On the synthesis of LaCl3 catalysts for oxidative chlorination of methane

LaCl₃ is an active and selective catalyst for oxidative chlorination of methane to methyl chloride, generated in situ by chlorination from LaOCl. The latter is prepared by precipitation of La(OH)₂Cl and subsequent calcination. The synthesis route was modified by using different bases in order to synthesize high surface area LaOCl catalyst precursors. Ammonium hydroxide and the organic bases tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide are used as precipitating agents. The marked increase of the specific surface area by using organic bases indicates also that they may act as templating agents. After chlorination the specific surface areas of pure LaOCl samples decrease drastically, lanthanum carbonate, however, acts as structural promoter stabilizing the specific surface area during chlorination.     

LaCl3-based catalysts for oxidative chlorination of CH4

LaCl₃ is an active, selective and stable catalyst for oxidative chlorination of methane to methyl chloride. Selective conversion to methyl chloride can be achieved by limiting methane conversion, for example, by using an excess of methane in the feed. Methylene chloride and carbon monoxide are the main side products at higher methane conversion levels. Transient OCl⁻ anion, formed by oxidation of Cl⁻ in LaOCl and LaCl₃ with molecular oxygen, is proposed to be the active site for the initial step of methane activation. CO _x formation is proposed to proceed through the formation of adsorbed multiply substituted chloromethanes.     

New efficient catalysts for the oxidative coupling of methane

During calcination of OCM catalyst precursors, Li...Cs spectacularly lower the amorphous silica -cristobalite phase transition temperature, shown here to be a critically important requirement for production of effective catalysts. Incorporation of W switches on OCM activity and newly discovered K/W and Rb/W formulations exhibit unsurpassed ethylene selectivity at high methane conversion. Addition of Mn significantly improves the performance of the former. An alkali-stabilised tungsten oxo species is thought to be the OCM active site.     

Low temperature catalysts for oxidative coupling of methane

A simple review is given to the recent work of the oxidative coupling of methane at low temperature. Emphasis is laid on the different systems of low-temperature catalysts under conventional CH₄/O₂ co-feed conditions, and on the investigations of low-temperature oxidative coupling of methane in the presence of steam in the feed. Other approaches, e.g. oxidative coupling of methane at elevated pressure and moderate temperature, preparing ethylene by oxidative coupling reaction of methane on laser-activated solid surface, are also included.     

High-temperature parallel screening of catalysts for the oxidative coupling of methane

The oxidative coupling of methane (OCM) was investigated with a specifically designed multi-channel device operating fixed-bed reactors at high temperature and atmospheric pressure. The device allows precise temperature measurement in each channel selected for analysis and possesses a quench cooling unit right after the reaction zone. Analysis is based on a mass spectrometer allowing a time resolution of only 3 s per analysis and 30 s per reactor channel. Successful screening is demonstrated using a reactant feed of O₂ and CH₄ diluted in Ar at flows between 100 and 166 mL/min per reactor channel. As expected, Li/MgO-based catalysts showed good initial performance, but rapid deactivation at 800 °C excludes their use in high-temperature applications. Good C₂ selectivity up to 80% and high yields up to 20% were observed for La/Sr/CaO catalysts. Even more interesting, no decline in performance was observed for those formulations identifying 10% La/20% Sr/CaO as best catalyst in an initial library. Screening of various La and Sr loadings at different operating conditions identified a optimal content of 5–10% for La and 20% for Sr. The exploration of operating conditions showed increasing C₂ productivities with increasing reactant partial pressure, reaching at 800 °C values up to 1.3 × 10⁻⁵ mol (C₂) s⁻¹ g(cat)⁻¹.     

Transition metal-doped TiO2 nanowire catalysts for the oxidative coupling of methane

The catalytic oxidative coupling of methane (OCM) on transition metal-doped TiO₂ nanowire catalysts was performed and the effects of metal dopants were studied. With transition metal doping, the electric and optical properties of nanowires were adjusted, which seemed to improve the catalytic activity and selectivity of the OCM reaction. A Mn-doped TiO₂ nanowire catalyst exhibited the highest C₂ yield with the highest (ethylene)/(ethane) ratio because of its moderate oxidation activity, while a highly active Rh-doped TiO₂ nanowire catalyst converted methane into fully oxidized CO and CO₂. The electric conductivity assessed by UV–vis absorption represented the oxidation activity of the nanowire catalysts.     

Catalytic properties of various MgO catalysts for oxidative coupling of methane

A series of MgO catalysts for the oxidative coupling of methane prepared by different methods have been investigated. Specific surface area, XRD and XPS measurement results reveal that at lower temperatures catalysts with larger specific surface area, larger lattice distortion, smaller crystal dimension, and higher amount of unsaturated coordinated surface oxygen give higher catalytic activity. However, if we compare the catalytic properties of the samples in terms of unit surface area, the dependence of catalytic properties of the samples will be different.     

