加氢催化剂的器外再生

介绍了国内外再生技术的发展状况,对比器内和器外再生技术的优缺点以及催化剂活性恢复率的差异,说明器外再生技术是催化剂再生的发展方向。     

Structure and catalytic properties of Cu-Ni bimetallic catalysts for hydrogenation

The dependence of catalytic activity and selectivity of Cu-Ni bimetallic catalysts for oil hydrogenation on CuNi ratios have been investigated while they were reduced at low temperature (230 °C). Two maxima occurred at Cu₂Ni₁ and Cu₁Ni₃ in the activity-CuNi curve. Cu riched catalysts have higher selectivity than Ni riched ones, and may cause dehydrogenation and isomerization of linoleate at the beginning of the reaction. The structures of the catalysts reduced at different temperatures have been studied by means of XRD, XPS, EXAFS and FMR et al. The structure of the catalysts reduced at 230 °C can be described as an aggregate of Cu particles inlaid with Ni atoms and unreduced NiO, and the easily reduced Cu always segregates on the surface, while homogeneous solid solution particles can be formed in the case 400 °C being used as reduction temperature.     

催化裂解汽油加氢催化剂及工艺研究

根据催化裂解汽油组成特点,开发了“切C5-脱砷-切C9-两段加氢”工艺技术路线及配套的一、二段加氢催化剂.采用该工艺技术路线,利用自制催化剂对催化裂解汽油进行加氢处理,500 h稳定性评价结果表明,开发的工艺技术路线合理、可靠,催化剂性能稳定,产品溴价小于1.0 g Br/100 g,硫含量小于1.0 μg/g,满足芳烃抽提要求.     

Novel cluster-derived catalysts for the selective hydrogenation of crotonaldehyde

The controlled pyrolysis of transition metal cluster substituted metal carboxylates, e.g., M₄O[(CO)₉Co₃CCO₂]₆, where M = Co and Zn, and M'₂(CO)₉Co₃CCOO₄, where M' = Co, Mo, and Cu, results in the formation of high surface area, amorphous solids that are active and selective catalysts for the hydrogenation of crotonaldehyde. In contrast to conventional metal catalysts that are selective for the double bond hydrogenation, these new solids exhibit high regioselectivities for the conversion of crotonaldehyde (2-butenal) to crotyl alcohol (2-butenol). Further, the observed selectivities depend on the metal cluster carboxylate structure.     

Diastereoselective catalytic hydrogenation on heterogeneous metal catalysts

The application of diastereoselective hydrogenation catalyzed by heterogeneous catalysts for the asymmetric synthesis of organic compounds is illustrated in the reduction of several functional groups. In that approach, the chiral information is provided by the prior attachment of a chiral auxiliary to the substrate to be hydrogenated. The optically active hydrogenated product is then disconnected from the chiral auxiliary. Proper choice of the inductor, of the catalyst and of reaction conditions may result in high diastereoselectivities. This revised version was published online in June 2006 with corrections to the Cover Date.     

The hydrogenation of triglycerides using supported alloy catalysts. II. Silica-supported Pd-Cu catalysts

Palladium-copper catalysts supported upon silica, containing 2–6% (w/w) total metal, have been prepared by (i) precipitation and (ii) impregnation methods. The catalysts were employed for the hydrogenation of soyabean oil at 1 bar H₂ pressure and at 160°C in a stirred batch reactor. Temperature-programmed reduction studies provided evidence of alloying of palladium and copper and metal surface area measurements exhibited evidence of a slight maximum in the metal surface area at around 90 at. % Pd content. In addition, it was observed that the presence of copper seemed to prevent sintering of palladium, giving a more stable or even enhancing metal surface area compared with palladium alone. Activity measurements showed that there was evidence of a maximum at around 80–90 at. % Pd content. However, selectivity measurements showed that the latter parameter was dominated by the presence of palladium and except at very high copper contents the superior selectivity of the latter for linolenate chain hydrogenation was hardly evident. It is thought that the palladium may cause the copper to be present largely as Cu°, which is not as effective as Cu¹ in catalysing selective hydrogenation of multiply unsaturated species.     

