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Noname manuscript No.

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Methane Activation by Heterogeneous Catalysis
Raimund Horn · Robert Schlögl

Received: date / Accepted: date

Abstract Methane activation by heterogeneous catal- mediated by oxygen and sulfur, the direct oxidation of
ysis will play a key role to secure the supply of en- methane to formaldehyde and methanol, the halogena-
ergy, chemicals and fuels in the future. Methane is the tion and oxy-halogenation of methane to methyl chlo-
main constituent of natural gas and biogas and it is also ride and methyl bromide and finally the non-oxidative
found in crystalline hydrates at the continental slopes methane aromatization to benzene and related aromates.
of many oceans and in permafrost areas. In view of this Opportunities and limits of the various activation strate-
vast reserves and resources, the use of methane as chem- gies are discussed.
ical feedstock has to be intensified. The present review
Keywords methane · heterogeneous catalysis ·
presents recent results and developments in heteroge-
synthesis gas · steam reforming · dry reforming ·
neous catalytic methane conversion to synthesis gas,
autothermal reforming · partial oxidation · hydrogen
hydrogen cyanide, ethylene, methanol, formaldehyde,
cyanide · oxidative coupling · methanol · formaldehyde ·
methyl chloride, methyl bromide and aromatics. After
halogenation · oxy-halogenation · aromatization
presenting recent estimates of methane reserves and
resources the physico-chemical challenges of methane
activation are discussed. Subsequent to this recent re- 1 Introduction
sults in methane conversion to synthesis gas by steam
reforming, dry reforming, autothermal reforming and Methane, CH4 , the most simple hydrocarbon, exists in
catalytic partial oxidation are presented. The high tem- enormous quantity on our planet. It occurs as the prin-
perature methane conversion to hydrogen cyanide via cipal component of natural gas with a concentration
the BMA-process and the Andrussow-process is con- between 70 % and 90 % by volume. According to the
sidered as well. The second part of this review focuses annually published BP Statistical Review of World En-
on one-step conversion of methane into chemicals. This ergy [1], proven world natural gas reserves were spec-
includes the oxidative coupling of methane to ethylene ified for the year 2013 to 187.3 · 1012 m3 . Reserves
denote only all that natural gas that can be recov-
Prof. Dr. Raimund Horn ered from known reservoirs under existing economic,
Institute of Chemical Reaction Engineering technical and operating conditions. It does not include
Hamburg University of Technology
Eißendorfer Straße 38, 21073 Hamburg, Germany
reservoirs yet to be discovered or natural gas which
Tel.: +49-(0)40-428-78-3242 is currently too expensive for exploitation. In partic-
Fax: +49-(0)40-428-78-2145 ular this number does not include natural gas found in
E-mail: horn@tuhh.de crystalline hydrates at the continental slopes of many
Prof. Dr. Robert Schlögl oceans and in permafrost areas. Estimates of the amount
Department of Inorganic Chemistry of methane stored in hydrates differ widely ranging
Fritz-Haber-Institute of the Max-Planck-Society
Faradayweg 4-6, 14195 Berlin
from 2500 · 1012 m3 [2] to 15000 · 1012 m3 [3]. Methane
Tel.: +49-(0)30-8413-4400 chemistry experiences a boom not only because of its
Fax: +49-(0)30-8413-4685 enormous reserves and resources but also because of im-
E-mail: acsek@fhi-berlin.mpg.de proved production technology. Natural gas extraction

In the electronic ground state (X 1 A1 ). Direct methane conversion into chemicals and fuels is e. Unfortunately. The latter can be carried out in presence of gas-phase rinated methane.1 · 1010 m3 natural gas. Methane chemical raw material is still underrepresented. the use of methane as Due to symmetry. Today. facile but still challenging is the removal of electrons jority amount of natural gas. industrial methane conversion path. oxygen (Andrussow-Process) or without oxygen (BMA- ways are not yet competitive to oil based production process).471◦ ). nature.ng ≈ 0. activated. Direct methane conversion in in- tively. methane con. is burned from the C–H σ bond by strong electrophiles.7 − 0. methane is often considered the ‘holy grail’ of chemistry and catal- the main component of biogas formed by anaerobic di. The obtained CO/H2 mixtures are used for .ng ≈ 30 − 40 MJ · m−3 ) is high temperatures or aggressive reactants like superacids about three orders of magnitude lower than that of oil or radicals are almost inextricably linked to selectivity (ρm. electron configuration.8 ktoe was cupy binding molecular orbitals in a (1a1 )2 (2a1 )2 (1t2 )6 produced in 2010 in the European Union correspond.8−0. has a very low proton affinity (544 kJ · mol−1 ) and is an tion purposes or for electricity production. are currently following.9 kg · m−3 .090 Å. direct transformation routes of methane into nation into the high lying C–H σ ∗ orbital is energeti- chemicals and fuels.185) and the hydrogen atoms are slightly pos- itively charged (δH = +0. cally difficult and sterically hindered. The ma. are directly reflected in a small number of industrial gasoline. If this hydrogen atom transfer (HAT) from methane to oxy- number is compared to the percentage of natural gas gen centered gas-phase ion clusters and all gas-phase used as chemical feedstock (less than 10 % of the world radical-ions possessing sufficient spin density at an oxy- production). idation. conversion pathways. Somewhat more mediate synthesis gas generation. more profitable conversion routes of natural gas dustry is restricted to unselective radical chlorination to into valuable chemicals at the consumer site would jus. [9] reviewed thermal annual production of 3364 · 109 m3 /year [1]. residues and wastes [5]. more than 90 %. drastic conditions such as (ρm.oil ≈ 0. all electrons oc- ter [6]. gen cyanide. biogas with a heating value of 10085. (δC = −0. ρe. sists of a central carbon atom surrounded by four hydro- pending on the raw material digested. sion routes existed to convert natural gas/methane right The difficulties of methane activation discussed above at the wellhead into transportable liquids (methanol. losses. Why is this so? Methane con- gestion of energy crops. of CH4 oxidation to CH3 OH on Fe-ZSM-5 catalysts in- dicate that this mechanism could also be operational in The reason for this wasteful handling is of economic heterogeneous catalysis[10]. If the inert CH4 molecule can be activated. cooking and transporta. The mass and energy density of natural gas Whatever way is chosen. Other countries in possession of huge shale gas resources. Alterna. and the reaction with ammonia to hydrogen cyanide. eliminating the expenses of inter. 2 Challenges in Methane Activation turing triggered the so called ‘shale gas revolution’ [4]. way of methane activation is the homolytic C–H bond timates exist that about 100 · 109 m3 /year natural gas cleavage and hydrogen atom transfer to a radical as are flared world wide [7] which is about 3 % of the reaction partner. gen atoms forming a regular tetrahedron (pointgroup centration in biogas ranges from about 50 % to 70 % Td .g. CH2 Cl2 and CHCl3 . autothermal reforming or partial ox- istry with focus on heterogeneous catalysis. hydro. are missing.9 kg·dm−3 . A declining extremely weak acid (pKa ≈ 40) rendering methane ac- but still significant amount of natural gas is flared in tivation by acid/base catalysis difficult.2 Raimund Horn. it can be seen that both numbers are of gen atom were reactive in this transformation. the dipole moment vanishes.. steam reforming.046) (Hirshfeld method [8]). ρe. Finally. C–H bond length 1. If economic conver. In par. the ing handling and transportation in pipelines or LNG. The most prominent use of methane in the of chemicals and fuels. The purpose of this review is to chemical industry is for synthesis gas production by provide a subjective account on today’s methane chem. Despite its vast availability. by volume. acetylene and in minor amounts to chlo.. Iran. Robert Schlögl from shale rock in the United States by hydraulic frac. China. According to the ‘EurObserv’er’ barome. The most facile countries like Russia. is resistant to nucleophilic attacks because electron do- ticular. Iraq and others. The carbon atom is slightly negatively charged could also become a chemical feedstock in the future. Es. bond angle ∠109. Methane to create energy for heating. The four C–H bonds are very ing to 1. a mixture of CH3 Cl. Schwarz et al. methane par- tify higher transportation costs as well. more reactive target molecules will be even more readily tankers comparatively expensive. tial combustion or electrothermal pyrolysis to acetylene apart from methane conversion to synthesis gas.) less natural gas would be flared. Results the same order. biogas is almost stable (∆d H = 440 kJ · mol−1 ) and only weakly po- exclusively used for energy production but bio methane larized.oil ≈ 40 MJ·dm−3 ) mak. De. ysis in the 21st century. Nigeria.