Gamma-initiated chlorination of methane

Gamma radiation has been used to initiate the gas phase reaction between chlorine and methane. The products consist of hydrogen chloride, and the four chlorinated methanes, in yields depending on the experimental conditions. Experiments were conducted over a range of temperatures, pressures, concentrations and absorbed doses. G values as high as 1.2 × 10⁶ were found, indicating the formation of a chain reacting system. Two hypothetical reactor models were used to obtain an estimate of the energy cost of the process. On the basis of the reactor models studied, a one-pass gamma reactor appears uneconomical for the production of carbon tetrachloride, but the energy cost for methyl chloride production is less than one percent of the product value.     

Basic sites on the surface of oxide catalysts responsible for oxidative methane coupling

The basic sites of various oxide catalysts for the oxidative dimerisation of methane were studied by FTIR spectroscopy of adsorbed molecular probes (chloroform and CO₂). The methods used are compared and the advantage of CO₂ as probe for specifying the basic sites is demonstrated. The strengths of the basic sites were seen to correlate with the spectral parameters of the surface carbonates. Differences in spectral responses of carbonates are attributed to the different states of oxygen participating in their formation. The concentration of the strongest sites was estimated. A study of the catalytic activity of this system indicates that the system's activity in oxidative methane coupling depends on the presence and concentration of strong basic sites on the catalyst surface.     

Cation effects in the oxidative coupling of methane on phosphate catalysts

The conversion of methane and the selectivities to the various products have been measured at 700 and 775 °C on a variety of phosphates of La(III), Zr(IV), V(V), Cr(III), Mn(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), B(III), Pb(II), Bi(III) and Sm(III) in the presence and absence of carbon tetrachloride. The conversions reach as high as 30 and 49% at 700 and 775 °C, respectively, with methane and oxygen at partial pressures of 200 and 25 Torr, respectively. The highest C₂₊ selectivities (61 and 82%, respectively) were obtained for lead(II) phosphate at 700 and 775 °C, respectively. In general the conversions and C₂₊ selectivities are enhanced on addition of carbon tetrachloride (1.1 Torr) to the feedstream, although there are notable exceptions. Significantly high selectivities to formaldehyde are observed with a number of the catalysts, in particular 32% with boron(III)phosphate.     

Kinetic-transport models and the design of catalysts and reactors for the oxidative coupling of methane

The design of catalytic pellets and reactors using detailed kinetic-transport models is illustrated for the oxidative coupling of methane to form ethane and ethylene. Oxygen sieving within diffusion-limited pellets and staged oxygen injection reactors increase C₂ selectivity by inhibiting full oxidation homogeneous pathways that lead to CO and CO₂ products. Our simulations suggest that high densities of surface sites with kinetics that depend weakly on oxygen concentration are required to benefit from oxygen-sieving catalyst and reactor schemes. These sites favor beneficial surface activation processes even at the low oxygen concentrations present within staged injection reactors and diffusion-limited pellets. Controlled introduction of stoichiometric oxygen reactants leads to C₂ yields as high as 50%; the reactions, however, occur at much slower rates and require much greater reactor volumes than in conventional cofeed reactors.     

The oxidative coupling of methane by sodium promoted lanthanide catalysts

The characteristics of La₂O₃ catalysts with three different supports (BaCO₃, MgO, and ZnO), two different alkaline metal promoters (Na₂O and Na₂CO₃), and a china clay have been investigated. The relationship of the surface basicity of the support to the activity and selectivity of the catalyst were studied by TPD. The results showed that the surface basicity of these three supports decreased in the following order: BaCO₃ > MgO > ZnO. The choice of Na₂O as a promoter in La₂O₃/(BaCO₃ or MgO) had a better effect than the choice of Na₂CO₃. The Na₂O promoter could increase not only the catalytic activity and the C₂ selectivity, but also lower the optimal reaction temperature. Addition of 15% clay into the La₂O₃–alkaline metal catalysts could increase the strength of the catalyst and lower the optimum reaction temperature.     

The effect of alkali metal salts promoted MgO catalysts for the oxidative coupling of methane

Catalytic activities of the alkali metal salts are discussed based on experimental observations in a fixed bed flow reactor at atmospheric condition and instrumental analysis. LiCl (30 wt%) and NaCl (30 wt%) promoted MgO catalyst showed superior activity to mono alkali metal salts promoted MgO catalysts based on the C₂ yield. This suggests that the bialkali metal salts neutralize the nonselective acid sites due to synergistic effect. Moreover, it is estimated that the active sites is O^- ions.     

