Dehydrogenative Cracking of n-Butane over Modified HZSM-5 Catalysts

Dehydrogenative cracking reaction of n-butane was studied using HZSM-5 catalyst modified with various metal oxides. Alkaline earth (magnesium), transition metal (cobalt) and rare earth (lanthanum) elements are used for the modification. The selectivity of the products was studied at low conversion (20%). Methane, ethane, ethylene, propylene, butenes and butadiene were the main products. With the use of the cobalt- or magnesium-containing HZSM-5, dehydrogenative cracking was observed and the selectivity of ethylene was much larger than that of ethane. On the other hand, the selectivity of ethylene and ethane were almost the same in the reaction using the lanthanum-containing HZSM-5. It is considered that the cobalt- and magnesium-loaded sites on HZSM-5 played an important role in the dehydrogenative cracking.     

金属负载HZSM-5催化剂上乙烯芳构化反应研究

报道了15种负载不同金属的HZSM-5催化剂对乙烯芳构化的催化效果,以Ga(Zn)/HZSM-5催化剂为例,研究了载体酸性、金属含量、反应温度等因素对催化剂催化性能的影响。并对金属负载的HZSM-5催化剂在乙烯芳构化反应中的作用进行了深入研究讨论。     

An Improved Catalytic Cracking of n-hexane via Methanol Coupling Reaction Over HZSM-5 Zeolite Catalysts

The coupling transformation of n-hexane and methanol over HZSM-5 has been investigated with a pulse-reaction system. In the temperature range of 400–500 °C, kinetic data was collected and reaction order was determined. Compared with the pure n-hexane cracking, the increased rate constant and the lowered apparent activation energy clearly demonstrate an improvement of n-hexane activation using methanol as co-reactant and an increased contribution of faster bimolecular mechanism to the n-hexane transformation due to methanol introduction. Similarly, the results of coupling transformation performed over HZSM-5 with different Al content further confirm the transition between reaction mechanisms of n-hexane on account of the introduction of methanol. Moreover, the further investigation suggests that the enhancement of n-hexane activation and the change of reaction mechanism are attributed to the presence of intermediate species evolved from methanol. Thus, a proposed reaction pathway of n-hexane activation with methanol as co-reactant was put forward.     

磷镍复合改性HZSM-5催化乙醇脱水制乙烯

在离子交换法制备的Ni改性HZSM-5的基础上,采用等体积浸渍法引入不同含量的H3PO4改性,制备了磷镍复合改性的HZSM-5并用于乙醇脱水制乙烯。采用XRD、N2吸附脱附、PyTPD、27Al MAS NMR等表征手段考察了改性对分子筛的影响。结果显示:P添加后促进了骨架铝的脱离,导致强酸量进一步减少,提高了催化剂的使用寿命。活性评价结果表明,以8%磷酸改性的催化剂催化效果最好。然后考察了反应条件对其催化乙醇脱水制乙烯的影响,得到最适宜反应条件为温度260℃、质量空速1.5 h-1、进料乙醇体积分数为50%。在此条件下进行了稳定性测试,50 h内乙醇转化率大于97%,乙烯选择性高于98%,和仅用镍改性相比稳定性显著提高。     

Dynamic Chemical Counting of Active Centers of Molybdena–Alumina Metathesis Catalysts

A dynamic method of chemical counting of active centers of alkene metathesis is proposed and applied to study MoO₃/Al₂O₃ and MoO₃/Al₂O₃-SnMe₄ systems. For the MoO₃/Al₂O₃ catalyst, the estimated number of the active sites is less than 1% of the total number of the Mo atoms. MoO₃/Al₂O₃-SnMe₄ catalysts have a larger percentage of active centers, compared with the system not treated with SnMe₄. This increase of the active sites number approximately corresponds to improvement of the metathesis activity of the MoO₃/Al₂O₃-SnMe₄ catalyst.     

