程序升温还原法制备MoP催化剂及加氢脱硫性能

采用共沉淀法将钼酸铵和磷酸氢二铵盐的前驱体,通过程序升温还原法(TPR)制备了Mo P加氢脱硫(HDS)催化剂。以质量分数为0.8%的二苯并噻吩/十氢萘溶液为模型化合物,考察了催化剂的HDS反应性能,并用XRD对催化剂晶相进行了表征。实验证明,TPR还原法制备的Mo P催化剂具有较高的加氢脱硫活性。XRD表征结果表明,制备的Mo P催化剂与标准卡片(PDF 24-0771)具有完全吻合的特征衍射峰。     

氢等离子体法还原Ni(H_2PO_2)_2制备高活性Ni_2P加氢脱硫催化剂

以次磷酸钠和氯化镍为原料,采用氢等离子体还原法(PR)制备了高活性加氢脱硫(HDS)Ni_2P-PR催化剂,以质量分数为0.8%的二苯并噻吩(DBT)/十氢萘溶液为模型化合物,考察了催化剂的加氢脱硫反应性能,并用X射线衍射(XRD)对催化剂晶相进行表征。新制备的催化剂在移入固定床反应器之前用10%H2S/Ar钝化,以保护其结构不被破坏。实验证明,PR还原法制备的Ni_2P-PR催化剂的加氢脱硫活性高于程序升温还原(TPR)法制备的Ni_2P-TPR催化剂。XRD表征结果表明,Ni_2P-PR的粒度较小,活性中心较多,导致其高活性增加。在Ni_2P-PR催化剂上,DBT主要通过直接脱硫(DDS)路径脱硫。     

不同磷源等离子体制备高活性Ni_2P加氢脱硫催化剂

以氯化镍(硝酸镍)和次磷酸铵(磷酸氢二铵)(Ni:P摩尔比为1)为原料,氢等离子体还原法(PR)制备高活性加氢脱硫Ni_2P催化剂,新制备的催化剂在移入固定床反应器之前用质量分数10%H_2S/Ar钝化,以保护其结构不被破坏。以质量分数为0.8%的二苯并噻吩(DBT)/十氢萘溶液为模型化合物,考察了不同磷原催化剂的加氢脱硫(HDS)性能。X射线衍射(XRD)对制备的催化剂晶相进行了表征。实验证明,低价态P源制备的Ni_2P催化剂(N_2P-1-PR)的加氢脱硫(HDS)活性高于高价态P源制备的Ni_2P催化剂(N_2P-2-PR)。XRD表征结果表明,N_2P-1-PR粒度较小,导致其高活性增加。在Ni_2P催化剂上,DBT主要通过直接脱硫路径(DDS)。     

以B_2O_3改性γ-Al_2O_3为载体制备低P/Ni摩尔比磷化镍加氢脱硫催化剂的研究

采用等体积浸渍法在γ-Al_2O_3中引入了B_2O_3,以较低P/Ni摩尔比(1.2)的磷酸盐作前驱体,利用程序升温还原法制备了以Al_2O_3为载体的磷化镍催化剂,并考察了催化剂的加氢脱硫反应性能。结果表明,B_2O_3抑制了Al_2O_3与磷酸盐之间的反应,降低了磷损失。获得Ni_2P所需的最低B_2O_3质量分数在10%～20%之间。当B_2O_3质量分数≤10%时,主要得到Ni_(12)P_5。在γ-Al_2O_3载体中引入B_2O_3显著提高了催化剂的加氢脱硫活性,但B_2O_3质量分数大于10%时催化剂的活性降低。二苯并噻吩在磷化镍催化剂上主要通过直接脱硫路径进行反应,引入B_2O_3提高了磷化镍催化剂酸性和加氢选择性。     

Ni2P催化剂的制备及加氢脱硫性能研究

通过共沉淀并用原位程序升温还原的方法制备了体相Ni2P催化剂,用二苯并噻吩(DBT)作为模型化合物进行加氢脱硫(HDS)活性评价,结果显示Ni2P具有比较低的加氢活性和相对高的脱硫活性,且有很高的稳定性。     

