Applied Catalysis A: General 212 (2001) 161174

Deactivation of supported copper metal catalysts for hydrogenation reactions

Martyn V. Twigg a, , Michael S. Spencer b
a b

Johnson Matthey, Orchard Road, Royston, Herts, England SG8 5HE, UK Chemistry Department, Cardiff University, Cardiff, Wales CF10 3TB, UK

Abstract Laboratory and industrial results are used to elucidate the general features of the deactivation of supported copper metal catalysts in hydrogenation reactions. Hydrogenations with copper catalysts are milder than with their nickel or platinum counterparts, and they have selectivities that are exploited commercially. They are used in single stream plants for production of hydrogen via the low-temperature water shift gas reaction, and for methanol manufacture from synthesis gas, and also in hydrogenation of speciality organic compounds. Common catalyst types are based on Cu/Cr2 O3 (copper chromite) or Cu/ZnO formulations that contain stabilisers and promoters such as alkaline earth oxides and Al2 O3 . These have several roles, including inhibition of sintering, and poison traps that prevent poisoning of the active metal surface. The best understood are Cu/ZnO formulations that have improved sulphur resistance due to formation of thermodynamically stable ZnS. Copper catalysts are susceptible to thermal sintering via a surface migration process and this is markedly accelerated by the presence of even traces of chloride. Care must be, therefore, taken to eliminate halides from copper catalysts during manufacture, and from the reactants during use. Operating temperatures must be restricted, usually to below 300 C when catalyst longevity is important with large catalyst volumes. Water can soften some Cu/ZnO formulations during use, and cause particle breakage that leads to high-pressure drop and maldistribution of ow through large catalyst beds and impaired performance. Commercial copper catalysts are not acidic, and since they operate under mild conditions, carbon deposition (coking) is uncommon. However, conventional site blocking poisoning with sulphur compounds, and particularly by H2 S, is common. The initial phase involves interaction with surface hydroxyl groups and elimination of water. Sulphur is retained strongly on the catalyst, and when partially sulphided they can exhibit selectivity in hydrogenation of organic hydrogenations. A variety of other sulphur compounds, and some chlorinated organic compounds, can cause complete deactivation or enhanced selectivity. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Copper catalyst; Deactivation; Sintering; Poisoning; Sulphur; Chloride; Chromia; Zinc oxide; Water-gas shift; Methanol synthesis

1. Introduction Supported Cu metal catalysts are used in a variety of industrial hydrogenation processes, and currently the
Corresponding author. Tel.: +44-1763-253-141; fax: +44-1763-253-492. E-mail address: twiggm@matthey.com (M.V. Twigg).

main groups are methanol synthesis, low-temperature water-gas shift, and the selective hydrogenation of various organic compounds. The rst two of these are of major importance in industrial large single stream production units, and this is reected in the literature on catalyst deactivation. Other hydrogenation processes using various copper catalysts are found mainly in the ne chemicals area. These are mostly batch processes,

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 8 5 4 - 1

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so catalyst deactivation, when it occurs, is usually less important than in continuous ow processes. There are few studies of Cu catalyst deactivation in ne chemicals processes. Further, the literature on the deactivation of, for example, platinum and nickel catalysts is much more extensive than that for the deactivation of copper catalysts. The 8th International Symposium on Catalyst Deactivation (Brugge, October 1999) had no papers or posters on copper-catalysed hydrogenation reactions. A substantial source of information, used in this review, for catalyst deactivation in methanol synthesis and the water-gas shift process are Chapters 6 and 9 in the Catalyst Handbook, 2nd Edition (Manson Publishing, London, 1996). Most of the catalysts used commercially are based on CuO/ZnO or CuO/Cr2 O3 formulations that when reduced carefully can afford highly dispersed copper. Even the best formulations are easily subject to thermal sintering and to poisoning, especially by sulphur and chlorine compounds, although deactivation by coking or physical damage of well-formulated catalysts is rare. Typical operating lives of copper catalysts in large plants varies from a month or so to several years depending on the process concerned and the actual plant conguration [1]. All forms of deactivation are considered in this review, where we examine common features and process-specic features. Recent results from the surface chemistry of oxygen and sulphur compounds on copper single crystals are used to elucidate the mechanisms of sulphur poisoning. Copper catalysts are also used in a variety of oxidation and dehydrogenation processes, including oxychlorination (Deacon and related reactions), but are beyond the scope of this paper.

