ammonium salt precipitants

Nano-sized α-Al₂O₃ platelets have been produced by the precipitation method employing the starting material of Al(NO₃)₃·9H₂O and ammonium salt precipitants, such as the NH₄OH, (NH₄)₂CO₃ and NH₄HCO₃. The effects of chemical composition of ammonium salt precipitants and aging time of precipitated product on the formation of precursor and final product of α-Al₂O₃ particles were studied. The precursors with different crystal structures were formed depending on the chemical composition of precipitant and the agglomeration of final α-Al₂O₃ particles was found to be greatly affected by the precipitant. The aging time of precipitated precursor also influenced the agglomeration of final α-alumina particles.     

Effect of precipitants during the preparation of Cu-ZnO-Al2O3/Zr-ferrierite catalyst on the DME synthesis from syngas

The synthesis of dimethyl ether (DME) from biomass-derived model synthesis gas has been investigated on Cu-ZnO-Al₂O₃/Zr-ferrierite bifunctional catalysts. The catalysts are prepared by co-precipitation–impregnation method using Na₂CO₃, K₂CO₃ and (NH₄)₂CO₃ as the precipitants. The catalytic activity tests reveal that the best yield of DME can be obtained on the catalyst precipitated by using (NH₄)₂CO₃. Detailed characterization studies conducted on the catalysts to measure their properties such as surface area, acidity by temperature-programmed desorption of ammonia (NH₃-TPD), reducibility of Cu oxide by temperature-programmed reduction (TPR), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and copper surface area and particle size measurements by N₂O titration method. Increasing the number of moderate acidic sites and facilitation of easily reducible copper species with small particle size are found to be the prime reasons for the superior functionality of the (NH₄)₂CO₃ precipitated catalyst. The usage of (NH₄)₂CO₃ also leaves no residual ions, whereas the presence of residual K⁺ and Na⁺ ions in the case of K₂CO₃ and Na₂CO₃ precipitated catalysts leads to lower activity and selectivity.     

Precipitation ability to U(IV) and stability of 1,3-dimethyl-2-imidazolidone for selective precipitation of U(VI) in nitric acid media

As a part of the investigation of precipitants with selectivity to U(VI) in nitric acid media, a preliminary study on the precipitation ability of 1,3-dimethyl-2-imidazolidone (DMI) to U(IV), a simulant of Pu(IV), was performed. DMI is a ring compound like N-n-butyl-2-pyrrolidone (NBP) which is one of the pyrrolidone derivatives (NRPs) and a promising precipitant for U(VI). While DMI is known to precipitate U(VI) from 3 mol dm⁻³ (=M) HNO₃, no precipitate was observed in the solution containing 0.15 M U(IV) and 3 M HNO₃ by adding DMI at the ratio of [DMI]/[U(IV)] = 5. This indicates that the selectivity of DMI to U(VI) than U(IV) is much higher compared with that of NBP.On the other hand, the stability of DMI under γ-ray irradiation and heating in HNO₃ solutions (≤4 M) was also examined to evaluate the applicability of DMI to the practical process, because gradual acid hydrolysis of DMI is inevitable due to the nature of the chemical structure. As a result, it was found that the stability is strongly affected by the concentration of HNO₃. Namely, very few DMI in 2 M HNO₃ underwent the ring-opening by the irradiation up to 220 kGy and heating at 50 °C up to 5 h, respectively, indicating that these treated samples may still hold the precipitation ability to U(VI). On the contrary, the cleavage of the ring of DMI in 4 M HNO₃ was found to proceed easily. From the above results, it was concluded that DMI may be a candidate as a selective precipitant for U(VI) in HNO₃ solutions up to ca. 2 M.     

Design and construct CeO2-ZrO2-Al2O3 materials with controlled structures via co-precipitation method by using different precipitants

To design and construct CeO₂-ZrO₂-Al₂O₃(CZA) materials with controlled structure via co-precipitation method, the NH₃·H₂O and (NH₄)₂CO₃ were worked as precipitants, respectively. And the influence of the precipitants on nucleation, growth and thermal behavior of the CZA materials were investigated. Results of H₂-TPR, XRD, XPS, UV–Vis, TEM and HAADF-TEM elemental mapping show that using NH₃·H₂O as precipitant facilities to form homogeneous CeO₂-ZrO₂(CZ) solid solution with better solid solubility but the resulting CZA materials sinters severely due to the “mechanical-like” mixing mode between Ce, Zr and Al. On the contrary, the CZA materials precipitated by (NH₄)₂CO₃ shows a better textural and structural stability due to the uniform distribution of Ce, Zr and Al. However, the H₂ consumption of CZA precipitated by (NH₄)₂CO₃ is limited by the inferior Ce and Zr solid solubility due to stronger interactions among the components. It is also found that the surface and subsurface reduction of CZA materials are controlled by specific surface area and crystal size, while the bulk reduction of CZA materials correlates with solid solubility of Ce and Zr, crystal size and surface Ce/Zr ratio simultaneously.