Selective hydrogenation of cyclopentadiene over supported metal catalysts

The selective hydrogenation of cyclopentadiene to cyclopentene has been studied in the liquid phase using Pd and Pd Me/Al₂O₃ bimetallic catalysts (Me = Mn, Ni, Co, W). The highest activity was obtained with Pd Co and Pd W/Al₂O₃. For these catalysts, no hydrogen or CO chemisorption was detected although Pd could be seen by XPS at 335·8 eV; it is considered that new species, more active for the selective hydrogenation of cyclopentadiene, appeared at the catalyst surface. The sulfur resistance towards thiophene has also been studied. It was observed that the highest sulfur resistance is coincident with the highest activity. XPS analysis shows that the poisoning species is thiophene adsorbed on the catalyst surface.     

硫化型NiMo加氢催化剂制备与表征

以四硫代钼酸铵溶液和硝酸镍溶液为浸渍液,根据活性组分Ni和Mo浸渍顺序的不同,采用真空饱和浸渍法制备了MN系列和NM系列 NiMoS/γ-Al₂O₃催化剂。在固定床加氢中试反应装置上研究了NiMoS/γ-Al₂O₃催化剂对二苯并噻吩加氢反应的催化性能,结果表明,NiMoS/γ-Al₂O₃催化剂对二苯并噻吩加氢反应具有良好的活性和选择性。Ni助剂的加入,有利于二苯并噻吩加氢反应的活性和选择性。MN-0.3为最优NiMoS/γ-Al₂O₃催化剂。在空速10 h^-1、反应压力2.0 MPa、氢油体积比300∶1、氢气预处理温度320 ℃和反应温度300 ℃条件下,催化剂对二苯并噻吩加氢反应转化率达83.9%,加氢反应活性较高。     

Preparation, characterization and reactivity of Pd/Nb2O5 catalysts in hexa-1,5-diene hydrogenation

Palladium/niobia catalysts are prepared by various methods involving either gas or liquid phase reduction. Although giving rise to average or low dispersion, the reduction of palladium precursors in a liquid medium (hydrazine or ethylene–glycol) appears to be a promising method since a low dispersion favors the activity in the hydrogenation of hexa-1,5-diene in liquid phase. The substitution of alumina by niobia improves the fractional selectivity and the yield of hex-1-ene in all cases. A very good global selectivity is also observed.     

Deactivation of fixed-bed nickel hydrogenation catalysts by sulfur

A series of fixed-bed nickel hydrogenation catalysts was tested in the dearomatization of hydrocarbon solvents. The mechanism of catalyst deactivation by aromatic sulfur compounds was studied in high-pressure micro-flow equipment by variation of the experimental conditions and the sulfur content of the feed. It is concluded that catalyst deactivation proceeds under mild but realistic conditions through formation of a surface sulfide which blocks the active surface. The rate of the disappearance of the active sites is a first-order process with rate constant 1.0 × 10⁻³ (ppm S)⁻¹ h⁻¹. Under more severe conditions, more sulfide layers are formed, but bulk Ni₃S₂ was not observed even after full deactivation of the catalysts. The poisoning of the active sites in the latter case is no longer a first-order process. Consequently, under the circumstances investigated, the sulfur resistance of nickel catalysts is determined by the nickel surface area per unit weight of catalyst.     

Coupled hydrogenation and ring opening of tetralin on potassium modified Pt/USY catalysts

Coupled hydrogenation and ring opening of tetralin (THN) on Pt/USY catalyst were performed on a high-pressure fixed-bed reactor. The effect of reaction temperature in range of 100–300 °C and the nature of the catalyst (metal and acid sites) on the catalytic performance were studied. The results indicated that the extent of hydrocracking, a sequential reaction of ring opening, should be reduced in order to maintain high yields of the ring opening products (ROP). Introduction of the Pt component accelerated the hydrogenation and ring opening of the THN significantly. It was also found to be an effective way to optimize the acid properties of the catalysts by introducing an appropriate amount of potassium to the catalyst, such that the strong acid sites of the catalysts were diminished, and a higher ROP yield could be obtained as a result of the inhibiting of the hydrocracking activity of the catalyst. When the yield of the C10 fractions could be maintained at 90 wt.%, then a maximal ROP yield of 35.6 wt.% could be obtained on a 0.5 wt.% Pt/USY catalyst loaded with 2.0 wt.% of K.     