2.1. Thermal sintering For metals, the predominant sintering mechanism in the bulk is vacancy diffusion, which suggests a relationship with cohesive energy. Hughes [2] gave the following increasing order of stability for metals: Ag < Cu < Au < Pd < Fe < Ni < Co < Pt < Rh < Ru < Ir < Os < Re It is, therefore, not surprising copper-based catalysts are more susceptible than other commonly used metallic catalysts, for example, the nickel and iron catalysts used in ammonia and hydrogen plants based on the steam reforming of hydrocarbons. This is also shown by coppers low Httig temperature [3], which reects a relatively low melting point (1083 C), compared with, for example, that of iron (1535 C) and nickel (1455 C). Therefore, copper-based catalysts have to be operated at relatively low-temperatures, usually no higher than 300 C. The catalytic activity of copper was appreciated at an early stage [4], and a comparison of performance of various formulations showed copper chromite was easily reduced to give a hydrogenation catalyst with good low-temperature activity, and better resistance to poisons than the unsupported metal [5]. Later, highly dispersed Cu/ZnO catalysts obtained via precipitation of hydroxides or carbonates were employed in some mild low-temperature hydrogenations [6]. Subsequently, when an intensive effort was made to develop industrial low-temperature shift catalysts (LTSCs) (Eq. (1)) copper was CO + H2 O CO2 + H2 (1)

2. Deactivation modes Compared with nickel or platinum catalysts, copper catalysts usually are less aggressive in hydrogenation reactions, and often can provide desirable selectivities, but they are sensitive towards a variety of deactivation processes. In this section the main thermal sintering, poisoning, and other deactivation processes are reviewed before considering the actual deactivation of industrial charges of copper catalysts in selected applications.

shown to be the most appropriate catalytic phase with the necessary activity and selectivity, there being effectively no hydrocarbon formation. However, the rst Cu/ZnO LTSCs lacked sufcient thermal stability for operation in steam just above the dew point prevailing in ammonia plans, typically between 200 and 250 C. The necessary long-term operating conditions were considerably more forcing than those previously encountered in the mild hydrogenations and dehydrogenations of organic compounds. New formulations were developed containing Cr2 O3 , and later Al2 O3 , in addition to CuO and ZnO in the unreduced catalyst. The thermal stability of these catalysts was signicantly higher. It is

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Fig. 1. Relative activities of typical copper/zinc oxide low-temperature water-gas shift catalysts under poison-free conditions. (A) Cr2 O3 -based catalyst; (B) conventional Al2 O3 -based catalyst; (C) high copper-content Al2 O3 -based catalyst; (D) optimised Al2 O3 -based catalyst. For clarity, experimental points are shown on only one of the curves.

apparent from data shown in Fig. 1, as well as extensive other results, thermal sintering can be controlled in well-formulated catalysts manufactured under optimal conditions, provided they are operated under well-controlled conditions. Thermal stability depends strongly on the manufacturing procedures used, not only on composition [7]. Details of the mechanism of the thermal sintering of Cu catalysts emerged from in situ EXAFS studies [8]. The local structure of the Cu/ZnO catalyst was studied under hydrogen at elevated temperatures. The structure around the Cu atoms assumed several forms depending on the temperature, and was best explained by assuming three structures. 1. Below a quasi-two-dimensional layer epitaxially developed over the ZnO support. 2. Between 127 C and at least 227 C, small copper metal clusters dispersed over the ZnO. 3. At higher temperatures, large copper metal crystals dispersed on the support. The active species for both methanol synthesis (Eq. (2)) and the water-gas shift reaction CO/CO2 + H2 CH3 OH (2) 127 C,

zinc oxide. Monophasic CuOZnO solid solutions (Cux Zn1x O) were prepared at high temperatures, and then supercially reduced at 287 C to give catalysts for H2 /CO2 reactions (methanol synthesis and the reverse water-gas shift reactions). Activities in both reactions were markedly superior to those of catalysts derived from biphasic systems containing additional CuO (that is, CuO/Cux Z1x O). The enhanced activity in the former case was ascribed to very nelydivided Cu crystallites present in intimate contact with the zinc oxide matrix. 2.2. Sulphur poisoning Operating catalysts at low-temperature thermodynamically favours adsorption of poisons, giving high surface coverages. As a result, copper catalysts are extremely sensitive towards site-blocking poisons, and they are particularly sensitive to even very low levels of poison such as reduced sulphur or phosphorus species. Under normal operating conditions, sulphur is a powerful poison for Cu, as indicated by the change in enthalpy in Eq. (3); sulphiding is very favoured, and the corresponding equilibrium constant is about 1105 . Sulphur from H2 S or other sulphur compounds accumulates on the catalyst, and it is, therefore, important to prevent even very low levels of sulphur

is dispersed small copper metal crystallites. Work from Stones group [9] further demonstrated the strong stabilising interaction between copper and

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contacting the Cu catalysts during use. It was for these reasons the introduction of LTS Cu catalysts in hydrogen and ammonia plants was delayed until sufciently pure process gas became available. This occurred with the change of feedstock from coal to naphtha or natural gas, and the associated introduction of high-pressure hydrocarbon/steam reforming, for which effective desulphurisation of feedstock was essential. 2Cu + H2 S Cu2 S + H2 , H 0 = 59.4 kJ mol1 (3)

ZnO is very effective in limiting poisoning of copper catalysts by the removal of H2 S from gas streams by the formation of zinc sulphide. Indeed, it is used in ammonia and other plants for sulphur removal from natural gas feeds [10]. The efciency of this reaction in preventing poisoning has been conrmed by equilibrium calculations [11]. The absorption reaction is shown in Eq. (4). ZnO(s) + H2 S(g) ZnS(s) + H2 O(g) ,
0 H4 = 76.7 kJ mol1 , 0 S4 = 3.0 J mol1 K 1