The nature of the active phase in supported neodymium catalysts for oxidative coupling of methane

Catalytic properties of supported neodymium oxide in oxidalive coupling of methane were studied. The most efficient catalysts contain NdzO3 as separated phase. The efficiency increases with the rise of oxidative sites concentration in catalyst     

Lithium-doped sulfated-zirconia catalysts for oxidative coupling of methane to give ethylene and ethane

Li-doped sulfated-zirconia catalysts were found to be effective for oxidative coupling of methane (OCM). The catalyst performances depend on the sulfate content and calcination temperature. A maximum C₂ yield is attained over the catalysts, which contain 6 wt.% sulfate and calcined at 923–973 K, being closely related to the preparation conditions of sulfated-ZrO₂ as solid super-acids. When the performances of the Li-doped sulfated-ZrO₂ (Li/SZ) catalysts were tested at 1023 K as a function of reaction time, both the C₂ and CO_x selectivities remained constant over the range of 8 h, but the CH₄ conversion decreased from 17.5% to 11.9%. The nature of Li/SZ catalysts for the OCM was investigated by X-ray diffraction, XPS, and NH₃ and CO₂ TPD measurements. It could be postulated that the sulfated-ZrO₂ surface could play an important role in the formation of a catalytically active structure by Li-doping.     

Active-oxygen species on non-reducible rare-earth-oxide-based catalysts in oxidative coupling of methane

From supplementary in situ Raman spectroscopic studies of active-oxygen species on non-reducible rare-earth-oxide-based catalysts in the oxidative coupling of methane (OCM) and structural adaptability considerations, further support has been obtained for our proposal that there may be an active and elusive precursor (of O₂ ^– and O₂ ^2– adspecies), most probably O₃ ^2– formed from reversible redox coupling of an O₂ adspecies at an anionic vacancy with a neighboring O^2– in the surface lattice. This active precursor may initiate H abstraction from CH₄ and be itself converted to OH^–+O₂ ^–, or it may abstract an electron from the oxide lattice and be converted to O₂ ^2–+O^–. The prospect of developing this type of OCM catalysts is discussed.     

甲苯定向氯化催化剂的研究

对甲苯定向氯化的催化剂进行了研究,找到了一种新型助催化剂,对助催化剂合成的主要影响因素进行了探讨,得到了最佳合成工艺条件,这种助催化剂与SbCl3共同作用,催化甲苯氯化反应时,对氯甲苯的选择性由原来的46%提高到60%。     

Surface modification of Ni catalysts with trace Pt for oxidative steam reforming of methane

Hysteresis of catalytic performance with respect to temperature increasing and decreasing in oxidative steam reforming of methane (CH₄/H₂O/O₂/Ar = 40/30/20/10) over the monometallic Ni catalysts disappeared by the modification with Pt, and the additive effect of Pt by the sequential impregnation method (Pt/Ni) was much more significant than that by the co-impregnation method (Pt + Ni) in terms of catalytic performance and catalyst bed temperature profile. Characterization results by means of TEM, TPR, EXAFS, and FTIR suggest that the Pt atoms on the Pt/Ni catalysts were located more preferably on the surface to form a PtNi alloy than those on the Pt + Ni catalysts. The modification of Ni with Pt suppressed the oxidation of Ni species near the bed inlet in the oxidative steam reforming of methane at 1123 K, although the species on the monometallic Ni catalysts were oxidized under similar conditions. This can be due to the decreased oxidation rate of the species and the increased reduction rate caused by the surface modification of Ni with Pt. Consequently, the PtNi species can be maintained in the metallic state near the bed inlet, and the species can be the active site for the reforming reaction as well as the combustion reaction, which this leads to a lower bed temperature and smaller temperature gradient than those seen for the monometallic Ni catalysts.     

Acid-base properties and the directions of oxidative transformation of methane over nickel-based catalysts

The reactions of dry (CO₂) reforming and partial oxidation of methane have been investigated in a membrane reactor. The membrane is composed of a dense thin silica (SiO₂) film supported on porous Vycor tubes and was synthesized by chemical vapor deposition. The hydrogen permeance of the membrane was 0.2–0.3 cm³/(cm² min atm) at 600°C combined with a H₂/N₂ selectivity of 200–300. Significant increases in methane conversion were attained in both reactions at 500–750°C, albeit at very low space velocities. The membrane permeance declined by 50% after exposure to feeds containing H₂O, but otherwise exhibited excellent stability under reaction conditions.     

The oxidative coupling of methane on alkali- and alkaline earth-phosphate catalysts

The oxidative coupling of methane has been tested over alkali- and alkaline earth-phosphate catalysts at 700 and 775 °C with and without the introduction of a small quantity of tetrachloromethane (TCM) to the feedstream. In general, the conversion of methane was enhanced by the addition of TCM but the effect on selectivity was dependent on the catalyst being examined. The selectivity to C₂ and higher hydrocarbons and that to oxidation products have been shown to have a dependence on the cation radius/charge ratio.