1). The same and microkinetic modeling. methane. Jones In methane steam reforming. [19] been discussed in detail in several excellent reviews [14– 16] and books [17. CO2 . The reaction is highly en. 1) and the comes rate limiting at higher temperatures in line with watergas shift reaction (Eq. As. research results and challenges with focus on hetero. include an estimated 0. Both. 21]. experimental results and theroretical cal. Ni based catalysts are used in growth could be formulated [22]. Bengaard et al. for example steam reforming (Eq. Only some recent developments. SiO2 and alkali met- ∆Hr◦ (298 K) = −41 kJ · mol −1 als. line with experimental data presented in the same pa- per even though the TOF values were not quantita- tively reproduced. Sehested [21] showed that Ni-deactivation oc- metals.Methane Activation by Heterogeneous Catalysis 3 methanol or Fischer-Tropsch synthesis. ii) carbon blockage H2 O(g) + CO(g)  CO2 (g) + H2 (g) (2) and iii) poisoning by S. for steam reforming on these metals and concluced that dothermic and limited by thermodynamic equilibrium. Jones et al. CH4 (g) + H2 O(g)  CO(g) + 3H2 (g) (1) The major challenge in steam reforming remains −1 ∆Hr◦ (298 K) = +206 kJ · mol catalyst deactivation by i) sintering. CO formation C∗ + O∗  CO∗ + ∗ is the rate limiting Two stoichiometrically independent reactions can de. Much insight has been gained on Ni-deactivation from in situ TEM and DFT studies [14. a mixture of H2 . the experimental results obtained by Wei and Iglesia at 823 − 1023 K [20]. step at the investigated temperature of 773 K but that scribe the mole number changes of the five species in. S and Au on Ni-particles to calculate a 2D-volcano plot showing the turn over and there is theoretical evidence that these additives . The calculated reactivity order was in following.2 eV uncertainties in the adsorption Syngas production is a mature technology and has energies. 1 Two-dimensional volcano-plot of the turn over fre- needed for production of liquid fuels by Fischer-Tropsch quency (log 10) as a function of O and C adsorption energy. hydroformula- tion reactions or the CO is removed to produce pure hydrogen for ammonia synthesis or hydrogenation re- actions. Increasing amounts of synthesis gas are Fig. idence that Ni–OH is most likely the carrier for Ni-atom Co and Fe are also active but prone to oxidation under migration and a mathematical model for Ni-particle reaction conditions [14]. TOF values increased linearly with 3. showed that graphene layer growth on Ni(111) origi- By combining DFT calculations. 18]. DFT calculations gave ev- intermediate activity and Pt and Pd are less active [19]. P. The error bars synthesis (40·106 t world GTL plant capacity 2011[13]).1 Steam Reforming dispersion indicating a structure sensitive reaction with stepped sites being more active than terrace sites. curs both by particle migration and coalescence but culations show that Rh and Ru are the most active also by atom migration from small particles to larger transition metals for steam reforming. [19] also reported an elementary step mechanism a mixture of CO. H2 . viz. is a key intermediate in the chemical in- dustry and is produced from methane catalytically by steam reforming. 3 Progress in Heterogeneous Catalytic Syngas Production Synthesis gas (short syngas). autothermal reform- ing or partial oxidation. The hydrogen used for am- monia production (198 · 106 t NH3 in 2012 [11]) and the syngas for methanol production (65 · 106 t CH3 OH in 2013[12]) stems almost exclusively from natural gas. [19] were able authors studied adsorption of K. scaling relations nates from Ni(211) steps as nucleation sites. dissociative CH4 adsorption CH4 + 2∗  CH∗3 + H∗ be- volved. 2). [23] industry due to the high price of Rh and Ru. 10 % conversion. p = 1 bar. T = 773 K. frequency as function of the O∗ and C∗ adsorption en- geneous catalysis will be selected and discussed in the ergies (Fig. For ex- Steam reforming is catalyzed by group VIII transition ample. dry reforming. Pb. Ni and Ir show particles (Ostwald ripening). CH4 reacts with H2 O to et al. Figure reproduced from Jones et al. CO and some CO2 .

3). surface defects such hydrocarbons are to be produced by Fischer-Tropsch as steps are more reactive than closed packed transi- synthesis. Polanyi relation with the total adsorption energy of a Both methane pyrolysis (Eq. methane literature that CO2 activation proceeds through elec- dry reforming is of general interest to the chemical in. At re- both molecules on transition metal surfaces has been action temperature of dry reforming CO2 dissociates studied in great detail. Because a low work steam reforming which is desirable. These features are attributed their calculations. Adopted from [25] CH4 (g) + CO2 (g)  2CO(g) + 2H2 (g) (3) ∆Hr◦ (298 K) = +247 kJ · mol−1 In this highly endothermic reaction. Methane activation on transi. Instead solar-thermal reactors are an interesting development [24] and could be used in the future. Hence it was concluded that minute amounts of these promotors could make steam reforming catalysts resistant to coking. The examples listed above show how novel exper- imental and theoretical methods provide new insight into atomistic details of catalytic reactions and pave the way for improvements even to such established tech- nologies like methane steam reforming. 5) are potential sources of carbon for- At high kinetic energies (high temperatures) the pre. at the surface to CO and O. through an energy barrier [25]. tion metal surfaces [29].g. [30] computed the entire reaction pathway and barrier. e. CH4 (g)  C(s) + 2H2 (g) (4) −1 27]. CO2 dissociates at the surface to CO to a precursor mediated dissociation (PMD) mecha. Robert Schlögl bind to step sites as well. increasing environmental awareness. and O while CH4 dissociates sequentially to CH + 3H. 3 Simplified Mechanism of CO2 Reforming on Ni(111). [26. nism of the rate limiting step in which CH4 (ads) → CH + O form CHO which splits off the remaining H CH3 (ads) + H(ads) occurs by tunneling of an H atom atom. has rekindled at T = 500 K and the sum of the H and CH3 adsorption interest in methane dry reforming (Eq. equlibrium (Eq.2 Dry Reforming In recent years. In order to achieve a net CO2 con- Fig. 2CO(g)  C(s) + CO2 (g) (5) CO2 activation on transition metal surfaces is also a −1 structure sensitive reaction. mation [28]. According to kinetic isotope effect [25]. 4) and the Boudouard CH3 fragment and an H atom as catalyst descriptors. Strong evidence exists that the reaction is structure ∆Hr◦ (298 K) = +75 kJ · mol sensitive[28]. version. By means of DFT. The biggest challenge for catalysis research in dry the rate constant for PMD follows a Brønsted-Evans. reforming is catalyst deactivation by carbon blockage. energies (in eV). two strong green- house gases. The COδ− 2 precursor anion can CH4 activation. the heat of reaction must not be created by Adopted from [30] burning fossil fuels. if long chain function enhances charge transfer. dissociation (DD) mechanism as indicated by molecular beam and thermal bulb experiments of Seets et al. a low sticking coefficient and a high hydrogen energetics for CO2 reforming on Ni(111). Temperatures above 1000 K and excess cursor mediated dissociation shifts gradually to a direct CO2 are required to reduce carbon formation [31]. 3. CO2 activation and the reaction of only be observed far below room temperature. As shown in Figure 2. Figure 3 summarizes this simplified mechanism. CO2 and CH4 are converted to syngas which can be used for methanol production or Fischer- Tropsch synthesis. 2 BEP relationships between the rate constant (in s−1 ) particular with view on global warming. Broad agreement exists in ∆Hr◦ (298 K) = −171 kJ · mol .4 Raimund Horn. in Fig. tron donation from the transition metal to the CO2 dustry because it delivers a lower H2 /CO ratio than molecule forming a COδ− 2 anion. Aside from environmental aspects. Wang tion metal surfaces is characterized by a high activation et al.

