Coal Science

Coal Science

VOLUME 3

MARTIN L. GORBATY

Corporate Research Science Laboratories, Exxon Research and Engineering Company, Annandale, New Jersey

JOHN W. LARSEN

Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania

IRVING WENDER

Chemical and Petroleum Engineering Department, The University of Pittsburgh, Pittsburgh, Pennsylvania

Table of Contents

Cover image

Title page

CONTRIBUTORS

Copyright

Contributors

Preface

Contents of Previous Volumes

Chapter 1: Fischer–Tropsch Synthesis and Some Related Heterogeneous Reactions

Publisher Summary

I INTRODUCTION

II ADSORPTION OF REACTION COMPONENTS

III INTERMEDIATES AND MECHANISMS OF THE FTS OF HYDROCARBONS

IV KINETICS AND PRODUCT DISTRIBUTION

V SOME PARTICULAR CATALYTIC EFFECTS

VI SOME PROBLEMS OF THE ACTIVITY OF METALS

VII SYNTHESIS OF OXYGENATES

VIII CONCLUDING REMARKS

Chapter 2: An Essay on the Organic Geochemistry of Coal

Publisher Summary

I INTRODUCTION

II PEAT ACCUMULATION: THE ORIGINS OF COALS

III GEOLOGICAL FACTORS IN COAL CHEMISTRY

IV ORGANIC GEOCHEMISTRY OF THE PRECURSORS OF COAL MACERALS

V SOLUBLE BIOLOGICAL MARKERS IN COALS

VI STRUCTURAL FEATURES OF VITRINITE MACERALS

VII FUNCTIONAL GROUPS

VIII EXTRACTABILITY OF COALS AND REDUCTION PRODUCTS: THE EXTRACTS

IX MOLECULAR WEIGHT DETERMINATION FOR COAL DERIVATIVES

X THE STRUCTURE OF COAL: AN ATTEMPT AT A NEW SYNTHESIS

XI SOME FURTHER COMMENTS ON THE GEOCHEMISTRY OF MACERALS

XII THREE MAJOR STUDIES OF COAL GEOCHEMISTRY

XIII A FEW REMARKS ON THE GEOCHEMISTRY OF MINERAL MATTER IN COALS

XIV THE PRINCIPAL NEW DEVELOPMENTS

ACKNOWLEDGMENTS

Chapter 3: Oxygen in Coals and Coal-Derived Liquids

Publisher Summary

I OXYGEN IN COAL STRUCTURES

II OXYGEN IN COAL-DERIVED LIQUIDS

III ROLE OF OXYGEN FUNCTIONALITIES IN COAL LIQUEFACTION

IV THERMAL REACTIONS OF OXYGEN COMPOUNDS RELATED TO COALS AND COAL LIQUIDS

V CATALYTIC HYDROGENOLYSIS OF OXYGEN COMPOUNDS IN COAL LIQUIDS

VI HYDROGEN CONSUMPTION AND COKE FORMATION IN COAL LIQUID UPGRADING

VII ALTERNATIVE METHODS FOR REMOVING OXYGEN COMPOUNDS FROM COAL-DERIVED LIQUIDS

Chapter 4: Coal Conversion in Carbon Monoxide–Water Systems

Publisher Summary

I INTRODUCTION

II BACKGROUND

III AQUEOUS COAL CONVERSIONS

IV CONVERSION MECHANISM

ACKNOWLEDGMENT

ADDENDUM TO AN ESSAY ON THE GEOCHEMISTRY OF COAL BY PETER H. GIVEN

Index

CONTRIBUTORS

B.L. Crynes

O.C. Dermer

Peter H. Given

V. Ponec

David S. Ross

P. Zhou

Copyright

COPYRIGHT © 1984, BY ACADEMIC PRESS, INC.

ALL RIGHTS RESERVED.

NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER.

ACADEMIC PRESS, INC.

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United Kingdom Edition published by

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ISBN 0-12-150703-3

ISSN 0730-5397

PRINTED IN THE UNITED STATES OF AMERICA

84 85 86 87 9 8 7 6 5 4 3 2 1

Contributors

Numbers in parentheses indicate the pages on which the authors′ contributions begin.

B.L. Crynes,     (253) School of Chemical Engineering, Oklahoma State University, Stillwater, Oklahoma 74078

O.C. Dermer,     (253) Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078

Peter H. Given,     (63) Fuel Science Program, Department of Materials Science and Engineering, College of Earth and Mineral Sciences, The Pennsylvania State University, University Park, Pennsylvania 16802

V. Ponec,     (1) Gorlaeus Laboratories, Rijksuniversiteit Leiden, 2300 RA Leiden, Netherlands

David S. Ross,     (301) SRI International, Menlo Park, California 94025

P. Zhou*,     (253) School of Chemical Engineering, Oklahoma State University, Stillwater, Oklahoma 74078

*Present address: East China Petroleum Institute, Shandong, China.