还原气氛及温度对Ni2P催化剂加氢脱硫性能的影响

采用等体积浸渍法制备了Ni_2P加氢脱硫催化剂,在固定床上以二苯并噻吩作为反应探针,研究了加氢脱硫反应。对催化剂进行了XRD,BET表征。实验结果表明,600℃真空碳热还原的Ni_2P催化剂由于具有较大的比表面积,较小的晶粒尺寸而展现了最优异的加氢脱硫性能。真空碳热还原法为制备Ni_2P催化剂提供了新方法。     

溶胶-凝胶法制备MoP/SiO_2催化剂及其加氢脱硫催化活性的研究

以正硅酸乙酯为硅源,以钼酸铵和磷酸二氢铵为钼源和磷源,采用溶胶-凝胶法,经干燥、焙烧处理后,程序升温还原制备得到二氧化硅负载磷化钼(MOP)催化剂,并以二苯并噻吩为模型化合物,对催化剂的加氢脱硫活性进行初步评价,考察了负载量、反应压力、反应温度等因素对催化活性的影响.结果表明,溶胶-凝胶法制备负载催化剂最佳磷化钼负载量为20%(质量分数);升高反应压力和温度均有利于提高二苯并噻吩的转化率,但降低了产物中联苯的含量.     

碳化钼基合金催化剂的催化加氢脱硫研究

本文研究了利用通过程序升温研制的不同碳化钼基合金催化剂,在以二苯并噻吩为模型化合物,用微库仑硫分析仪测定硫含量,评价比较了碳化钼基合金催化剂的加氢脱硫性能,并且研究了碳化钼基合金催化剂的再生性能。     

氢等离子体法制备Ni_2P催化剂及加氢脱硫性能

采用氢等离子体还原法制备了体相Ni2P,新鲜制备的Ni2P在移入固定床反应器之前用体积分数10%H2S/Ar钝化,以保护其结构不被破坏。实验证明:氢等离子体(PR)还原法制备的Ni2P催化剂的加氢脱硫活性高于程序升温还原(TPR)法制备的催化剂。XRD表征结果表明,氢等离子体还原法制备的Ni2P的粒度较小,活性中心较多,其高活性可归于其活性中心数量的增加。氢等离子体还原法制备的Ni2P具有良好的反应稳定性。     

La-Ni2P/SBA-15/堇青石整体式催化剂及加氢脱硫性能

以介孔分子筛SBA-15为载体,制备一系列不同La含量的La-Ni₂P/SBA-15催化剂前驱体,将La-Ni₂P/SBA-15前驱体涂覆在预处理的整体式载体堇青石上,在H2气氛程序升温还原,制备不同La含量的La-Ni2P/SBA-15/堇青石整体式催化剂。对合成的催化剂进行X射线衍射和N2吸附-脱附结构表征,并评价对二苯并噻吩的加氢脱硫活性。结果表明,Ni₂P存在于所有的La-Ni2P/SBA-15/堇青石整体式催化剂中,且随着La含量的增加,La-Ni2P/SBA-15/堇青石整体式催化剂的比表面积和孔体积均有一定程度的提高,催化活性也提高。对于Ni2P/SBA-15/堇青石整体式催化剂,在300 ℃和380 ℃时,二苯并噻吩加氢脱硫转化率仅为27.2%和91.3%;而1.5%La-Ni₂P/SBA-15/堇青石催化剂在300 ℃和380 ℃时,二苯并噻吩转化率分别为36.8%和96.3%,显示出较好的二苯并噻吩加氢脱硫活性。La-Ni₂P/SBA-15/堇青石整体式催化剂在对二苯并噻吩的加氢脱硫过程中,以直接脱硫和加氢脱硫两种脱硫方式同时进行,并且以直接脱硫为主。     

Synthesis,characterization and hydrotreating performance of supported tungsten phosphide catalysts

Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H₂ and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH₃-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO₂, ?-Al₂O₃ supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/?-Al₂O₃ catalyst. The WP/?-Al₂O₃ catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO₂ catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/?-Al₂O₃ catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/?-Al₂O₃ catalyst. In general, a support or promoter in the WP/?-Al₂O₃ catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.     