(4)

There are two forms of zinc sulphide, wurtzite ( -ZnS) and sphalerite ( -ZnS), and both forms are seen in discharged plant samples of zinc oxide absorbents. Sphalerite is the more stable form, and data given here relates to this form. The equilibrium constant K4 is 7.4 107 at 500 K, indicating the reaction is strongly favoured thermodynamically. To retain the long-term activity of Cu catalysts, it has been found empirically that gas-phase sulphur concentration needs to be kept below 1 ppm and preferably below 0.1 ppm. For typical values of total pressure of 20 bar and steam pressure of 10 bar, the equilibrium concentration of H2 S over ZnO is only 0.007 ppm at 227 C. Thus, at equilibrium, the ZnO in low-temperature water-gas shift catalyst gives excellent protection from H2 S to the copper crystallites. The small crystallite size of ZnO, coming from the method of manufacture, ensures fast reactive absorption [12]. Sulphur poisoning is rarely a problem in methanol synthesis (see Section 4.1), and little plant data has been published. Experimental work [13] demonstrated that sulphur compounds such as H2 S and thiophene poison copper-based catalysts. However, in practice

most well-formulated Cu/ZnO type catalysts can retain a high proportion of their activity in the presence of sulphur compounds as the sulphur is taken up eventually as zinc sulphide. It was found [14] that Cu/ZnO/Al2 O3 methanol synthesis catalysts retain a high proportion of their activity even when they have accumulated quite large amounts of sulphur. With an average of 2% sulphur, the methanol synthesis activity of a Cu/ZnO/Al2 O3 catalyst was approximately 80% of the unpoisoned activity, and with an average of 12% sulphur activity was approximately 25% of the unpoisoned activity. In contrast, a Cu/Al2 O3 catalyst was completely deactivated with only 0.2% sulphur in the catalyst, showing one of the major benecial effects of having ZnO in Cu-based catalysts. Fundamental aspects of the interactions of sulphur compounds with Cu surfaces have been studied in detail by Roberts group. The reactions of H2 S and sulphur compounds such as methyl mercaptan with Cu surfaces can involve various oxygen species. At room temperature and above, oxygen reacts with Cu(1 1 0) to cause surface reconstruction with the formation of stable OCuOCuO strings [15]. Low-temperature STM studies [16] identied in addition various reactive, transient oxygen species on Cu(1 1 0), isolated oxygen adatoms: pairs or dimers, separated by about 0.6 nm, and clusters of ve or six oxygen atoms arranged anisotropically. These species play an essential role in the poisoning of Cu surfaces by the reactions of sulphur compounds, and also of chlorine compounds. Disputes over the coverage of adsorbed oxygen on copper surfaces during methanol synthesis and the water-gas shift reaction [13,17] are not relevant here; fast reactions of oxygen transients have been observed [18] at very low surface concentrations. Early XPS studies [19] showed H2 S reacts with a Cu(1 1 1) surface which had been pre-exposed to oxygen, initially by hydrogen abstraction with the formation of surface hydroxyl species. Subsequent reactions involve dehydrogenation and eventually desorption of water. All the chemisorbed oxygen is removed and replaced by chemisorbed sulphur in reactions with negligible activation energy (<18 kJ mol1 ) at low-temperatures (68 to 100 C). Partial or complete poisoning of the Cu surface at catalytic temperatures can be reached depending on the amount of H2 S available. The recent use of combined XPS/STM techniques [20,21] on sulphided

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Fig. 2. STM images of (a) disordered chemisorbed mobile sulphur adatoms ( s = 3 1014 cm2 ; = 0.28) at a Cu(1 1 0) surface at 22 C, note the resolved copper atoms in the (1 1 0) direction; (b) ordered structures of (2 1) O and c(2 2) S formed an exposure of (a) to 20 L oxygen at 22 C; (c) high resolution image of chemisorbed sulphur adatoms separating (2 1) O strings; (d) disordered oxygen states present at a Cu(1 1 0) surface at 193 C; (e) ordered (2 1) O and (6 2) O states present after warming (d) to 22 C ([20]) (1 L (langmuir) 106 Torr s).

Cu(1 1 0) surfaces have given much further information. Both H2 S and methyl mercaptan were used as sources of sulphur. It was established that chemisorbed sulphur, co-adsorbed with oxygen, can inuence the structure of chemisorbed oxygen states at a Cu(1 1 0) surface, and simultaneously, these oxygen states can activate a disorderorder transition in the sulphur adlayer. In Fig. 2 [20], the rst image, Fig. 2(a), was taken after the adsorption of H2 S above at 22 C. There is no evidence of adsorbed sulphur despite a concentration of 2.41014 S adatoms cm2 . This is consistent with the high mobility of the sulphur adatoms, which persists up to about one-third monolayer. However, on exposure to oxygen, ordered structures were immediately observed (Fig. 2), c(2 2) structures due to chemisorbed sulphur and (2 1) string or chain structures characteristic of chemisorbed oxygen. In some cases, the oxygen strings are separated from each other by just a single row of S(a) (Fig. 2(c)), but in other cases, the strings were well-separated, and present ter-