Preface

The ultimate need to replace liquid and gaseous fuels now derived from petroleum and natural gas resources with synthetic fuels from coal is generally recognized. Although technological bases already exist for utilizing coal directly in combustion and for converting it to liquid and gaseous fuels, we feel that considerable improvements in these technologies (such as greater overall thermal efficiency, hydrogen utilization, and selectivity to specific products) are needed. These improvements, along with new, more efficient routes to coal utilization, will only come about if we are able to gain more fundamental knowledge of the structure and reactivity of coal.

Because coal is such a heterogeneous material, coal science in its broadest sense embraces many scientific disciplines, including chemistry (organic, inorganic, and physical), physics, and engineering (chemical and mechanical). Consequently, the literature of coal science is vast and complex, containing a great deal of information—but only rarely in a form in which this information is logically assembled, reviewed, and evaluated. Because of the current interest in coal, we felt that critical reviews written by experts and aimed at the professional chemist or engineer now working (or contemplating working) in coal science would be both timely and useful. These reviews not only would pull together what has been reported in the past into a coherent picture, but would also point out the original reports′ significance as well as areas where more research is needed. Ultimately, coal science should furnish data and clues for solving or bypassing many of the problems now associated with coal conversion technologies.

This is the third in a series devoted to presenting and evaluating selected fundamental scientific areas involved with our understanding of coal structure, reactivity, and utilization. Included are reviews describing current state-of-the-art knowledge of the organic geochemistry of coal, the role oxygen functionality plays in coal and coal liquids reactivity, as well as contributions on the chemistry of hydrocarbon syntheses from carbon monoxide and hydrogen and the chemistry of coal in carbon monoxide/water systems. It is our hope that this series of volumes will not only be a valuable source of information and a guide to the coal literature, but will also stimulate research and serve as a basis for further advances in coal science and technology.

The editors would like to thank the contributing authors for their time and diligence in helping to make this volume a reality. We may have acted as catalysts, but the major share of the credit belongs to them.

Contents of Previous Volumes

Volume 1

Coal Plasticity Mechanism: Inferences from Liquefaction Studies

Richard C. Neavel

The Physical Structure of Coal

Warren R. Grimes

Magnetic Resonance Studies of Coal

H. L. Retcofsky

Molecular Structure of Coal

Robert M. Davidson

The Reductive Alkylation Reaction

Leon M. Stock

Index

Volume 2

The Science of Mineral Matter in Coal

Stephen C. Mraw, John P. De Neufville, Howard Freund, Zeinab

Baset, Martin L. Gorbaty, and Franklin J. Wright

Chemistry of Hydrogen Donor Solvents

Bradley C. Bockrath

The Role of Noncovalent Bonding in Coal

Virgil I. Stenberg, Richard J. Baltisberger, Kundan M. Patal,

Krishna Raman, and Neil F. Woolsey

Solvent Extraction of Coal

Janet R. Pullen

Index

Fischer–Tropsch Synthesis and Some Related Heterogeneous Reactions

V. PONEC,     Gorlaeus Laboratories, Rijksuniversiteit Leíden, Leiden, Netherlands

Publisher Summary

This chapter discusses Fischer–Tropsch synthesis (FTS), which consists of complex syngas reactions occurring with metallic, though not necessarily pure metal, catalysts. The Fischer–Tropsch-type reactions lead to very broad product distributions, including alkanes, alkenes, oxygen-containing derivatives, CO2, and H2O. The components involved in the FTS are hydrogen, hydrocarbons, and carbon monoxide. Adsorption characteristics of pure components and the adsorption features of mixtures are of importance. All metals active in hydrocarbon synthesis adsorb hydrogen at low temperatures up to full coverage. The hydrogen/surface atoms ratio can reach one, which can be also possible among other metals derived from the phase diagrams of H2 adsorption on single crystals. Adsorption on clean surfaces is fast, nonactivated, and dissociative. There is always atomically dispersed carbon on the metal surfaces, or a two-dimensional carbide sets in which it is sufficiently reactive to play the role of an intermediate in the FTS. The faster it can react with hydrogen, the lower the probability that it will coagulate and deactivate on the surface or become dissolved in the bulk.