g. are nucleation sites for methanol oder FT-synthesis. Oxygen-blown auto thermal re- forming of natural gas (methane) is the syngas pro. catalytic fixed bed reactor to a mixture of H2 and CO face is rather resistant with respect to carbon forma. ATR-catalysts In literature. CO2 reform- ing (Eq. 11) was not observed. Ru and non-noble metals like H atoms remove carbon deposits efficiently. From reactor exit ing and burner design.4 − 0.0 [35]. Spatially resolved XAS- and oxygen (or air) are premixed and converted in a measurements show the Rh oxidation state as function . which are often close to thermodynamic equilib- more on the side of minimizing pressure drop and find. An ∆Hr◦ (298 K) = +247 kJ · mol−1 ATR-reactor consists of a specially designed burner in CO(g) + H2 (g)  C(s) + H2 O(g) (12) which a sub-stoichiometric feed of natural gas. The syngas leaving the CO(g) + 0. ∆Hr◦ (298 K) = −803 kJ · mol LaNi1−x Cox O3 and La1−x Srx Ni1−y Coy O3 release nano. al.5O2 (g) → CO2 (g) (15) ATR-reactor has a temperature between 850−1100 ◦ C. CH4 (g) + 1/2O2 (g) → CO(g) + 2H2 (g) (7) particles of the corresponding transition metals under −1 ∆Hr◦ (298 K) = −36 kJ · mol CO2 reforming conditions and show stable reforming activity and syngas selectivity at high CO2 conversion [34]. CH4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(g) (6) −1 cursors such La1−x Srx NiO3 . The products. H2 O and CO2 are side carbon growth causing catalyst deactivation [32]. Ir. methane at the catalyst surface [38]. −1 ∆Hr◦ (298 K) = −283 kJ · mol is in thermodynamic equilibrium and basically free of higher hydrocarbons and soot-precursors[14]. steam −1 and oxygen (H2 O/C = 0. Catalysts for CPO are group VIII noble met- calculations of Wang et al. 7) vs. H2 (g) + 0. CH4 (g) + CO2 (g)  2CO(g) + 2H2 (g) (11) duction method of choice for large-scale FT-plants. CH4 (g) + O2 (g) → CO2 (g) + 2H2 (g) (8) −1 ∆Hr◦ (298 K) = −319 kJ · mol CO(g) + H2 O(g)  CO2 (g) + H2 (g) (9) 3.3 Autothermal Reforming (ATR) −1 ∆Hr◦ (298 K) = −41 kJ · mol Low temperature FT-synthesis of wax and diesel on CH4 (g) + H2 O(g)  CO(g) + 3H2 (g) (10) shift-inactive Co-catalysts requires syngas with a H2 /CO ∆Hr◦ (298 K) = +206 kJ · mol−1 ratio close to 2. Pd. ing the optimum pellet shape for minimizing intraparti. in a ratio of nearly 2 : 1. the syngas formation pathway cannot be judged. route (Eq.Methane Activation by Heterogeneous Catalysis 5 While the closed packed and defect free Ni(111) sur. thought to play a role in methane CPO. In CPO. Pt. erated Rh and Pt coated α − Al2 O3 foam catalysts show that H2 and CO are formed in a short oxidation zone at the entrance of the foam and upon complete 3. at Ni(211). Challenges in catalyst design lie data. Due to the high operation temperature. steps. La2−2x Sr2x NiO4−δ . The formation of H2 in Catalytic Partial Oxidation (CPO) of methane is a presence of gas-phase O2 is due to a strong film trans- promising but not yet industrially applied method for port limitation leading to a vanishing O2 concentration converting methane to synthesis gas. [30] show that surface O and als such as Rh. Enger et. steam reforming. e.5O2 (g) → H2 O(g) (16) −1 The catalyst used in ATR-reactors is in most cases ∆Hr◦ (298 K) = −242 kJ · mol Ni supported on magnesium alumina spinel (MgAl2 O4 ). Eq. favorable for downstream tion [30].5.5 − 3. a combus. CH4 (g)  C(s) + 2H2 (g) (13) tion chamber in which slower homogeneous gas-phase ∆Hr◦ (298 K) = +75 kJ · mol −1 reactions like CO oxidation. rium.4 Catalytic Partial Oxidation O2 consumption by steam reforming [37]. Perovskite based pre. Ni and Co. Research chal. syngas formation by methane CPO ist are less prone to poisoning and deactivation than the often discussed in terms of a direct partial oxidation Ni-catalyst in a primary steam reformer. nation of Eq. watergas 2CO(g)  CO2 (g) + C (14) shift and pyrolysis occur and a heterogeneous catalytic −1 zone in which methane and higher hydrocarbons are ∆Hr◦ (298 K) = −172 kJ · mol removed by steam reforming. Spatial profile measurements through adiabatically op- cle transport than on new catalyst formulations. ing resistant dry reforming catalysts builds on the idea that very small metal nano-particles are less prone to coking than larger particles [33]. [36] listed reactions that are One currently followed approach to synthesize cok.6) is ∆Hr◦ (298 K) = −131 kJ · mol burned at temperatures of 2500 ◦ C or more. O2 /C = 0. 6. 11). a combustion-reforming route (combi- lenges in ATR lie mainly in the field of reactor engineer. 10 and Eq.