races occupied predominantly by c(2 2) S structures Fig. 2(b)). Thus, there is the ability to control the structural nature of the chemisorbed oxygen state through co-adsorbed sulphur at less than complete coverage. It follows that the low levels of sulphur, below those giving poisoning, may act as promoter modifying selectivity or activity. There is some experimental evidence of this in processes using copper catalysts (see Section 4.3). The benets of low sulphur levels in processes using Ni or Pt catalysts are well-known [2225]. 2.3. Chloride poisoning The chloride poisoning of Cu catalysts can operate by several parallel mechanisms. 1. Reaction to give adsorbed chlorine atoms that can block or modify catalytic sites. 2. The low melting point and high surface mobility of Cu(I) chloride (Table 1) mean that even extremely small amounts of copper halide are sufcient to

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Table 1 Melting points of copper, iron and nickel and some of their compounds Melting point ( C) Metal Copper Iron Nickel
a b

ZnO(s) + 2HCl(g) ZnCl2(s) + H2 O(g) ,

0 H6 = 121.8 kJ mol1 , 0 S6 = 117.2 kJ mol1 K 1

(6)

Chloride 430a 674 1001

Bromide 492a 684 963

Sulphide 1100a 1195b 790c

1083 1535 1455

Cu(I) compounds. FeS. c Ni S . 3 2

provide mobile species that accelerate the sintering of Cu catalysts. 3. Poisoning of Cu catalysts by reduced sulphur compounds (e.g. H2 S) is exacerbated by traces of mobile Cu(I) chloride. 4. Further, ZnO, often present in Cu catalysts, reacts to form Zn halides, which also have low melting points, and causes further poisoning and sintering problems. As a result, halides are particularly virulent poisons for Cu catalysts, and this is important with catalysts for the low-temperature water-gas shift reaction. In practice, the only halide usually encountered in hydrogen and ammonia plants is chloride in the form of HCl. Reaction of bulk Cu metal with HCl to form CuCl as in Eq. (5) is thermodynamically much less favourable than the reaction of Cu with H2 S. However, the low melting point of CuCl (430 C), and by inference other Cu(I) chloride species, gives them high mobility under operating conditions. Consequently, even extremely small amounts of chloride provide the species necessary for a surface migration sintering mechanism of Cu crystallites. Similar processes involving ZnO take place when chloride is present because zinc chloride species (ZnCl2 , mp 283 C) also have high surface mobility, and this also contributes to a destructive destabilisation of catalytic activity via structural changes that decrease thermal stability. In keeping with the thermodynamics for the bulk chlorides indicated in Eqs. (5) and (6) under normal operating conditions almost all of the chloride present in low-temperature water-gas shift catalysts is associated with zinc rather than copper species.
1 Cu(s) + HCl(g) CuCl(s) + 2 H2(g) , 0 H5 = 43.5 kJ mol1

In contrast to the case of sulphide poisoning, ZnO gives no protection against chloride poisoning. In this case, the absorption reaction (6), ultimately gives ZnCl2 , and the equilibrium constant, K6 , is 4.1 106 at 227 C and 1 bar. In practice, depending on the amount of water present, hydroxychloro species may be formed rather than ZnCl2 . As above for H2 S, the equilibrium concentration of HCl in the gas phase can be calculated to be about 80 ppm if ZnCl2 is formed. The limits on HCl content to avoid catalyst poisoning are more severe than for H2 S poisoning, of the order of 1 ppb. The large difference in concentration emphasising again that ZnO can give no protection to Cu catalysts against HCl poisoning. An XPS study [19] showed chemisorption of HCl on a Cu(1 1 1) O surface follows a similar pattern to the chemisorption of H2 S, as shown in Eqs. (7)(9). The initial facile hydrogen abstraction reaction gives surface hydroxyl species. Subsequently, these dehydroxylate to give water, which desorbs. There is a total removal of O(a) and replacement by Cl(a) . In the absence of surface oxygen, no reaction was found with HCl. Only molecular adsorption occurred. HCl(g) + O(a) OH(a) + Cl(a) OH(a) + OH(a) H2 O(a) + O(a) H2 O(a) H2 O(g) (7) (8) (9)

(5)

The results of laboratory experiments shown in Fig. 3 illustrate the decrease of water-gas-shift activity following introduction of a small amount of HCl into the feed gas. Chloride poisoning is a particularly difcult problem for water-gas shift plant operators, because it is usually present in process gas in amounts below the normal levels of detection. However, depending on the actual catalyst concerned, chloride can be retained at the top (inlet region) of the catalyst bed, usually in the form of zinc hydroxychlorides, with the result the overall catalyst charge is partially self-guarding. These species are, however, soluble in hot water, and it is, therefore, important to avoid conditions that give condensation, otherwise condensation will wash chloride further into the bed. It is clear

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Fig. 3. Effect on activity of very small amount of HCl on the water-gas shift activity of a Cu/ZnO/Al2 O3 catalyst.