I. Introduction

II. Adsorption of Reaction Components

A. Hydrogen

B. Hydrocarbons

C. Carbon Monoxide

D. Gas Mixtures

III. Intermediates and Mechanisms of the FTS of Hydrocarbons

A. Intermediates

B. Mechanisms of Hydrocarbon Synthesis

C. Transient-State Measurements

D. Types of Carbon

IV. Kinetics and Product Distribution

V. Some Particular Catalytic Effects

A. Effect of Alloying

B. Particle Size and Carrier Effects

C. Effect of Sulfur

D. Effects of Promoters

VI. Some Problems of the Activity of Metals

A. Activity Patterns of the Periodic System

B. Some New Catalytic Materials

VII. Synthesis of Oxygenates

A. Synthesis of Methanol

B. Higher Oxygenates

VIII. Concluding Remarks

References

I INTRODUCTION

It is certainly not necessary to explain to a reader of this series publication why much attention has turned toward coal in the recent past. It suffices to remind the reader that the massive use of crude oil in the production of gasoline and electricity stimulated the development of oil-based production of various petrochemicals. One can then expect that a massive reintroduction of coal as a source of energy would also be reflected in at least a partial return to coal-based chemicals. There are several ways in which coal, a relatively unreactive and hydrogen-lean material, can be converted into intermediates of chemical reactions, useful products, or other more suitable gaseous or liquid energy carriers.

Wender mentioned in his review (1) the following ways of converting coal into chemicals:

1. Via gasification, essentially highly endothermic reactions of the following type:

(1)

2. Via liquefaction, a direct high H2 pressure hydrogenation (e.g., the Bergius process), or extraction and dissolution by reactive solvents.

3. Partial oxidation.

4. Carbonization (devolatilization in an inert atmosphere).

5. Production of acetylene, e.g., via calcium carbide.

Of these, only topics related to the gasification route will be discussed below.

The mixture of CO and H2, called synthesis gas or syngas, can also be made from other sources of carbon. For example, methane or biomass

(2)

can serve as a raw material, the former being used for almost all of the present-day production of methanol. However, this review will be mainly concerned with the reaction represented by Eq. (2) from right to the left for the production of hydrocarbons from syngas.

More specifically, we understand that the Fischer-Tropsch synthesis (FTS) consists of complex syngas reactions occurring with metallic (though not necessarily pure metal) catalysts. Fischer-Tropsch-type reactions lead (2) in general to very broad product distributions, including alkanes, alkenes, oxygen-containing derivatives, CO2, and H2O. With some catalysts (Ni, Ru) and at high temperatures the distribution can be made very narrow, with CH4 strongly dominating the hydrocarbon products; in that case one speaks of methanation [reaction (2) from right to left].

More than generally expected, the above-mentioned reactions are probably mechanistically closely related to the synthesis of methanol. Therefore, some attention will be paid in this article to methanol synthesis and other heterogeneous reactions leading to oxygenated aliphatics. There are also other more practical reasons to discuss methanol synthesis and the production of oxygenates in parallel with the Fischer-Tropsch synthesis. A recent paper (3) brings convincing arguments that, of all reactions of syngas, the most efficient utilization of CO and H2 is achieved in producing ethylene glycol and other oxygenates including methanol, for which coal-based syngas may become a feasible raw material by the end of this century.

Let us mention in passing the main stoichiometric equations describing the reactions of syngas that occur during the Fischer-Tropsch synthesis. These reactions lead to alkanes [Eq. (3)], alkenes [Eq. (4)], alcohols and ethers [Eq. (5)], aldehydes and ketones [Eq. (6)], and acids [Eq. (7)]. They are accompanied by the water gas shift reaction [Eq. (8)] and carbon deposition by the Boudouard reaction [Eq. (9)], ester formation, etc.

(3)

(4)

(5)

(6)

(7)

(8)

(9)

Thermodynamics favors the shorter paraffins and longer alcohols and, in reactions leading to water, always paraffins over alcohols. Some thermodynamic relations are evident from Fig. 1. For example we observe that only when kinetics dictates the mechanism would a catalyst selectively produce methanol and not methane. Phenomenologically, we observe reactions and the catalysts used as summarized in Table I.

TABLE I

Some Heterogeneous Reactions of Syngas

Fig. 1 Gibbs free energies ΔG° of carbon monoxide hydrogenation at 600 K, per gram-atom of carbon in the products of the reactions: (•) nCO + 2nH2 → CH3(CH2)n-1OH + (n ) (2n − 1)CO + (n + 1)H2 → CH3(CH2)n-1OH + (n ) nCO + (2n + 1)H2 → CH3(CH2)n-2CH3 + nH2O. (diam;) 2nCO + (n + 1)H2 → CH3(CH2)n-2CH3 + nCO2. [From D. R. Stull, E. F. Westrum, and G. C. Sinke, The Chemical Thermodynamics of Organic Compounds. Wiley, New York, 1969.]