Adopted from [37] 4 Direct Conversion of Methane to Chemicals of the oxygen concentration in the gas stream [39]. Pure O2 is the preferred oxidant for methane CPO but air separation is costly. e. methyl is extremely fast and mass and heat transfer artifacts bromide and benzene. still at the research stage. very detailed elementary step mi- crokinetic models were postulated based on hierarchical multiscale modeling.6 Raimund Horn. Hence integrated O2 /N2 separation.5 wt% Rh/Al2 O3 . such as Rh [40. temperature and coke resistant CPO catalysts are required. methane to chemicals such as hydrogen cyanide. can hardly be eliminated. 4 Spatially resolved species and temperature profiles for methane CPO on Rh/α−Al2 O3 foam catalysts at CH4 /O2 = 2. On Rh. Robert Schlögl Fig. methyl chloride. 41] and Pt [42. 44]. 43].5 mm diameter fixed bed CPO reactor filled with 2.7 slpm flow rate. What are the challenges in future CPO research? In industrial reality methane CPO would have to be conducted at pressures between about 20 bar for down- stream FT-synthesis and 50 bar for downstream methanol synthesis. Rh is in the oxidation state Rh3+ lenges in catalytic conversion of methane to synthesis but becomes gradually reduced with decreasing O2 con. Rh3+ . with the ex- unified mechanistic picture for methane CPO could be ception of HCN synthesis. model predictions are in excellent agreement with experimental data [38. On Pt.e. From the catalyst per- spective. gas. 5 Distribution of oxidized Rh-species (i. Pt nanoparticles embedded in a high tem- perature stabilized barium hexaaluminate support [47] or nobel metal free catalysts such as Co/Ca/Al2 O3 [48] are interesting developments. agreement between elementary step models and experimental data is less good [45] mainly due to deac- tivation of Pt by coking at low oxygen partial pressure being not yet included in the kinetic model.0 and 4. Compared to syngas production. ethy- Kinetic studies render difficult because methane CPO lene. Now we focus on direct conversion pathways of centration and increasing H2 concentration to Rh metal. 1. In Chapter 3 summarized status quo and research chal- the oxidation zone. On selected systems.g. blue) in a 10 mm long. by membranes would be highly desirable[46]. red) and reduced Rh-species (i. formaldehyde. Adopted from [39] formulated yet. methanol.e. Rh0 . As reviewed by Enger [36] no direct methane conversion processes are. Fig. 41. . The safe premixing of O2 and CH4 at elevated pressure remains a safety issue.

8 s CH4 (g) + NH3 (g) → HCN(g) + 3H2 (g) later than CH4 . showing that H2 ad- is formed. In the . The exothermic cess to date. CH4 (g) + NH3 (g) + 3/2O2 (g) → HCN(g) + 3H2 O(g) They suggest that HCN formation occurs through the (18) following pathways: ∆Hr◦ (298 K) = −481 kJ · mol−1 N∗ + CH∗ → HCN(g) + 2∗ (19) ∗ ∗ The endothermic BMA process is conducted in exter. The lower sequence is purely catalytic. Because H2 is formed as a HCN + H2 in the gas-phase. Adopted from [53] al. In an be sufficient. Eq. H2 acts as sacrificial fuel reducing NH3 experimental study by Horn et al. process was suggested by Schuurman et al. Schwarz et al. [51] concluded that CH4 adsorbs and ∆Hr◦ (298 K) = +251 kJ · mol−1 dissociates rapidly on Pt while NH3 dissociation is slow.8 s after an NH3 pulse and a slow HCN formation if NH3 was pulsed 0. H2 C=NH was indeed detected 4. HCN formation rate by several orders of magnitude. By combining ex.1 Methane to Hydrogen Cyanide to be studied. [49]. To which extent OCM with Dioxygen The direct conversion of methane the upper and lower HCN formation sequences in Fig. Ni and Re and also alternative supports such established processes conducted essentially unchanged as Si3 N4 or SiC have a positive effect on the HCN since decades. marized in Figure 7. Compared to syngas formation relatively yield [52].and the Andrussow process are industrially as Ir. alyst. Au. 6 Mechanism for the platinum-catalyzed Rh gauze catalyst proposed by Kondratenko [53] based on methane/ammonia coupling proposed by Schwarz et TAP and isotope labeling experiments. Much atomistic insight on the BMA process came Hence the Andrussow-Process uses adiabatically oper- from the work of Schwarz et al. 6) in which HCN Schmidt et al. [49]. [49]. acting gases in a model BMA reactor were quenched and analyzed by molecular beam mass spectrometry and threshold ionization. On the practical side. The upper sequence involves dehydrogena. Both. [51] based nia in absence of oxygen (BMA-process. 7 Reaction network of the Andrussow process on a Pt- Fig. Adopted from [49] contribute to the overall HCN formation rate remains 4. a recycle would reaction. 18). the result of identified two reaction sequences (Fig. [54] is important. [50] in which the re. mation upon admitting a CH4 pulse 0. ance and regression trees revealed that additives such the BMA. However. an almost thermoneutral side product in the Andrussow process. ated catalytic gauze reactors with Pt/Rh gauzes as cat- periments in a Fourier Transform Ion Cyclotron Reso. little fundamental or applied research has been devoted Addition of oxygen to a CH4 /NH3 feed enhances to HCN synthesis. A different HCN formation pathway in the BMA- Hydrogen cyanide is formed from methane and ammo. labeling provided interesting insight into the reaction tions on the reaction of methane and ammonia with Pt+ network of the Andrussow process [53] which are sum- ions as model catalyst in the gas-phase. tion combined with genetic algorithm. high throughput experimenta- Andrussow process uses adiabatic catalytic gauze reac.Methane Activation by Heterogeneous Catalysis 7 Fig. CN + H → HCN(g) + 2∗ (20) nally fired tubular reactors at about 1200 ◦ C with a Platinum remains the best catalyst for the BMA pro- Pt catalyst coated to the tube wall.2 Methane Oxidative Coupling (OCM) in the gas-phase supporting the dehydrogenation step proposed earlier by Schwarz et al. analysis of vari- tors (Pt/Rh gauzes) at millisecond contact times. 17) or in on TAP experiments. dition increases the HCN selectivity from 74 to 82 % tion of the intermediate methanimine H2 C = NH → in the Andrussow Process. conversion and N2 formation. From this and other TAP experiments (17) Schuurman et al. TAP experiments in combination with isotope nance (FTICR) mass spectrometer and B3LYP calcula. They observed a rapid HCN for- presence of oxygen (Andrussow-process. 6 to ethylene would be of high industrial interest. Eq.