The hydrogenation of triglycerides using supported alloy catalysts. I. Silica-supported Ni—Ag catalysts

Silica-supported Ni-Ag catalysts with a loading of 2·1·0.6% (w/w) total metal have been prepared using the precursors nickel dimethylglyoxime and silver nitrate by means of a simple impregnation method. The resulting catalysts were activated by calcination at 260°C in air, followed by hydrogen reduction at 450°C. They were then employed for soyabean oil hydrogenation at 1 bar H2 pressure and 160°C in a stirred batch reactor. Characterisation of the catalysts using temperature-programmed reduction and electron microscopy indicated that alloying of nickel and silver had occurred, but metal particle composition, for a given overall composition, varied with metal particle size and smaller metal particles were nickel rich. The hydrogenation activity and selectivity measurements revealed that the catalysts were more active and selective than a commercial nickel catalyst. Furthermore, the specific activities of the alloy catalysts were a maximum for alloys in the range 70–90 at. % Ni. However, the supported alloy catalysts also gave rise to greater trans isomerisation than the commercial catalyst. This is attributed to hydrogen deficiency caused by large triglyceride molecules blocking hydrogen chemisorption on small nickel particles (10–50 Å in diameter), leading to enhanced cis-trans isomerisation.     

Bench-scale continuous hydrogenation of Australian coals — study of iron catalysts and recycle solvent composition

The inter-relations between iron catalysts, recycle solvent composition and product yield and composition have been investigated in bench-scale (1–2 kg h^?1) continuous hydrogenation of Australian coals at process severity of 21–22 MPa at 400–430°C. Products and recycle solvent are recovered in batch distillation (atmospheric and vacuum) and the distillate solvent is returned to slurry feed without further treatment. Successive samples of recycle solvent are analysed by g.c.-m.s., i.r. and titrimetry. The effect of adding iron catalysts in the form of red mud - sulphur mixtures or compounds after a short period of continuous operation without catalyst is demonstrated. Distillate yields from black coals increase from 24–34 wt% daf under non-catalytic conditions to 35–53 wt% daf by adding iron catalysts. The composition of the almost equilibrated recycle solvent also changes and a new equilibrium is approached after the iron catalyst is added. The effect of solvent composition on distillate yield can not be determined from these data. The ratio of hydroaromatic components to hydroaromatic plus aromatic components in the solvent increases from ≈0.2 at non-catalytic equilibrium to ≈0.5–0.6 at catalysed equilibrium after adding iron. Other compositional parameters in the recycle solvent do not show any clear responses to the addition of iron. Equilibrium solvent composition under constant operating conditions is attained at ≈10 passes at 1 kg ^h?1 throughput with total system holdup of ≈20 kg. Paraffins for the Queensland subbituminous coal equilibrated at 18–24% in the solvent, phenolics at 16–21%, basic nitrogen at ≈0.4% (as N), and the balance a mixture of aromatics and hydroaromatics. The total aromatics neglecting phenolics in the equilibrium recycle solvent consists of ≈40–50% each of two-and three-ring and 5–10% four-ring members.     

Influence factors on activity of Ru–Zn catalysts in selective hydrogenation of benzene

Selective hydrogenation of benzene is an atom economic green route to produce cyclohexene. The control of Zn species is the key to the catalytic performance of Ru–Zn catalysts. The influences of ZnO crystals on selective hydrogenation of benzene were explored. A series of Ru–Zn catalysts with different Zn contents and ZnO morphologies were prepared by changing the amount of NaOH in the co-precipitation process. The catalysts were characterized by N_2 physisorption, X-ray powder diffraction(XRD), inductively coupled plasma optical emission spectrometer(ICP-OES), scanning electron microscope(SEM), temperature-programmed reduction(H_2-TPR)and Malvern laser particle size analyzer. It is found that with increasing the amount of NaOH, the Zn content first increased then decreased, and the ZnO crystals changed from relatively thicker pyramidal-shaped crystals to slimmer needle-shaped crystals. The catalyst had the highest Zn content(22.1%) and strongest interaction between ZnO crystals and Ru particles at pH 10.6 of the solution after reduction. As a result, it had the lowest activity. The activity of Ru–Zn catalysts is affected by both the Zn content and the interaction between ZnO crystals and Ru particles. The effect of reduction time was also investigated. Prolonging the reduction time caused no significant growth of ZnO crystals but the aggregation of catalyst particles and growth of Ru nanocrystals, thus resulting in the decrease of catalytic activity.     