that admission of chloride to process streams involving Cu catalysts should always be kept to an absolute minimum. Strict attention has to be paid to feedstock purity, and traces of chloride have to be removed with an alkali absorbent that has high afnity for HCl during feedstock purication. Similarly, chlorinated solvents should not be used during maintenance operations, and on sites, where gases such as hydrogen are imported, care is necessary to conrm their quality. 2.4. Other poisons Other poisons for Cu catalysts include arsenic, which might come from some types of CO2 removal systems in hydrogen or ammonia plants, and trivalent phosphorus, which could originate from boiler water feed treatment, but in practice, these are seldom actually encountered. Silica, transition metals such as iron, cobalt and nickel may also occur as poisons in some processes (see Section 3). 2.5. Carbon deposition (coking) Unlike reactions involving transition metal catalysts such as those containing iron, nickel or cobalt, or acidic catalysts such as zeolites or sulphated zirconias, Cu catalysts have no strong tendency to catalyse

FischerTropsch reactions, or processes involving carbonium ion chemistry. Copper also has a very low activity for breaking CO bonds or forming CC bonds, and as a result, wax formation is not usually a major problem in CO/H2 reactions, nor is formation of coke from hydrocarbons. These potential problems are further reduced by the fact Cu catalysts must be operated at fairly low-temperatures to minimise thermal sintering. 2.6. Physical damage Physical damage is rarely a signicant cause of deactivation in Cu catalysts. The main causes of physical damage in other catalytic systems are 1. the formation of carbonaceous deposits within the catalyst pore system, 2. catalyst attrition in uidised or moving bed processes. Copper catalysts, for reasons given in Section 2.5, rarely suffer from carbonaceous deposits. None of the main hydrogenation processes using copper catalysts were designed as uidised or moving bed processes, so this cause of damage is not encountered, but some kinds of plant maloperation can lead to physical damage of any catalyst. For example, inadvertent

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exposure to hot liquid water can sometimes cause physical breakage of catalyst pellets. Copper catalysts are especially susceptible to careless temperature excursions, that lead to excessive sintering of the copper crystallites (Section 2.1) and irreversible loss of activity. 3. Control of poisoning 3.1. Feedstock purity Both sulphur- and chlorine-containing compounds can originate in the feedstock. For example, steam or process air for an ammonia or hydrogen plant can be a source of poison, so even location of a plant is relevant. Steam can be eliminated as a source of poisons by ensuring the boiler design prevents carry-over of solids into the process steam system. Process air can be ltered. In particularly contaminated environments that may result from adjacent plants, the process air could be washed. In locations close to the sea, salt-water spray must be prevented from being drawn into the air compressor. Sulphur compounds in the feedstock will normally be reduced to <0.1 ppm by desulphurisation before the primary reformer in hydrogen, ammonia and methanol plants. However, there can be other sources of sulphur. Unless special care is taken, some sulphur compounds may pass to the LTSC from newly installed reformer catalyst or high temperature shift catalyst (HTSC). With conventional HTSC, it is usual to reduce the catalyst and so remove almost all of the sulphur from it before the low-temperature shift converter is brought on-line. The problems of excluding poisons from the feedstock can be more difcult in batch hydrogenations typical of the ne chemicals industry. Poison removal from reactive liquid feedstocks to very low levels may not be possible. However, catalyst life requirements for batch processes are not as severe as for ow processes since fresh catalyst can be used for each batch. 3.2. Guard beds As indicated in Section 2.2, ZnO incorporated into supported Cu catalysts is very effective in restricting sulphur poisoning. In contrast, ZnO is not capable of retaining chlorine poisons to give sufciently low

gas phase levels (Section 2.3), so other techniques have to be used to eliminate chlorine poisoning. One method, which has found wide use in low-temperature water-gas shift and other plants, is the provision of guard beds. The feed for the main reactor, which contains the Cu catalyst, passes through a guard bed (either in a separate reactor or a separate bed within the main reactor) before reaching the main catalyst bed. Alkalised alumina has been used in the guard bed to remove chlorine poisons, but the catalyst itself, as in the main reactor, has usually been found in practice to be as good an absorbent. As a result, a guard bed of the same catalyst removes all the poisons for the main catalyst charge, and there are examples of such main catalyst changes maintaining performance over many years. When a separate guard reactor is used, replacement of the absorbent while the main reactor is kept on line can be achieved. This technique gives extended catalyst life and continuous peak performance. Reactions of poisons with catalysts are normally strongly diffusion-limited, so the use of small pellets of absorbent can be advantageous in some plant situations due to the high poison capacity of the small pellets [26]. 3.3. Catalyst formulation Catalyst formulation can in many instances be controlled to give increased resistance to poisoning as well as high and stable activity. With LTSCs containing reactive ZnO, sulphur is trapped at the top of the bed as ZnS, which is more stable than sulphided copper. The equilibrium constant for formation of bulk ZnS is almost three orders of magnitude larger than that for formation of Cu2 S from Cu metal, and H2 S (Section 2.2). There is some evidence to suggest initially sulphur is preferentially adsorbed on active small copper crystallites (about 5 nm), and then transferred to ZnO where it reacts to form the thermodynamically more stable ZnS. To facilitate this, the catalyst pellets need to be porous to minimise diffusion effects, and to have small Cu crystallites, and the highest possible surface area of reactive ZnO. If a LTSC has a limited amount of free ZnO, or if it combined with another component as a thermodynamically more stable compound than ZnS, sulphur will not be retained by the catalyst so readily, and it will be held in a broad poisoned region of the bed.