II ADSORPTION OF REACTION COMPONENTS

The components involved in the Fischer-Tropsch synthesis are hydrogen, hydrocarbons, and carbon monoxide. Adsorption characteristics of pure components as well as the adsorption features of mixtures are of importance. A complete discussion of all these subjects would be much longer than the planned extent of this review, and therefore, only those selected topics will be discussed which are believed by the reviewer to be most relevant with regard to hydrocarbon synthesis.

A Hydrogen

This topic can be covered briefly. The most relevant pieces of information are the following. All metals active in hydrocarbon synthesis adsorb hydrogen at low temperatures up to full coverage. The hydrogen/surface atoms ratio can reach one, as can be possible among other metals derived from the phase diagrams of H2 adsorption on single crystals (4–6). Adsorption on clean surfaces is fast, nonactivated, and dissociative. Several types of particles are formed with different effective dipoles of the chemisorption bonds, different effects on the electric conductivity of metals, etc. The dipole moment of the chemisorption bond is small and the bond can be considered as covalent (7–10). From about 150 K, atoms of hydrogen are fully mobile (7–10), and they influence each other by attractive as well as repulsive forces (4–6). Heats of adsorption are moderate and there is rather great similarity in the heats of adsorption of all group VIII metals. As a rule heats decrease with increasing atomic number in each period of the periodic table (for a full list of thermodynamic and kinetic parameters see Ref. 11).

B Hydrocarbons

Olefins are adsorbed readily at rather low temperatures. The dissociative adsorption of olefins has been proven (9–12) in several ways (volumetric measurements of surface reaction, TPD, LEED, etc.) and the discussion relates only to the question of whether the dissociatively adsorbed molecules are sufficiently reactive to be responsible for fast exchange, hydrogenation, and double-bond isomerization reactions at low temperatures (about room temperature); see Ref. (13) for a review of this subject. The most likely conclusion is that a part of the dissociatively adsorbed molecule is, indeed, of sufficient reactivity, although some other forms of adsorption (the so-called associative forms as π-complexed olefins and similar ones) might be operating to a great extent in the overall reaction (13). In any case formation of multiple metal-carbon bonds can be considered as a well-established aspect of the hydrocarbon adsorption mechanism.

(10)

The same holds also for the adsorption of saturated hydrocarbons, except that with these molecules the temperature at which they react with metal surfaces is slightly higher than those of olefins. Nevertheless, except perhaps with CH4, the temperature at which saturated hydrocarbons react with metals is well below the temperatures at which Fischer-Tropsch synthesis can be observed, namely 150–250°C (13, 14). Multiple bonds are more easily formed on Ni, Co, Ru, and Rh than on Pt and Pd (13–15) at temperatures of the Fischer-Tropsch synthesis and even at temperatures below this.

C Carbon Monoxide

For several reasons this is the most essential step of the heterogeneous reactions of syngas.

1. As will be shown below, the ease with which CO dissociates is of crucial importance for the catalytic performance of a metal.

2. CO adsorption is rather strong and can regulate surface coverages by hydrogen, weakly adsorbed olefins, etc.

3. The CO bond is rather strong and there are probably only a limited number of ways to activate this molecule for subsequent reaction; dissociation of CO and adsorption by positively charged centers seem to be the two possibilities most strongly supported by experimental data.

The CO molecule has two highest occupied levels, 5σ and 1π, and the lowest unoccupied level is 1π* (in some papers this is called 2π or, incorrectly, 2π*), which determines its modes of bonding. The 5σ, essentially a nonbonding orbital, is strongly localized on the carbon atom and is responsible for the good properties of CO as a donor ligand. The low-lying antibonding 1π* orbital is a suitable acceptor of electrons wherever the directly donated charge has to be compensated for by back-donation. This picture of bonding, first suggested only on semiquantitative grounds, was later quantitatively justified by quantum mechanical calculations in high approximations (16–21). These calculations also demonstrated a great similarity between bonding in carbonyls and bonding in chemisorption (see, e.g., Refs. 19–25).