The selective hydrogenation of acetonitrile on supported nickel catalysts

The catalytic behavior of several supported nickel catalysts in the hydrogenation of acetonitrile was studied. It was established that the selectivity of this process is greatly influenced by the nature of the support used. Catalysts consisting of nickel supported on acidic supports catalyzed the formation of condensation products, diethyl- and triethylamine. Nickel supported on basic supports was highly selective with respect to the formation of the primary amine, ethylamine. It was shown that modification of the intrinsic acidity of alumina-based supports by the application of alkaline additives has a large impact on the selectivity of the resulting catalyst. Based on the results obtained from measurements on a basic catalyst diluted with either an acidic or a basic support, a dual-function mechanism is suggested. The mechanism implies that the hydrogenation function of the catalyst is located on the metal, while the acid function, responsible for the condensation reactions, is located on the support. A mechanism, accounting for the occurrence of the acid-catalyzed condensation reactions, is proposed.     

氢气高温还原制备的负载型镍基催化剂用于苯酚加氢的性能

通过等体积浸渍法分别将Ni(NO₃)₂、NiCl₂、NiSO₄ 3种镍前体浸渍于A1₂O₃或SiO₂载体上,然后通过H₂高温还原法制备了负载型镍基催化剂,考察了镍前体、载体种类、镍负载量、反应条件等对镍基催化剂苯酚加氢性能的影响。结果表明,对比3种镍前体,在H₂高温还原体系中Ni(NO₃)₂最容易被还原,制备的镍基催化剂苯酚加氢活性最高。SiO₂负载的镍基催化剂活性远高于γ-Al₂O₃催化剂。适宜的Ni负载量有助于活性组分的分散和催化活性的提高。镍基催化剂的苯酚加氢产物以环己醇为主,相对缓和的反应条件更容易生成环己酮。在非极性溶剂正庚烷或环己烷存在下,苯酚加氢反应速率远远高于极性溶剂水或乙醇存在下的结果,而且环己酮的选择性更高。     

丁辛醇装置辛烯醛液相加氢精制国产化应用

介绍了中国石油吉林石化公司化肥厂丁辛醇装置辛烯醛加氢单元工艺技术特点,通过对辛烯醛加氢催化剂国内外情况对比分析,采用了辛烯醛液相加氢国产催化剂应用情况,取得了良好的经济效益,证明辛烯醛液相加氢催化剂国产化应用是成功的。     

Preparation and investigation of Pd doped Cu catalysts for selective hydrogenation of acetylene

A series of PdCu bimetallic catalysts with low Cu and Pd loadings and different Cu: Pd atomic ratios were prepared by conventionally sequential impregnation (CSI) and modified sequential impregnation (MSI) of Cu and Pd for selective hydrogenation of acetylene. Characterization indicates that the supported copper (II) nitrate in the PdCu bimetallic catalysts prepared by MSI can be directly reduced to Cu metal particles due to the hydrogen spillover from Pd to Cu(NO₃)₂ crystals. In addition, for the catalysts prepared by MSI, Pd atoms can form PdCu alloy on the surface of metal particles, however, for the catalysts prepared by CSI, Pd tends to migrate and exist below the surface layer of Cu. Reaction results indicate that compared with CSI, the MSI method enables samples to possess preferable stability as well as comparable reaction activity. This should be due to the MSI method in favor of the formation of PdCu alloy on the surface of metal particles. Moreover, even Pd loading is super low, <0.045 wt-% in this study, by through adjusting Cu loading to an appropriate value, attractive reactivity and selectivity still can be achieved.