Study of W/HZSM-5-Based Catalysts for Dehydro-aromatization of CH4 in Absence of O2. I. Performance of Catalysts

With incorporation of Zn (or Mn, La, Zr ) into the W/HZSM-5 catalyst, highly active and heat-resisting W/HZSM-5-based catalysts were developed and studied. Under reaction conditions of 0.1 MPa, 1073 K, GHSV of feed-gas CH₄+10% Ar at 960 h^–1, the conversion of methane reached 18–23% in the first 2 h of reaction, and the corresponding selectivity to benzene, naphthalene, ethylene and coke was 56–48, 18, 5 and 22%, respectively. Addition of a small amount of CO₂ (2%) to the feed-gas was found to significantly enhance the conversion of methane and the selectivity of benzene, and to improve the performance of coke-resistance of the W/HZSM-5-based catalysts. Heavy deposition of carbon on the surface of the functioning catalyst was the main reason leading to deactivation of the catalyst. Reoxidation by air may regenerate the deactivated catalyst effectively. In comparison with the Mo/HZSM-5 catalyst, the promoted W/HZSM-5-based catalyst can operate under reaction temperature of 1073 K, and gain a methane conversion approximately two times as high as that of the Mo/HZSM-5 catalyst operating at 973 K. It can also operate at 973 K and have about the same methane conversion as that of the Mo/HZSM-5 catalyst at the same reaction temperature. Its main advantage is its heat-resistant performance; the high reaction temperature did not lead to loss of W component by sublimation.     

Study of W/HZSM-5-Based Catalysts for Dehydro-aromatization of CH4 in Absence of O2. II. Action of Promoters Zn and Li

By correlating the results of the NH₃-TPD characteristic study and the catalyst activity assay of the W/HZSM-5-based catalysts, we confirmed that the intensity and concentration of the surface B-acid sites have pronounced effects on the catalyst performance for dehydro-aromatization of methane (DHAM). It was found experimentally that, by addition of a proper amount of Mg²⁺, the strong B-acid sites at the catalyst surface could be effectively eliminated, whereas the addition of a proper amount of Zn²⁺ or Li⁺ resulted not only in eliminating most of the strong surface B-acid sites but also in generating a kind of new medium-strong acid sites, mostly B-acid sites, simultaneously. The latter could serve as the catalytically active sites for dehydro-aromatization of methane; on such medium-strong surface B-acid sites, the formation of coke would be also alleviated to a greater extent. By simultaneous addition of Mg²⁺ and Zn²⁺, optimized adjustment in surface acidity of the catalyst could be realized. On the other hand, the doping of the Zn²⁺ or Li⁺ component to the tungsten oxide matrix would facilitate inhibiting aggregation of the W-containing active species and improving dispersion of the W component at the surface of the catalyst, thus leading to a pronounced decrease in the reduction temperature for the hard-to-be-reduced W⁶⁺ species and an increase in quantity of the reducible W⁶⁺ species at the reaction temperature for DHAM, as has been evidenced by the results of a H₂-TPR study on the reducibility of the Zn²⁺ (or La³⁺, Li⁺, Mn²⁺)-promoted W/HZSM-5 system. The above two roles that Zn²⁺ and Li⁺ as promoters played both contributed to the persistence of high methane conversion and benzene selectivity, and the alleviation of coke deposition, as well as the prolongation of the catalyst lifetime.     

Correlation between acidic properties of nickel sulfate supported on TiO2-ZrO2 and catalytic activity for ethylene dimerization

A series of catalysts, NiSO₄/TiO₂-ZrO₂, for ethylene dimerization was prepared by the impregnation method using an aqueous solution of nickel sulfate. For NiSO₄/TiO₂ -ZrO₂ sample, no diffraction line of nickel sulfate was observed up to 30 wt%, indicating good dispersion of nickel sulfate on the surface of TiO₂-ZrO₂. The addition of nickel sulfate to TiO₂-ZrO₂ shifted the phase transition of TiZrO₄ from amorphous to orthorhombic to a higher temperature because of the interaction between nickel sulfate and TiO₂-ZrO₂. The number of acid sites of NiSO₄/TiO₂-ZrO₂ increased in proportion to the nickel sulfate content up to 20 wt% of NiSO₄. Nickel sulfate supported on TiO₂-ZrO₂ was found to be very active even at room temperature, giving a maximum in both activity and acidity when the catalyst containing 20% NiSO₄ was calcined and evacuated at 500°C The asymmetric stretching frequency of the S=O bonds for NiSO₄/TiO₂-ZrO₂ samples was related to the acidic properties and catalytic activity. That is, the higher the frequency, the higher both the number of acid sites and the catalytic activity for ethylene dimerization.