As with metal carbonyls, adsorbed CO can also be singly coordinated on the surface of metals (sitting on the top of atoms) or multicoordinated: between two atoms (bridged); between three atoms, in the valley position; and, a case not completely excluded, among four atoms on the {100} face-centered cubic (fcc) planes. It seems that in most cases the main part of the chemisorption-bond dissociation energy originates from the 5σ direct donation. However, the back-donated electrons are (being delocalized into the far-reaching 1π* orbitals) responsible for the pronounced increase of the metal work function upon CO adsorption (the dipole layer is oriented with the negative charge outside the metal) and for the decrease in the C-O bond strength. The latter manifests itself by a decrease in the vibrational frequency (a downward shift of bands in the IR spectra) upon chemisorption and by a positive contribution to the heats of adsorption.

There has been some discussion in the literature on whether the frequency of the IR adsorption bands can be related to CO coordination. Most probably, the situation is as suggested by Bradshaw and Hoffman (25). At the lowest coverages, the CO position on the surface is mainly determined by the optimal coordination. At high coverages, the CO/CO interaction pushes CO molecules out of the optimal positions, predominantly by repulsive interactions. The main contribution to this repulsion comes from a dynamic interaction of parallel-vibrating dipoles which is partially mediated by the metal (26–31). The optimal coordination seems to be single at low coverage on various low index planes of Pt and Ir (see Ref. 29 for a review) double (or bridged) at high CO coverage on Pd {100}; and multiple at low coverages on Pd {111}, Ni {111}, etc. (11, 25, 32–37, and Refs. cited therein).

It is predicted (19–25) that back-donation increases with increasing coordination and that it is very strongly dependent on the metal-CO distance; back-donation is much stronger at sites at which CO can more closely approach the surface. Since back-donation is mainly mediated by the diagonal (T2g, in a fcc structure) metal d orbitals, all these conclusions are easily understandable on grounds of the CO orbital geometry. Figure 2 shows the frontier orbitals of CO, according to Jorgensen and Salem (38).

Fig. 2 Molecular orbitals (as indicated) of the CO free molecule. [From Jorgensen and Salem (38), p. 78, with permission.]

In carbonyls as well as upon chemisorption, the main contribution to bonding comes from the orbital localized on the carbon atom. The predominant CO adsorption form is thus carbon down (39–42). Within only a few degrees, CO remains perpendicular to the surface (40); with increasing temperature the amplitude of bending vibration increases (43); at still higher temperatures CO can finally dissociate, with C and O being bound on different sites on the surface (a high CO coverage seems to block dissociation (44)). Carbon monoxide lying side-on is most likely the transition state form of CO, which is evidently a very short-lived state; positive and definitive experimental evidence for its existence is still missing.

Although the Boudouard reaction, 2CO → C + CO2, has been known from the beginning of the century and its occurrence on clean metal surfaces has been repeatedly confirmed (45, 46), the possibility of a low-temperature, fast CO dissociation was doubted by many authors who preferred to explain results on the basis of hydrogen-assisted CO dissociation (47). However, CO dissociation does not seem to be a problem on metals active in the Fischer-Tropsch synthesis. XPS/UPS data showed that (1) some metals dissociate CO at low temperatures (ambient or lower); (2) other metals dissociate CO above ambient but below 200°C; and finally (3) some metals are poor at dissociating CO or they do not dissociate it at all. The UPS spectra of molecular CO on metals of the second group above reveal an activation of adsorbed CO. The activity patterns in CO adsorption are summarized (46) in Fig. 3.

Fig. 3 Periodic system and activity patterns in the Fischer-Tropsch synthesis. Left of (1): metals dissociating CO at low temperatures (T < 300 K): except Fe, all of low activity. Right of (2): no dissociation of CO at low or slightly enhanced temperature: inactive or low activity in FTS. Between (1) and (2): dissociation of CO after activation: the most active metals.

Heats of CO adsorption at ambient temperature can be subdivided into three groups (11): (1) metals of the III-VI group, with clearly higher heats of adsorption, and dissociation occurring at the temperature of measurement, (2) metals of group VIII, with rather similar heats of CO adsorption, and (3) metals of the Ib group, with clearly lower heats than the second group. Again, there is a tendency within each period for the heats of CO adsorption to decrease with increasing atomic numbers. This is important since adsorbed CO (COads) might be a precursor of insertion steps (in M-H, M-alkyl, or other bonds), and it is certainly a precursor of dissociation; the heat of adsorption determines, then, in a decisive way the population on the surface of the COads precursor.