新型磷化钨加氢精制催化剂的研究

以γ-Al₂O₃为载体,磷酸氢二铵和偏钨酸铵为原料,通过化学浸渍法制备系列磷化钨催化剂。以噻吩加氢脱硫反应为探针,考察浸渍顺序、WP负载量、焙烧温度和还原温度等因素对磷化钨催化剂加氢性能的影响。研究表明,WP负载质量分数为30％的WP-1催化剂具有较高的噻吩加氢脱硫活性, P的加入在一定程度上能够改善催化剂加氢活性。     

WP/γ-Al2O3催化剂的制备、表征及加氢脱硫和加氢脱氮活性

Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%-37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA, XPS and 31p MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W species was in a high valence state W6 on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31p MAS-NMR results indicated that 31p shift from 85% H3PO4 of 2.55 × 10-4 for WP and 2.57 × 10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activities and lower HDS activities than those prepared by the impregnation method under the same loading of WP.WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.     

FDS-4型加氢脱硫催化剂的研制

以混合氢氧化铝粉为载体原料，采用部分混捏、部分浸渍法负载CoMo活性组分制得FDS-4型加氢脱硫催化剂。将该催化剂用于高硫中间馏分油深度加氢脱硫及重质馏分油加氢精制时，显示出优良的加氢脱硫活性和稳定性。     

Zeolite beta synthesized with acid-treated metakaolin and its application in diesel hydrodesulfurization

A new type of zeolite beta (denoted as MB) with multi-pore system was synthesized by using in situ synthesized method from kaolin mineral in this study. NiW/Al₂O₃–MB and NiW/TiO₂–Al₂O₃–MB catalysts were prepared and the hydrodesulfurization (HDS) activities of these catalysts were evaluated with FCC diesel feed. The samples were characterized by N₂ physisorption, XRD, SEM, TPR, FT-IR spectroscopy of pyridine adsorption, HRTEM and XPS techniques. The HDS results showed that the MB-containing catalyst exhibited much higher HDS conversion (98.7%) than that of NiW/γ-Al₂O₃ (97.5%). The incorporation of TiO₂ into the composite supports further increased the HDS conversion (99.3%) of NiW/TiO₂–Al₂O₃–MB. The higher HDS activity was mainly associated with the appropriate ratio of B/L (Brönsted acid/Lewis acid) and the enhanced hydrogenation activity.     

Rhodium phosphide catalyst for hydrodesulfurization: Low temperature synthesis by sodium addition

Effect of sodium (Na) addition on rhodium phosphide (Rh₂P) formation on MFI zeolite, SiO₂ and Al₂O₃ and hydrodesulfurization (HDS) activity were examined. The TPR results revealed that Na addition enhanced reducibility of phosphates. The XRD results indicated that Rh₂P phase was easily formed on NaMFI support as compared with on HMFI support. The maximum HDS activity of Rh–P/NaMFI catalyst was obtained at lower reduction temperature and this activity was higher than that of Rh–P/HMFI catalyst. We concluded that since Na would weaken interaction between Al and phosphate, high HDS activity of Rh–P/NaMFI catalyst was observed at lower reduction temperature.     

Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H₂ and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH₃-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO₂, γ-Al₂O₃ supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al₂O₃ catalyst. The WP/γ-Al₂O₃ catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO₂ catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al₂O₃ catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al₂O₃ catalyst. In general, a support or promoter in the WP/γ-Al₂O₃ catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.     