Ac. the conventional technology for Li/MgO was reviewed [66] and studied again in great ethylene production. spectroscopy [61. is shown in Eq. Both on The most severe technological barrier in terms of a Li-doped MgO film grown on a Mo(001) substrate but process development is the insufficient selectivity of all also on Li-doped MgO powders surface segregation of tested OCM catalysts at industrially relevant conver.0. All catalysts were research articles and about 140 patents at that time. called Oxidative Coupling of Methane (OCM). Li+ O− sites were up company called Siluria Technologies announced the thought to be the active centers without that there ex- completion of an OCM demonstration plant in fore. to naphtha reforming. and contact times from 0. ists any proof in literature that these sites exist under seeable future using novel nanowire catalysts [59]. not only CH4 but also under reaction conditions rendering Li/MgO and also the coupling products C2 H6 and C2 H4 are activated on other Li-based OCM catalysts unusable for process de- the catalyst leading to decreasing selectivity at increas. data of OCM catalysts and identified those for which p(CH4 )/p(O2 ) = 1. vation on OCM catalysts remains open. CH3 · radicals to the gas-phase where they couple to sulted so far. 21. cording to Siluria. According to homogeneous’ reaction. 9 shows the surface of such a Li-doped catalysts reported in literature that were scrutinized MgO-film upon heating to 700 K and 1050 K. ity and the CH3 · productivity was observed [65] leading mon is that all were oxides. itive effect on the OCM activity. Zavyalova and Baerns [57] reviewed the vast OCM literature in 2011 and reported more than 2700 Fig. methane (Eq. higher than 80 % at more than 5 % CH4 conversion [58]. Figure adapted from [57]. It can be summarized that Li- limit between 25 % and 30 %. Hence. no industrial process re. The identity of the active site for methane acti- Mechanistically OCM is discussed as a ‘heterogeneous. the C2 productiv- overcoming this limit.2 to the sum of methane conversion and C2+ selectivitiy was 5. C2 H6 . OCM reaction conditions. The re- action. OCM research has gained momentum again.7 − 9. to the conclusion that the Li/MgO catalyst released Despite intense research. no performance data or detail but neither experiment nor theory gave evidence any further information about the catalyst was revealed. This mechanistic pictures was Schwarz [68]. Robert Schlögl early 1980s.8 Raimund Horn. 22). However. defect formation on the MgO surface which has a pos- ready in 1988 [60] based on kinetic arguments that rad. velopment. Keller and Bhasin [55] as well as Hinsen and Baerns [56] reported that ethylene is formed from methane and oxygen on a variety of metal oxide cata- lysts at temperatures between 500 − 1000 ◦ C. Li was observed above 700 K and Li-desorption above sion levels. tested in a fixed-bed reactor in a co-feed mode under at- Already in 1993 Maitra reviewed global performance mospheric pressure at temperatures from 943 K to 1223 K. Fig. The for- by Zavyalova and Baerns [57] for being measured in ki.5 s. S-data of the best OCM 1050 K. ing conversion. that Li+ O− exists under OCM conditions [67]. oxygen centered radicals on metal ox- based on the detection of CH3 · radicals over Li/MgO ides are active for homolytic hydrogen abstraction from and Sr/La2 O3 OCM catalysts during reaction by EPR. 64]. 62] or molecular beam mass spectrom- etry [63. The only thing they have in com. Maitra listed 283 chemically vastly different materials concentration in Li/MgO catalysts. a San-Francisco based start. Indeed an inherent yield doping leads to a pronounced morphology change and barrier of about 30 % was predicted by Labinger al. 8 Elemental compositions of OCM catalysts with Y (C2 ) ≥ 25 % reported in the literature. These data indicate that angular surface defects left behind upon Li-desorption C2 selectivity (C2 H4 + C2 H6 ) decreases with increas. Only recently. are clearly seen and in line with ab-intio thermody- ing CH4 conversion resulting in a virtual one pass yield namic calculations [67]. Figure 8 shows X. the primary coupling product. However. the initially ical H· abstraction is insensitive to the nature of the high OCM activity cannot be sustained due to Li-losses hydrocarbon molecule. CH4 (g) + 1/2O2 (g) → 1/2C2 H4 (g) + H2 O(g) (21) −1 ∆Hr◦ (1073 K) = −139 kJ · mol Since this pioneering work OCM has been studied in- tensely. An apparent correlation between the Li MO · +H − CH3 → MO − H + CH3 · (22) . the technology would be superior Recently. mation of Li-rich surface oxides patches and the rect- netically sound experiments.

the unpaired electron formed in this reaction in Ar. tal oxidation to CS2 is considerably reduced. methane overoxidation to CO or CO2 is high. the cou- pling of two CH3 · radicals in the gas-phase is a rather inefficient step because a third collision partner is re- quired to carry away the excess energy CH3 · +CH3 · +M → C2 H6 + M∗ while the gas-phase oxidation steps of CH3 · radicals to HCHO forming finally H2 and CO are bimolecular. A linear but inverse relation between as a superoxide species in a very exothermic reaction the metal-sulfur bond strength. but the driving force for to- summarized by Equation 23. CH3 · + · O2 H → CH3 O · +OH·. [65]. Neurock and Marks [71] pro- show that Li+ O− MgO sites would be overly reactive posed elemental sulfur as a ‘softer’ oxidant for selec- for homolytic C–H cleavage with an activation barrier tive methane conversion to ethylene.g. known Mg O MgO + H − CH3 → HO− (Mg − CH3 )+ MgO  2+ 2−    as desulfurization catalysts in the petrochemical indus- (23) try. e. 11. such addition on an Mg2+ O2− pair. Eq. without any coreactant. CH4 /S = 5. [69] ing this line of thought. 24) such that the overall reaction (Eq. TiS2 and PbS. activation barriers and rate constants. and hence much more efficient.8) and that the active sites comprised on the magnesium ion could facilitate O2 chemisorption S–S pairs [71]. In fact. recent calculations by Sauer et al. 10 and temperatures. without Fig. showed activity and selectivity for sulfur mediated coupling of methane to ethylene. However. 1073 K. Fig. C2 D6 . HO− (Mg·− )+ MgO + O2 → O·− HO− Mg2+ MgO     2 (24) ·− −  2+ 2−   2+  Mg O MgO + CH4 + O2 → O2 HO Mg MgO + CH3 · (25) If one of these. simulations are of little value. phase or at the catalyst surface cannot be concluded from this product pattern and also not from the mere detection of gas-phase CH3 · radicals. Follow- On the other  hand. the oxidation of methane to ethylene by el- sults point to an alternative methane activation path. Figure adapted from [67]. Figure adapted from [69]. Instead the calculation re. Detailed microkinetic simulations combining surface and gas-phase reaction steps will be necessary to explore the heterogeneous- homogeneous nature of OCM further. 10 Reaction energy diagram for chemisorption of CH4 sound knowledge of the active center. 9 STM image of a 12 ML thick oxide film prepared by co-depositing Li and Mg in an O2 ambience after annealing However. Ab initio DFT calcu- CH3 · radical desorption requires 228 kJ · mol−1 and lations showed that all transition metal surfaces were would be. emental sulfur is thermodynamically feasible at high way on steps and corners of MgO shown in Fig. Transition metal sulfides like MoS2 . 25) would become almost thermoneutral.Methane Activation by Heterogeneous Catalysis 9 (−191 kJ · mol−1 . CD3 CH3 . OCM with Sulfur From a thermodynamic point of view. in Fig. RuS2 . e. surface elemen- onto corner/edge sites of a Mg9 O9 cluster showing C–H bond tary steps. The involvement of CH3 · radicals seems certain because la- beling experiments with CH4 /CD4 mixtures led exclu- sively to symmetrically substituted coupling products C2 H6 .g. 10). This mode of  methane activation would be in line with O2 is a very strong oxidant and the driving force for + − the Li O MgO site postulated by Lunsford et al. B3LYP energies in kJ·mol−1 . C2 H4 . CH2 CD2 and C2 D4 [70]. the rate of methane . both or another mechanism is respon- sible for methane activation remains subject to fur- ther studies including also more complex catalysts than Li/MgO such as Na2 WO4 /Mn/SiO2 for example. As summarized as low as 27 ± 7 kJ · mol−1 . highly sulfided under experimental conditions (5 % CH4 However. hardly feasible (Fig. whether this coupling step occurs in the gas- to 700 K and 1050 K (inset).