D Gas Mixtures

For obvious reasons CO/H2 mixtures are used most frequently in adsorption studies. Data are available on all relevant metals including Fe (48), Ni (49), Co (50), Pt (51), Rh (52), and Ru (53). The picture emerging from these data is as follows. At low temperatures (T ≤ 300 K), the only detectable interactions of CO and H2 in the adsorbed state are due to the physical attraction/repulsion forces. These forces are responsible for the CO and H2 island formation observed with some metals (54). However, the simultaneous presence of CO and Hads on the surface probably changes the character of bonding with the surface. The data available on this have been interpreted as evidence for the forced transition of Hads from one adsorption state to another (something like Hδ− → Hδ+) by coadsorbed CO (55–57).

When the adsorption temperature is slightly increased but still kept under that of a steady-state gas reaction, a mutual enhancement of adsorption of both H2 and CO occurs. In some cases, formation of weakly bound (reversibly decomposing) stoichiometric complexes of H2 and CO has been reported (48). In other cases, the TPD data show (58) a desorption peak which has been interpreted as desorption of CO from a dissociative adsorption state in which the C-O bond is broken but C and O stay so close to each other that they desorb again as CO when the temperature is raised. This type of adsorption also seems to be quite common with the group VI and lower group metals of the periodic table. This desorption is often of an apparent first order, a fact which obscured for some time the existence of the C-O bond dissociation (42). Similar mutual enhancements of adsorption were also reported for methanol synthesis catalysts (59). With metals, the enhancement is probably related to incipient CO dissociation; this probably differs with methanol catalysts.

When CO dissociates (and we shall see below that it does so under the conditions of the Fischer-Tropsch synthesis), we also have to consider the adsorption of mixtures and corresponding mutual interactions in the adsorbed layers of CO/O2 and O2/H2 mixtures. With group VIII metals, the interaction of Oads + Hads occurs easily and is observable at very low temperatures. With Pt and Ir this takes place at 78 K (7–10). Thus reduction of Oads by hydrogen at Fischer-Tropsch synthesis conditions can be considered as an easy step for almost all group VIII metals. Probably iron differs the most, but even the FeO bond is reducible under these conditions. The reducibility of group III-V metal oxides under Fischer-Tropsch conditions must be questioned and this is also a very difficult step for group VI elements. As with CO/H2 on some metals such as Pd, Ir, and Pt, formation of separate islands of CO and O has been observed at low temperatures (60–62).

Also, the reduction of M-Oads by CO is not a particularly difficult process under the conditions of the FTS. Reactions of oxygen and hydrogen, as well as that of oxygen and CO are, according to direct experimental evidence, examples of Hinshelwood-Langmuir type reactions, i.e., reactions in which all reacting components must be chemisorbed (for a review on this problem see Refs. 7, 10, and 63). Since CO is rather strongly adsorbed, more so than H2, the reaction of O2 (gas) with (CO)ads starts at higher temperatures than the reaction with adsorbed hydrogen. Nevertheless, the reduction of Oads by CO to form CO2 should be considered with group VIII metals as a rather facile reaction, but the reaction is, of course, difficult with group III-VI metals, due to the adsorption bond strength of oxygen.

When Oads is brought into contact with a CO/H2 mixture, whether Oads is removed by CO or by H2 is dependent on the pressure. The available data indicate that with Ni (64, 65), Co (66, 67), or Fe (68, 68a) Oads is removed preferentially by CO at low pressures and by H2 at higher pressures.

Finally, a few words about the last interesting combination: CO and hydrocarbons. There is practically no information on saturated hydrocarbons in this respect, but it is worthwhile mentioning that with metals like Pt or Pd, CO is able to displace adsorbed olefins from the surface of metals (69, 70). No such displacement is observed with Ni, Co, or Fe, on which either the olefins are adsorbed more strongly or the bond to the surface is ethylidyne-like.

At temperatures where a steady-state FTS can be run, or just below that, formation of observable intermediates could be expected by such techniques as in situ IR spectroscopy, electron tunneling vibration spectroscopy, and UPS/XPS. However, a review of the existing literature will inform us that it is actually quite difficult to obtain unambiguous information on the mechanism of the FTS and its intermediates by any of these techniques (69–74).

The early literature (72–74) claimed that essential intermediates—mainly oxygen-containing intermediates—had been identified by IR. However, the authors of the most recent literature are less definitive in their statements and, although they observed both the alkyl-like as well as the oxygen-containing species, the authors admit that it cannot be said definitely whether these species were (1) on the metal or on the carrier and (2) whether they were living intermediates of the FTS at all. In a number of cases they were probably not (75–78). Only Tamaru et al. (79) seem to have sufficient evidence favoring identification of active intermediates on Ru under operating FTS conditions. These authors also observed undissociated CO under these conditions.