CoMo catalysts supported on aluminosilicates: synergy between support and sodium effects

The structural properties and the hydrodesulfurization (HDS) activity of sodium doped and sodium free CoMo catalysts supported on amorphous aluminosilicates (ASA) were investigated as a function of different SiO₂:Al₂O₃ ratios. The support yielding the most active catalyst, (66% alumina) doped with different amounts of sodium, was used for a series of similar catalysts in order to study the effect of the alkali ion on the catalytic performance. The supports were prepared by sol–gel method and the catalysts were prepared by incipient wet impregnation method. The structure and the surface of the various samples were investigated by X-ray diffraction (XRD), temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). The catalytic behaviour was tested in the hydrodesulfurization of thiophene carried out in a continuous flow system at atmospheric pressure, in a range of temperature between 603 and 633 K. Changes of activity with the support composition were observed. The presence of sodium, modifying the Brønsted acidity of the supports, enhances such effect. Moreover, the increase of the activity with increasing amount of sodium was a clear indication of the promoting effect of the alkali ion.     

Hydrodesulfurization of hindered dibenzothiophenes on bifunctional NiMo catalysts supported on zeolite–alumina composites

A series of NiMo catalysts supported on HNaY(x)–Al₂O₃ composites with different amounts of HNaY zeolite (x = 0, 5, 10, 20 and 100 wt.% of HNaY) was prepared and tested in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyl-DBT (4,6-DMDBT). The catalysts were characterized by N₂ physisorption, X-ray diffraction (XRD), FT-IR spectroscopy of pyridine and nitrogen oxide adsorption (Py and NO-FT-IR), temperature-programmed reduction (TPR), scanning electron microscopy (SEM-EDX) and high-resolution transmission electron microscopy (HRTEM). It was found that the increase in the zeolite content causes changes in the acidic properties of the catalyst (number of acid sites) as well as in the characteristics of the deposited metallic species (location and dispersion). Different activity trends with the amount of the zeolite were found for the DBT and 4,6-DMDBT hydrodesulfurization on NiMo/HNaY-Al₂O₃ catalysts. As for the HDS of DBT the alumina-supported catalyst presents the highest activity. The incorporation of the zeolite causes an initial drop and then the recovery of activity with zeolite content. In contrast, for the 4,6-DMDBT the HDS activity always increases with zeolite content. These two different catalytic behaviors seem to be due to two opposite effects, which affect the contribution of the reaction routes available for the HDS of each reactant, these effects are: (i) the decrease of MoS₂ dispersion caused by the incorporation of zeolite to the catalyst and (ii) the increase of the proportion of Brönsted acid sites with zeolite content. The reaction product distribution indicates that both types of sites, coordinatively unsaturated sites (CUS) of the MoS₂ and zeolite Brönsted acid sites, participate in the 4,6-DMDBT and DBT transformations.     

Effect of Zr-SBA-15 support on catalytic functionalities of Mo, CoMo, NiMo hydrotreating catalysts

SBA-15 and ZrO₂ (10–50 wt.%) containing SBA-15 mesoporous materials were prepared by direct and post-synthesis methods. Characterization using low angle XRD, pore size distribution, CO₂ chemisorption indicate that hexagonal mesoporous structure is retained even after ZrO₂ addition (25 wt.%). Mo, CoMo and NiMo catalysts prepared using these supports were examined by XRD, oxygen chemisorption, temperature programmed reduction (TPR). The catalysts were tested for hydrodesulfurization (HDS) of thiophene and hydrogenation (HYD) of cyclohexene. HDS of thiophene for 8%Mo, 3%Co8%Mo, and 3%Ni8%Mo increases with increasing ZrO₂ loading in SBA-15 up to 25 wt.%. Oxygen chemisorption and TPR hydrogen consumption indicated that the molybdenum dispersion and anion vacancies, and catalytic activities are significantly influenced by ZrO₂ content in Zr-SBA-15. A comparison indicated that TiO₂-SBA-15, ZrO₂-SBA-15 supported CoMo catalysts show higher activities for hydrodesulfurization.