PbS showed the tions [76]. Modern experimental and theoretical methods pro- both are even further away from practical application vide molecular insight into methane activation on silica . Isolated monomeric transition metal ox- that should be followed on in the future. short residence times and the addition of steam have a positive effect on formaldehyde selectivity. ide species. MoOx /SiO2 and VOx /SiO2 are among (CH2 –S∗ . methane oxidative coupling to ethylene 48 [77]. k2 will be larger than k1 (typically k2 /k1 > 20) and methanol or formaldehyde yields will be a few percent at best. CH4 (g) + 1/2O2 (g) → CH3 OH(g) (26) −1 ∆Hr◦ (298 K) = −126 kJ · mol CH4 (g) + O2 (g) → CH2 O(g) + H2 O(g) (27) −1 ∆Hr◦ (298 K) = −368 kJ · mol Nature is far ahead of chemists and catalysis researchers for methanotrophic bacteria utilize methane as carbon and energy source with methane oxidation to methanol being the first step in their metabolism [72]. Even Formaldehyde with engineering ‘tricks’ such as formaldehyde quench- ing by water film adsorption on cooled reactor parts [82.2 % C2 H4 selectivity. heterogeneous catalysis but despite decades of research. among the four sulfides tested. 27) are ‘dream reactions’ for for process development. Robert Schlögl than OCM. VOx /MCM- Nevertheless. Methane Oxidation to Formaldehyde As reviewed by Vekki and Marakaev [74]. Off course.3 % CH4 conversion Higher HCHO space time yields than on precipi- and 18. VOx /SBA-15 [79]. best performance with about 15. Figure taken from [71]. these value are tated silica are obtained if mesoporous silica is used as very low are and far beyond any commercial interest. CuOx /SBA-15 [80] and FeOx / using sulfur as soft oxidant is an interesting strategy SBA-15 [81]. As the C–H bond strength in H–CH2 OH (≈ 95 kcal · mol−1 ) and in H–CHO (≈ 87 kcal · mol−1 ) is lower than in H–CH3 (≈ 105 kcal · mol−1 ). 78]. 12 suggest that PbS seems to make a oxidation to formaldehyde [75] and because ii) gas-phase good compromise between activity and selectivity and reactions occur in parallel to catalytic surface reac- indeed. support such as in VOx /MCM-41 [77. Figure the most thoroughly studied catalysts but formalde- taken from [71]. also on mesoporous catalysts the one pass 4. Fig. 12). The DFT nearly the same activity/selectivity pattern for methane results in Fig. Nevertheless. 12 DFT calculated activation barriers for methane C–H oxidation catalysts are uninspiring from an application activation (blue) and the coupling of methylene intermediates point of view. high temperature methane oxi- k 1 k2 dation is a consecutive reaction (A −→ B −→ C) pro- ceeding via homolytic C–H bond cleavage. 11 Gibbs free energy changes for methane oxidation by There is little hope that high temperature hetero- S2 (red) and O2 (blue) to C2 H4 and further to CS2 and CO2 geneous catalytic pathways will ever lead to acceptable respectively. hyde yields are on the order of 3−4 % at best. 26) 83] or reactant recycle [84] these values are still too low and/or formaldehyde (Eq. It is diffi- cult to assess the catalytic performance of MoOx /SiO2 and VOx /SiO2 catalysts and to establish structure ac- activation (CH4 conversion) and the rate of CH2 cou- tivity correlations because i) the SiO2 support shows pling (C2 H4 selectivity) was found (Fig.3 Methane Oxidation to Methanol and yields to formaldehyde are on the order of 3 %. methanol or formaldehyde yields because. as pointed out by Labinger [73].10 Raimund Horn. the results for gas-phase methane oxidation to formaldehyde on classical heterogeneous Fig. The direct oxidation of methane to methanol (Eq. red) as a function of the M–S bond strenght.

radical O·t activating methane by homolytic bond cleav- age and releasing a methyl radical into the gas-phase Methane Oxidation to Methanol Compared to methane (Eq. Palkovits et al. 6 − dicyanopyridine (DCP) in molten ZnCl2 . 30): sulfuric acid methanol yields of over 40 % at > 90 % selectivity were obtained (Eq. 14 a) Trimerization of 2. nation of unsatisfactory performance of these materials on the one hand and pointing out more promising re- search directions on the other hand. Periana [90] reported a Pt-based catalyst. 180 ◦ C with a 20 mM concentration of Hg(HSO4 )2 in peting reaction channels (Eq.03 eV) the ing a solid analog to Periana’s (bpym)PtCl2 system branching ratio is 65 % to 35 % respectively. conversion to a covalent triazine-based frame- work (CTF). hydrocarbons at low temperatures and with high selec- ported VOx /SiO2 catalysts the low one pass formalde. 13) was found to react with methane in two com. and subsequent platinum coordination (Pt- CTF). At (Fig. after workup.n = 2. 89]. the Pt-CTF is active in methane oxi- no results yet how the catalytic cycle will be closed and dation in oleum to methyl-bisulfate which. Again deed. discussed above. Dichloro(η− (30) 2−[2. 1) exist. that cleave the C–H bonds of methane and other If Eq. [86]. the [Al2 O3 ]·+ cation C–H activation at temperatures below 200 ◦ C [88]. b) Periana’s platinum bipyrimidine complex. of methane by strong electrophiles is probably the most An alternative and possibly more promising reac. Indeed. much more progress has been made in recent years in selectively oxidizing methane to [(V2 O5 )n (SiO2 )m ]+ + CH4 →[(V2 O5 )n (SiO2 )m H]+ methanol.34 eV vs. Periana showed that polarizable (‘soft’) strong by using a combination of mass spectrometric experi. In- tion channel was reported by Schwarz et al. As and sulfuric acid. adapted from [91]. m = 1 − 4. There are (Fig. oxidation to formaldehyde. the activation of the C–H bond gas-phase. 14). 13 Optimized ground-state structure of [Al2 O3 ]·+ (C2v) as revealed by DFT calculations. given in the reviews by Shilov [87] and Periana [88]. this pathway will result in low formalde. electrophiles such as [XHg+ ] ions in strongly acidic sol- ments and DFT calculations on reactions of CH4 with vents like sulfuric acid react readily with methane via gas-phase metal oxide cluster ions. 28).6-dicyanopyridine in CH2 O directly and because it is energetically favored molten ZnCl2 .Methane Activation by Heterogeneous Catalysis 11 Fig. Figure taken from [86]. A variety of homogeneous metal complexes (n = 1. the blue iso- surface indicates the spin-density distribution. m = 0. This solid ligand coordinates PtCl2 form- (∆E(30) = −2. A detailed account on this kind of chemistry is hyde yields could be the consequence of unselective con. Reaction (30) on the other hand liberates work (CTF) by trimerization of 2. [91] used Periana’s molecular tem- hyde selectivity due to unselective gas-phase radical plate and developed a covalent triazine-based frame- reactions. 29. Fig. 20 − bipyrimidyl])platinum(II)[(bpym)PtCl2 ]. facile and controllable way of methane activation. DFT calculations whether this reaction channel will also function on neu- and mass spectrometric experiments reacting CH4 with tral supported Al2 O3 clusters and on real catalysts but Vx Siy O+ z cluster ions in the gas-phase [85] show that this work might stimulate further research on the selec- these cluster ions possess a terminal oxygen centered tive one-step oxidation of methane to formaldehyde. . ∆E(29) = −1. (28) is the mode of methane activation on sup. Figure supported transition metal oxides providing an expla. tivity. Hg(II)/H2 SO4 [(Al2 O3 )]·+ + CH4 →[(Al2 O3 H)]+ + CH3 · (35 %) (29) CH4 + H2 SO4 −−−−−−−−−→ CH3 OH + H2 O + SO2 (31) [(Al2 O3 )]·+ + CH4 →[(Al2 O2 H2 )]·+ + CH2 O(65 %) Later. As secutive reactions of the generated CH3 · radicals in the outlined in Section 2. which gave 90 % methane conversion at 81 % selectivity to Reaction (29) liberates CH3 · radicals just like the methyl bisulfate which can be hydrolyzed to methanol terminal oxygen centered radicals in Reaction (28). 31) [88. The most promising heterogeneous catalytic + CH3 · (28) approaches today copy concepts from homogeneous or biocatalysis.