Electron spectroscopy studies accumulated important support for C-O bond breaking (46, 80) and showed further that most of the surface of working catalysts is covered by carbon or by hydrogen-lean species (CH, CH2) (80–82). This has been since confirmed by transient, isotopic labeling methods (83).

III INTERMEDIATES AND MECHANISMS OF THE FTS OF HYDROCARBONS

A Intermediates

We have already started a discussion on intermediates in the preceding section. However, the discussion was essentially confined to the results of adsorption studies and the detection of the potential intermediates by various spectroscopy methods. Let us now discuss other sources of information on the intermediates.

1 Carbon Atoms

This was a most controversial topic in the history of the development of the FTS mechanism. Actually, the inventors of the synthesis, Fischer and Tropsch, postulated that carbon atoms (carbidic carbon) were the intermediates but no experimental evidence could have been supplied at that time (84). When ¹⁴C became available attempts were made to arrive at a conclusion about the role of carbon atoms in the synthesis. That carbon was present as Fe carbide, amorphous carbon, and possibly other forms was already known. Since very little ¹⁴C has been found in the hydrocarbons when ¹⁴C was deposited by disproportionation of ¹⁴CO and later contacted with a ¹²CO/H2 reaction mixture, the authors (85) concluded that carbon is not an intermediate of the FTS and could, at best, only be an intermediate of part of the methane produced. However, a closer analysis of these data revealed that the low content of ¹⁴C in the gaseous hydrocarbons was a consequence of the special way in which the labeled carbon was deposited on the surface (86). Iron was an unfortunate choice for this type of experiment, as it can accommodate several types of carbon of very different activities.

When the same type of experiments were performed as in (85) but with Ni (64) and ¹³C-labeled CO, the results showed unambiguously that ¹³C deposited on the surface can be an intermediate in methane formation and that it reacts to form product faster than any other possible oxygen-containing intermediate. The same conclusion was also arrived at by other authors (65) and for other metals, such as Co (66). Indirectly, results of electron spectroscopy studies supported these ideas as well (80). The essential features of an isotopic experiment are shown in Fig. 4. In this experiment ¹³C was deposited on the surface by the Boudouard reaction and subsequently brought into contact with a ¹²CO/H2 mixture. As can be seen, ¹³C reacted much faster than anything else produced via the oxygenated intermediates from ¹²CO.

Fig. 4 Number of molecules formed of the compounds indicated as a function of time. T = 523 K. Ni film first covered by ¹³C (exception: 2COc→cC + CO2) and reaction mixture CO/H2 admitted; θ(Cs) is high, estimated as about 0.8 [From Araki and Ponec (64).]

There have been long discussions in the literature on whether carbon atoms are formed by an immediate CO dissociation or by a hydrogen-assisted dissociation. Many authors considered the C-O bond to be too strong (dissociation energy 1.06 MJ/mol) to be split at the moderate temperatures of the FTS and with its rather low activation energy, which is not higher than about 0.130 MJ/mol. Support for the assisted dissociation was sometimes seen (47) in the fact that both methanation and the FTS were (sometimes) faster than CO disproportionation, the rate of which was considered to be that of dissociation. However, one cannot forget the double role of hydrogen (1) to prevent recrystallization and dissolution in the metal of C (and its subsequent deactivation) and (2) to remove C and O from the surface, by which process sites are freed for more CO dissociation. One has to realize that hydrogen accelerates the catalytic decomposition of benzene on metals and yet it would be inappropriate to speak of a hydrogen-assisted decomposition (91).

Another important question is whether each metal surface atom is able to induce CO dissociation, or whether atoms situated near various defects (steps, vacancies, etc.) are required. The answer evidently depends on the metal. It seems that metals like Fe, Co, or Ni induce a fast, low-temperature dissociation, also by atoms of the low-index planes. However, for these metals it is likewise true that the presence of defects significantly accelerates the rate of dissociation (87–90). For some metals such as Rh, Ru, or Pt the presence of defects seems to be essential for a fast, low-temperature dissociation (92–98). With these metals the absence of dissociation on close-packed planes has been derived from the low pressure (PCO ∼ 10−6 Torr) data obtained in the UHV spectroscopic apparatus. However, the dissociation might have been too slow to be observed under these conditions.

Dissociation of CO bonds obviously takes place when the exchange reaction is running.

This exchange has been observed on Ru (99), Fe (100), Rh (101), and Ni (102, 103). If one can neglect (probably one can) the concerted exchange in intermediates such as the following:

the exchange reaction can be considered as evidence for a dissociative adsorption. It is interesting to note that it may occur at temperatures at which the Boudouard reaction is observable. Also, the exchange of oxygen between CO and H2O is a facile reaction, e.g., on Ni (104).