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Fig. 4. Effect of surface area of ZnO on the maximum sulphur absorbed by different Cu/ZnO/Al2 O3 water-gas shift catalysts under laboratory conditions.

On the other hand, a catalyst with a signicant content of reactive free ZnO will retain sulphur in a well-dened concentrated layer of the catalyst bed, so that the bulk of the charge remains completely unaffected by sulphur and will continue to operate satisfactorily. The kinetics of this process demand the ZnO surface be as high as possible, and indeed in some laboratory experiments the limiting amount of sulphur combined was a linear function of the surface area of free zinc oxide. This is illustrated in Fig. 4. In full scale plants process gas sulphur levels can be very much lower than those used in relatively short term laboratory experiments, with the result, the sulphur content of even well-formulated catalyst is rarely more than about 2% when discharged from the top of a reactor. Some representative analytical results for discharged LTSC are given in Table 2 but in problem

plants, such as those located in unfavourable locations with high atmospheric pollution levels, the sulphur content of discharge catalyst from the top of the bed can be as much as 7%.

4. Processes and catalysts 4.1. Methanol synthesis While such aspects of methanol synthesis catalysis as the kinetics and mechanism of reaction, and the nature of the catalytically active sites have been the subject of much recent investigation, the literature on the deactivation of methanol synthesis catalysts is in contrast, relatively sparse. The rate and mechanism of deactivation of such catalysts are important

Table 2 Sulphur content of discharged samples of a well-formulated low-temperature water-gas shift catalyst from different positions in the charge Type of plant Problem Life (years) Sulphur % (w/w) Top Ammonia Hydrogen Ammonia Ammonia
a

Mid NAa 0.2 0.3 0.3

Bottom 0.05 0.03 0.03 0.06

plant, plant, plant, plant,

1350 tonnes per day 80000 m3 h1 850 tonnes per day 900 tonnes per day

None None Air pollution Water quench and sulphur air pollution

4 3 1.75 2

0.8 0.5 0.9 1.6

NA: not available.

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parameters in their industrial use, indeed Cu/ZnO catalysts although known for many years were not exploited industrially for sometime, because their life-time was so poor. The early catalyst formulations had poor thermal stability, and were poisoned by sulphur compounds derived from the coal feedstock then used to produce synthesis gas. The loss of activity of the early Cu catalysts was almost certainly due to loss of copper surface area, despite the presence of ZnO and other stabilisers. The copper metal produced by careful reduction of the oxide (57 nm crystallites) readily sinter at synthesis temperatures with consequent loss Cu surface area and activity. One of the functions of the stabiliser is to separate the copper crystallites physically, and hinder the sintering process. However, it is desirable to minimise the amount of stabiliser, because if it has negligible activity itself, it dilutes the effective catalyst component. Although ZnO has activity for methanol synthesis, this is so much less than that of Cu, so it is effectively an inert diluent. There are possible other roles of ZnO [7]. In an oversimplied model, the catalyst can be considered [27] as particles of copper metal surrounded by, and kept apart by stabiliser particles. There is a rough geometric relationship [28,29] between the diameter of the metal and stabiliser particles, and the volumes of metal and stabiliser. The smaller the diameter of the refractory spacers, the higher is the practical Cu loading and the higher the activity. High metal concentrations are used in industrial catalysts: in use both metal and spacer dimensions increase, and the rough relationship still holds. While such calculations are not precise, they provide useful guidelines during catalyst development. The design of methanol synthesis catalysts is discussed in more detail by Andrew [27] and Chinchen et al. [13]. Catalysts made by a controlled precipitation procedure were used in the rst low-pressure synthesis plants, operating at 50 bar, which were started up in 1966. They had lives of more than 3 years and produced methanol of a higher purity than the older high-pressure process. Continued development resulted in catalysts suitable for operation at 100 bar, around the optimum operating pressure for high-capacity plants producing more than 1000 tonnes per day of methanol. Initial tests showed that the rate of catalyst die-off was higher at the higher pressure. ZnO/Al2 O3 is not sufciently refractory as a support