CO2 or CH3 OH are released upon ◦ −1 heating in absence or presence of H2 O. is responsible for CH4 activation. 2+ core. Nevertheless. On Cu-ZSM-5. is formed upon reaction with NO [93]. called oxy-chlorination. It was found that the O2 . structure of the active Cu-site was a function of the re- action conditions as summarized in Figure 16. only the reactions with the most thoroughly studied systems. ZSM-5 is the most prominent host lattice but other ze. Fe and Co. (32) and with bromine Eq. i. The reaction of methane with HCl and and desorption of methanol [96].0 kJ · mol ture (Fig. the space time yield of this batch process is much too low and the workup of the intermediate methyl- bisulfate and the re-oxidation of SO2 might be pro- hibitively expensive. (33) are of prac- and EXAFS indicate that a Bis-(µ-oxo)dicopper(III) tical interest. Alternatively. for methane oxidation at an industrial scale. resonance Raman spec- troscopy. most conveniently followed by the CH4 (g) + Cl2 (g) → CH3 Cl(g) + HCl(g) (32) −1 ◦ −1 UV-Vis absorption band at 22700 cm . The extra-framework transition metal ions decom. DFT and normal coor. 4. Eq. idation environment.12 Raimund Horn. disappears ∆Hr (298 K) = −99. cling step. 15 Fiber-optic UV-vis spectra of O2 -activated Cu- ZSM-5 with Si/Al=12 and Cu/Al=0. EPR chlorine Eq. Fluorine is too reactive. ◦ −1 ∆Hr (298 K) = −28. 15). is likewise feasible.6 kJ · mol on reaction with CH4 already at 398 K and methanol CH4 (g) + Br2 (g) → CH3 Br(g) + HBr(g) (33) can be extracted with a 1:1 water/acetonitrile mix. a reaction called oxy-bromination tive Cu sites in Cu-MOR during reaction with methane (OBM. the already known mono-(µ-oxo)-dicopper(II) CH Br(g) + CO(g) + 3H O(g) (34) 3 2 site activates CH4 . Re. It illustrates nicely how heterogeneous catal- ysis can benefit from concepts of homogeneous catal- ysis.e. Certainly. For a large scale process. The work of Palkovits et al. ∆Hr (298 K) = −686 kJ · mol . it is a first example of a hetero- geneous low temperature methane oxidation pathway with a technologically relevant yield. constrained and methyl iodide decomposes at elevated cently Quick X-ray Absorption Spectroscopy was used temperatures. a water stable CuII -oxide species A second interesting low temperature methane ox. 18 O2 oxygen labeling. methane reacts with HBr to follow the electronic and structural changes to the ac. In a dry 2CH4 (g) + 2O2 (g) + HBr(g) → environment. UV-Vis. In later studies. and O2 to CH3 Br. in particular Cu. The catalyst undergoes an activation period but eventually reaches TONs above 250.58 during reaction with CH4 . In a moist ox. 16 Methane activation and product desorption as func- tion of reaction conditions on a Cu − M OR catalyst. Another problem was that about Fig. one of ucts. Methane reacts with all halogens to halogenated prod- olites have been used as well. This site.4 Methane Halogenation and Oxy-Halogenation pose NO and N2 O but also activate O2 as oxidant. [91] is an example of a low tem- perature heterogeneously catalyzed methane oxidation pathway. corrosive and toxic while the dinate analysis was used to refine the active center to reaction of methane with iodine is thermodynamically be a bent mono-(µ-oxo)dicupric site [Cu2 O]2+ [95]. gives methanol. Figure 5−10 wt% of the CTF-Pt catalyst was lost in each recy- taken from [96]. Figure taken from [94]. [Cu2 (µ-O)2 ] . 34). Robert Schlögl Fig. idation pathway is that on zeolite catalysts contain- ing transition metal ions [92].