A much discussed question has also been whether the coadsorption of hydrogen or of hydrocarbons can weaken the C-O bond of COads. The argument in favor of such an idea was based on IR spectra: coadsorption of hydrocarbons decreased the wave number of adsorbed CO by about 50-100 cm−1 and hydrogen had a similar but smaller effect (106–110). However, the following has to be taken into account: carbon monoxide tends to form clusters and in these clusters, as well as under the conditions of full coverage, mutual CO-CO interactions leading to an increase in the wave number are quite strong and an effect (an upward shift) of 40-50 cm−1 can be expected. When a hydrocarbon is pre- or coadsorbed, it keeps molecules of CO away from each other and disturbs the CO-CO dipole interactions. Both effects can result in the lowering of the wave number of CO at full coverage below that of a pure CO layer. The size of the shift due to CO-CO interactions can be estimated from experiments with labeled CO (¹³CO) and it appears that at least 60% of the typical wave number decrease is due to suppression of the CO-CO interaction and not to the C-O bond weakening by hydrocarbon coadsorption. A part of the remaining (40%) effect can be caused by the corrosive character of hydrocarbon adsorption, which leads to roughening of the surface (111).

2 Carbon Monoxide

An adsorbed CO molecule is obviously the precursor of CO dissociation and of the formation of oxygen-containing intermediates wherever these can be formed. A particular question is whether CO as such can play a role in the FTS chain growth, e.g., by CO insertion. It has been already stated that on some metals there is little or no steady state adsorbed CO, so that in any case the insertion mechanism can hardly be the prevailing step (e.g., Ni). However, an insertion of CO into a metal-alkyl bond is a well-documented reaction (105) and thus must always be considered even though at present we have no direct evidence that this makes an important contribution to hydrocarbon chain growth in a heterogeneously catalyzed FTS (112).

3 CHx Intermediates

Auger Electron Spectroscopy (AES) investigations mentioned above (80) revealed that carbon of the same characteristics as the carbidic carbon and CHx species are most abundant on the surface of working FTS catalysts. Isotopic labeling and transient methods lead to the same conclusion (83). However, the question is, are these species the living intermediates or are they just reactive products of side chains? Several groups of authors showed that the CHx species can participate in chain growth of the steady state FTS, so they are living intermediates indeed. Biloen et al. (113) deposited ¹³C by ¹³CO disproportionation on a Ni surface (Ru and Co behaved in a similar way), carefully removed ¹³CO, and admitted a ¹²CO/H2 mixture. By using high-resolution mass spectrometry, they established that higher hydrocarbons (e.g., butanes) could contain more than one ¹³C atom. This shows that oxygen-free intermediates, CHx (x = 0−3), could contribute to chain growth. An example of results obtained in this way is given in Fig. 5. The mere presence of abundant products with two or more labeled carbon atoms is an evidence that oxygen-free intermediates can contribute to the hydrocarbon chain growth.

Fig. 5 Comparison of the observed (column) and calculated (line) yield of products (C1, C2, C3, …) with different amounts (0, 1, 2, …) of ¹³C atoms. Surface covered by predeposited ¹³C (exception: 2CO → C + CO2) ¹²CO/H2 admitted. Surface coverage by ¹³C, used in calculation, is indicated. [From Biloen et al. (113), with permission.]

Although the results just mentioned strongly support the idea that CHx are the units by which hydrocarbon chains grow, those favoring other mechanisms would raise the concern that, by predepositing carbon on the surface, one creates a situation very different from that which prevails during a steady-state reaction; the steady-state mechanism may actually have been suppressed by the predeposited carbon. It is, therefore, fortunate that there are now two other pieces of evidence pointing to CHx intermediates.

Brady and Pet tit (114) showed that an oxygen-free diazomethane/hydrogen mixture produced a very similar overall product distribution, including the distribution of isomers, as that derived from syngas. In a short but very important paper (115), the authors showed that addition of CH2N2 to an operating FTS increases the fraction of higher hydrocarbons, as if CH2N2 supplied an increased concentration of polymerizing units. The authors also analyzed the distribution of ¹³C atoms in propene formed when a mixture of ¹³CO/H2/¹²CH2N2 was passed over a cobalt FTS catalyst. In Fig. 6 note the similarity in the product distributions of the oxygen-containing (CO/H2) and oxygen-free (CH2N2) mixtures. The results clearly excluded CO insertion