at 100 bar, but a more refractory support is provided by introducing some of the zinc component as zinc spinel (ZnAl2 O4 ), which is produced in a nely divided state. In more recent work [30,31], claims are made for increased stability in CuO/ZnO/Al2 O3 catalysts containing further refractory oxides such as MgO. In normal operation of methanol synthesis plants, the only signicant mode of deactivation is sintering of the copper crystallites, and consequent loss of copper metal surface area (see Section 3.1). Catalyst activity for methanol synthesis under industrial conditions is proportional to the Cu surface area [32,33]. Thus, loss of Cu surface area results in direct equivalent loss of activity. Poisoning by sulphur, chlorine or other compounds is negligible in normal plant operation, because these are removed by the earlier stages of generation of synthesis gas. The selectivity of methanol synthesis is normally >99%. Various impurities, either left in the catalyst during its manufacture or accidentally introduced during use, can cause loss of catalyst activity and, usually more important, loss of selectivity. The presence of transition metals such as iron in methanol synthesis catalysts is particularly undesirable since they usually increase hydrogenation activity and promote the dissociation of CO and CO2 , leading to formation of methane and of long chain parafns and/or waxes by FischerTropsch reactions. Methanation was always a problem with the original high pressure methanol synthesis catalyst, and it is thought this was mainly caused by iron impurities. Iron is sometimes deposited on synthesis catalyst during use by the decomposition of the gaseous iron pentacarbonyl, Fe(CO)5 , formed from rust that may be present in the make-up gas system. The effects of a given level of iron impurity in a catalyst are strongly dependent upon its form, oxidation state, and distribution. Other transition metals, such as for example, cobalt and nickel, can also catalyse methanation, but they have been found [34] to have a further deleterious effect. Methanol synthesis itself is inhibited, probably by surface coverage of copper crystallites. Alkaline impurities in Cu methanol synthesis catalyst can result in the production of higher alcohols, and cause some decrease in activity. Similarly, acidic impurities (for example, any silica in the support material) can lead to formation of high molecular weight waxes on the catalyst, which cause loss of

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activity by blocking some of the smaller pores. The weaker acidity sites found on the surface of high area aluminas does not give waxes, but can catalyse the dehydration of methanol to dimethyl ether. These problems are eliminated by careful design and manufacture of the catalyst. 4.2. Low-temperature water-gas shift Unlike methanol synthesis, poisoning by sulphur and chlorine compounds is the major cause of catalyst deactivation of the Cu/ZnO/Al2 O3 catalysts used for the low-temperature stage of the water-gas shift process shown in Eq. (1). Details of poisoning by sulphur and chlorine compounds are described in Sections 2.2 and 2.3. The use of guard beds (Section 3.2) is normal practice for this process. Other poisons from maloperation, etc., can cause problems. Iron pentacarbonyl, Fe(CO)5 , as in methanol synthesis, can cause loss of activity, and care has to be taken to avoid its formation. Silica is frequently found in discharged LTSCs, and it can be a serious problem, because it deposits on the outer surface, and nally into the pores of the pellets where it reacts to form zinc silicate. In severe cases, this will result in a decrease in CO conversion, and more rapid movement of the reaction temperature prole through the bed. The presence of silica in a LTSC also has the more serious effect of exaggerating problems associated with both sulphur and chloride poisons. This is because the reaction of silica with zinc oxide reduces the quantity of available free ZnO at the inlet of the bed, which interferes with the normal absorption of poisons. The resulting transfer of sulphur and chlorine further into the bed shortens the life of a charge by decreasing the average concentration of poisons (particularly sulphur) required to cause deactivation. 4.3. Organic hydrogenation reactions Copper catalysts, typically Cu/ZnO and Cu/Cr2 O3 , are used industrially in a wide variety of organic hydrogenation processes. Unfortunately, there is comparatively little in the literature about these processes despite their use for decades, and even less is available on the deactivation of the catalysts. Here, we restrict the discussion to a few processes for which

information is available. Further, use of the copper chromite catalysts is declining, and substitutes are being sought [35,36]. In general, much of the discussion above (Section 2) applies to the catalysts used in these processes. Reaction temperatures are generally low because of the thermal sensitivity of organic feedstocks and products. Consequently, deactivation by sintering of copper metal crystallites is normally not a serious problem, but poisons, which are adsorbed more strongly at lower temperatures, are the main cause of deactivation. It is also difcult sometimes to get sulphur levels in feedstocks to very low values, particularly in those originating from natural sources such as oils and fats. Batch processing, with frequent replacement of poisoned catalyst, is common practise in this area. Copper chromite catalysts are often stabilised by the incorporation of barium oxide [37], typically about 10%, but it is not clear how this promoter functions. From the above discussion, it seems likely that it can function as a poison (probably H2 S) absorbent more than as an inhibitor of sintering. Possibly, it fulls a similar role in this respect to zinc oxide in Cu/ZuO catalysts (Section 2.2). Other functions for barium have been claimed in the literature. The activity of copper chromite catalysts is inuenced by the oxidation state of Cr and Ba oxide inhibits its reduction, so stabilising the catalysts [38,39]. Calcium is not as effective a promoter as barium [4042]. Rao et al. [35,36] found that both Cu(0) and Cu(I) sites on the catalyst were required for maximum activity in selective hydrogenation of furfural, but they did not explore barium oxide promotion. It is also possible that BaO could inuence the populations of Cu(0) and Cu(I) sites. Aldehydes and ketones form a group of unsaturated compounds, which can be reduced by the use of pre-reduced copper chromite catalyst [37]. The most important aldehyde reduced by this technique at ambient temperature is furfural, which gives furfuryl alcohol, reaction (10)