aromatics. with and without coke removing agents like H2 O. On BaO/SiO2 . halogenation or oxy-halogenation will have to meet the aromatics. Representative of this strategy is the heterogeneous cat- ple. alcohols and liquid hydrocar.5 Methane Aromatization CH3 Br(g) + CO(g) + H2 O(g) → CH3 COOH(g) + HBr(g) (38) The oxidative methane conversion routes discussed in ◦ −1 the preceding Sections 4. heterogeneous catalysts can be used intermediate which is subsequently aromatized at the to convert methane selectively to methyl chloride and Brønstedt acid sites of the zeolite. In reality 1000 h time on stream [103]. However. Recently. structure of the zeolite induces shape selectivity. Selective bromination of methane to methyl like benzene. 39. route they applied led to formation of a Na3 Fe2 (PO4 )3 Re or Co/Ga are among the most active and selective phase which showed even a better catalytic performance MA catalysts. ethers. alcohols. Rh/SiO2 [100] or noble-metal free sup. For exam. The selective formation of CH3 Br is very important A thermodynamic analysis of methane aromatization because CH2 Br2 leads to coking in subsequent reac. is activated at the transition metal ions forming a C2 Hx In summary. troscopy and temperature programmed reduction. By Zeolites doped with transition metal ions are active chance they discovered that the fluoride based synthesis for MA. sum- bromide is possible on SO2− 4 /ZrO2 modified SBA-15 marized by the term ‘methane aromatization’ (MA). 35-37. Methane oxy-bromination (Eq. Molybdenum was methyl bromide which can. network with a pore diameter close to the kinetic di- bons. Mo. ameter of a benzene molecule (∼ 6Å) as in ZSM-5 and . FePO4 /SiO2 was found to be even ∆G◦r (298 K) = +434 kJ · mol−1 more active and selective for methane oxy-bromination (X(CH4 ) ≈ 50 %. ∼ 15 % CH4 conversion at ∼ 98 % combined time on stream [102]. magilov [105]. naphthalene.selectivity to benzene and naphthalene will be possible mally synthesized FePO4 -SBA-15 was stable for even from a thermodynamic point of view [108]. time on stream due to coke formation. Ba or W [101].2-4. 4. challenges of the toxicity and high corrosiveness of the X=Cl. gle step. nonoxidative methane aromatization has severe ported metal-oxide catalysts MOx /SiO2 with M being thermodynamic constraints.all or lowering the oxidation potential of the feed mix- tioned above can be conducted on heterogeneous cata. xylenes etc. proach for methane conversion is using no oxidant at All halogenation and oxy-halogenation reactions men.Br). CH3 OH and CO was obtained for about 25 h ∆Hr◦ (298 K) = +532 kJ · mol−1 time on stream [101]. [108]. As illustrated by by Ru/SiO2 [99]. compared to syngas based processes. a methane con- version of 44 % at a combined selectivity of 95 % to 6CH4 (g)  C6 H6 (g) + 9H2 (g) (39) CH3 Br. W. An alternative ap- recycled. HBr and HCl are liberated and could be molecules because of overoxidation. HZSM-5 and HMCM-22 containing Mo. CO tions. There is also no real cost advantage in substituting established syngas based technology for CH3 X + H2 O(g) → CH3 OH + HX (35) halogenation or oxy-halogenation routes because they CH3 X + CH3 OH → CH3 OCH3 + HX (36) are also multistep processes requiring expensive feed 2CH3 X → CH2 CH2 + 2HX (37) preparation. ture by distributed oxygen supply or milder oxidants. A catalyst with 25 wt% SO2−4 /ZrO2 showed Details on this reaction can be found in reviews by Is- 99 % selectivity to CH3 Br at 69 % CH4 conversion. which can be converted to acetic acid. 34) is catalyzed and CO2 can be found in Ref. Ding et al. The pore sts. ethers or liquid hydrocarbons (Eq. methane-oxychlorination is catalyzed by LaOCl or alytic conversion of methane to a mixture of aromatics LaCl3 [97]. Eq. be transformed into valuable chemicals such as ole. chemicals involved. all potential methane conversion processes based on mediates which can be converted to olefines. MA catalysts are bifunctional. toluene. Mössbauer spec. Bao [106] or Spivey and Hutchings [107]. Methane than the FePO4 phases tested before. hydrother. catalysts [98]. A pore fines. the selectivity to aro- studied the very rich solid state chemistry on bulk model matics is much lower and all catalysts deactivate with iron phosphate catalysts using XRD. [104] carbon formation is inevitable. S(CH3 Br+CO) > 95 %. again by using solid catyl. At similar performance. CH3 Br/CO ≈ If no solid carbon is formed at 1000 K and 1 bar pres- 1) and showed no signs of deactivation during 200 h sure. lysts at temperatures between 450 − 650 ◦ C. CO and H2 O forms. found to be reduced to Mo2 C or MoOx Cy .Methane Activation by Heterogeneous Catalysis 13 Methyl chloride and methyl bromide are valuable inter. reactors and seperation units for each sin- In oxy-bromination of methane a mixture of CH3 Br.4 are thermodynamically ∆Hr (298 K) = −89 kJ · mol feasible but suffer from low selectivities to the target In each case.

Jha. S. rep. T. methane activation is also key if biogas is to 9. Oyewo. BP (2013) further research.C. Tech. J.org 7. The combination channel system which showed even a higher benzene se. M. formaldehyde. The design of coke re- taining single iron sites in a silica matrix. viz. Rogers. [110] are repro. high level computational methods brought about sev- A promising novel high temperature MA route was eral important results in the quest for heterogeneous recently reported by Bao et al. 217 (2007) 3. Weiland.A. CH3 · radicals were detected by vac. Y. 17 The reaction results of methane aromatization over decades. E. one-step methane 11. Due to the chemical Ed. No new process has been de- veloped in the past years converting methane directly to ethylene. the published re- sults are very interesting and will definitely stimulate 1. of methane to aromatics on single iron sites in a sil- eration of CH3 · radicals followed by product formation ica matrix are just a few examples of this successful in the gas-phase.1 % nano-particles as dry reforming catalysts. Hum. Reimer. K. methane could sistant steam reforming catalysts by selective poison- be converted to ethylene and aromatics at > 99 % selec. Aside from the 8. A. hydrocyanic acid. advanced micro- lectivity and more importantly a higher stability than scopic and spectroscopic catalyst characterization and Mo/ZSM-5 (Fig. Schwarz. 51. 849 (2010) importance to secure the future supply of energy. Angew. Makogon. Renew. Holditch. Mo/TNU-9 and Mo/ZSM-5 catalysts at 60 and 300 min.F. Energ. Nature is still far ahead in methane chem- are typical for methane pyrolysis and the absence of istry but catalysis researchers are catching up. Bell. Chem. S.N. catalytic methane activation. X. Reaction steps from methane activation far away from any industrial application. 2. Janicke. If the reaction occurs by radical reactions in the gas-phase the question arises why it would stop at References the stage of naphthalene. 17). 14 (2007) 5 Summary and Outlook 4. J. B.A. Source Part A 29. Fig- ure taken from Reference [109]. inertness of the CH4 molecule compared to the desired Ott.14 Raimund Horn. Int. a closer look into methane activation. However. be used as chemical raw material. (2014). 5544 (2012) 10. Microbiol. Biotechnol. H. Nevertheless.T. Wang. methanol. URL www. shows. [110]. in particular with the aid of heterogeneous catalysts as in the present review. fuels 6. M. to naphthalene were rationalized by DFT-simulations. 85. A. 30(1-28) (2014) Methane activation by heterogeneous catalysis is of great 5. Petrol.. ing. Sci. that enormous progress has MCM-22 seems to be beneficial.A. BP Statistical Review of World Energy June 2013. [109] used been made in terms of understanding and applying con- a Mo/TNU-9 catalyst with a three-dimensional 10-ring cepts of catalytic methane activation. Eng. aromatics or liquid hydrocarbons. Energ. at high and low temperatures become more and more ducible has to be seen. Makogon. The catalyst showed sta. BP. M. Large studies/agriculture/ammonia . Rev. Broctawik. Wood. the molecu- at 48. Q. Chen. approach. most results and developments dis- action conditions and was verified by HAADF-STEM cussed in this review are at a very early stage and and XANES. However. S. Dietl. 225. Robert Schlögl scale industrial methane conversion still relies on syn- thesis gas which can be converted to fuels and chemicals in downstream processes.eurobserv-er. Catal. lar inspired design of supported electrophiles to oxidize ble performance for 60 h time on stream. Ecol. of knowledge based catalyst synthesis. Liu et al. 300 (2004) target products. The reaction methane to methanol or the non-oxidative conversion mechanism was postulated to comprise catalytic gen. very few direct.A.Y. On catalysts con.R. Schlangen. Sus.com/en/market- conversion processes have been realized so far. N. H. At 1363 K methane conversion peaked at 48. 33(1).T. Dawe. uum ultraviolet soft photoionization molecular-beam Apart from methane conversion to synthesis gas and mass spectrometry. The reaction products found transparent. Thomas. Superficially viewed not much progress has been made in industrial methane chemistry since Fig. Appl.ceresana. Oni. J.I.4 % ethylene selectivity. R. 56. acetylene can be attributed to the still moderate tem- perature. URL http://www. J. the molecular details of catalytic methane activation Whether the results of Bao et al. 21 (2011) and chemicals for our modern society. 349 vast reserves and resources of fossil methane in natu. (1998) ral gas. P. perovskite based precursors for coke-resistant Ni tivity. Advances in Quantum Chemistry 33. Fe-site isolation occurred under re.

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