(10) Several studies of this reaction with copper chromite catalysts have shown that catalyst deactivation occurs

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readily [35,36,43,44]. Rao et al. [35] found the reciprocal of the reaction rate was linearly dependent on time-on-stream, and suggested two possible reasons for catalyst deactivation. The formation of coke and/or poisoning of the catalysts (adsorbed furfural or some reaction product), or a change in the oxidation state of the copper during the course of the reaction. Another possibility not considered by them is poisoning by traces of sulphur, chlorine, etc. This group in a later paper [36] compared Cu/carbon catalysts with copper chromite catalysts. Surprisingly, two of the carbon-based catalysts lost activity similarly to copper chromite, but the Cu/activated carbon catalyst gave negligible deactivation. They stated that none of the possible causes of deactivation can yet be ruled out. Rao et al. [35,36] also examined the selective hydrogenation of crotonaldehyde to butanal shown in Eq. (11) over the same catalysts, but found little deactivation, in contrast to furfural hydrogenation. Selectivity to crotyl alcohol (selective reduction of the aldehyde group while leaving the olenic bond intact), reaction (12), has been obtained with a Cu/Cr2 O3 catalyst [45]. CH3 CH=CHCHO + H2 CH3 CH2 CH2 CHO CH3 CH=CHCHO + H2 CH3 CH=CHCH2 OH (12) CH3 CH=CHCHO + 2H2 CH3 CH2 CH2 CH2 OH (13) Hutchings, Rochester and co-workers [4651] used selective poisoning of Cu catalysts to achieve a higher selectivity to crotyl alcohol. With a 5% Cu/Al2 O3 in the absence of sulphur poisons they obtained 1-butanol preferentially, reaction (13). Catalysts pre-dosed with a suitable amount of thiophene moved the product distribution towards the formation of crotyl alcohol, while signicantly decreasing crotonaldehyde conversion [46]. It was shown that the increased selectivity to crotyl alcohol was not merely a function of the decreased conversion level observed with the sulphided catalyst. The activities of both unsulphided and sulphided catalysts decreased with time-on-line. Similar experiments [47] with various chloromethanes gave either total deactivation (CH3 Cl) or an enhanced selectivity to butanal (CCl4 and CH2 Cl2 ), in contrast (11)

to sulphur poisoning. This is in accordance with the general observations (Sections 2.2 and 2.3) that chlorine compounds are more effective poisons for copper catalysts than sulphur compounds. Further work on sulphur poisoning in this system demonstrated [48] the effect on selectivity is broadly independent of the support used for the copper. The same effect was also found [49] with all of a variety of sulphur compounds, with some dependence of selectivity on sulphur compound. Thiophene gave the highest selectivity to crotyl alcohol, at constant temperature and conversion. The authors conclude that modication by sulphur compounds creates Cu0 S and Cu+ S surface sites that are more selective for the hydrogenation of the carbonyl bond in preference to the carboncarbon double bond. In further catalyst modication in this system, a PdCu alloy supported on SiO2 was tested with thiophene deactivation [50]. No selectivity to crotyl alcohol was found, because the Cu component was preferentially poisoned leaving active Pd sites which favoured C=C bond hydrogenation. There are several organic substrates for which nickel catalysts are generally the preferred catalysts for hydrogenation, but nevertheless copper catalysts are sometimes used commercially. One example is the hydrogenation of nitrobenzene to aniline in a gas-phase process. Deactivation of the catalyst occurs in several ways [52]: carbonaceous deposits, catalytic poisons, sintering and destruction of pellets, but carbonaceous deposits and sintering of copper crystallites are most important. Deactivation has been modelled [53]. Copper catalysts have been used to a limited extent [54,55] in the selective hydrogenation of double bonds in natural oils and fats (i.e. margarine manufacture). Nickel catalysts are normally used because copper catalysts are much less active than nickel, they are more sensitive to poisoning (primarily traces of sulphur in the feedstocks) and traces of copper in the product catalyse subsequent autoxidation reactions. Copper chromite catalysts are also traditionally used [56] for the more extensive hydrogenation of fats and oils to the corresponding alcohols. 4.4. Dehydrogenation reactions Copper catalysts are not widely used for organic dehydrogenation reactions. In many cases, especially with hydrocarbon feedstocks, thermodynamics limits

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on conversions [57,58] force the use of high temperature for which copper catalysts are inappropriate (see Section 2.1). The main dehydrogenation processes in which copper catalysts are used are methyl formate from methanol, and methanol decomposition to synthesis gas that is used on a small scale to produce hydrogen. These processes are, respectively, a variation on methanol synthesis, and the reverse of methanol synthesis. Typical catalysts are similar to methanol synthesis catalysts, that is, Cu/ZnO/Al2 O3 . Little has been published on the deactivation of these catalysts, but the features discussed above (Sections 2.1 and 4.1) can be expected to apply.

Acknowledgements The authors thank Professor M.W. Roberts and Dr. P.R. Davies for many helpful discussions and for unpublished results. References
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