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Catalysts for cost-effective hydrogen production

Processes now used in the new generation of hydrogen plants make a wide choice of catalysts necessary in order to meet the requirements of particular
Leif Storgaard and Hans Christian Nielsen Haldor Topse A/S

ydrogen plants have traditionally experienced long catalyst lifetimes. In older plants, where purification of the hydrogen is taking place by methanation, the stress on the installed catalyst has been low due to ample design of the plants and to relatively mild operating conditions, ie high steam to carbon ratio. During the past 10 years, the demand for hydrogen has been increasing and many new hydrogen plants have been constructed. The demand for more cost-effective hydrogen production has increased and the new generation of hydrogen plants is operated under more critical conditions (lower steam to carbon ratio) and a variety of hydrocarbon feeds is applied as feedstock. Old hydrogen plants have been designed with CO2 removal and methanation for final purification of the hydrogen. A typical process layout is

shown in Figure 1. The steam to carbon ratio is normally 4.06.0. New hydrogen plants are designed with pressure swing absorption (PSA) for purification of the hydrogen. The offgas from the PSA unit can be used as fuel for the steam reformer. A Topsedesigned designed hydrogen plant is shown in Figure 2. The steam to carbon ratio is 2.5. Traditionally, the feedstock for the hydrogen plants has been natural gas, LPG or naphtha. However, at the refinery, there are normally various offgases available deriving from other units in the refinery. These offgases have in the past been used as fuel or been flared. In order to reduce cost for the hydrogen production, they are today widely used as feed for hydrogen production and LPG or naphtha is used only as make-up/backup. This means that the catalysts in todays hydrogen plant must be able to operate on

Figure 1 Traditional hydrogen technology: typical process layout

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Figure 2 Typical process layout, Topse hydrogen technology

various types of hydrocarbon feeds or a mixture thereof. Furthermore, the catalyst must cope with feedstocks containing olefins as well as various levels of sulphur and chlorine.

hydrocarbon feedstock may contain various levels of sulphur, chlorine or olefins, which have to be removed since these components will create problems for the downstream units. For hydrogenation of organic sulphur and Purifying hydrocarbon feed chlorine compounds into H2S and HCl and for The first catalytic step in hydrogen production is saturation of the olefins, Topse has TK-250 purification of the hydrocarbon feed. The catalyst. This catalyst is based on a high surface area alumina carrier impregnated with cobalt and molybdenum. Under normal operating conditions, the TK-250 only deactivates very slowly and lifetime will be many years. The offgases containing olefins may have to be treated in a special way. The hydrogenation of the olefins is a strongly exothermic reaction. It is generally recommended to limit the operating temperature for TK250 catalyst to 400C in order to prevent possible hydrocracking or carbon formation. The inlet temperature, on the other hand, should preferably be higher than 280C. If the olefin content in the feed is high, the adiabatic temperature increase across the catalyst may be higher than the operating temperature range foreseen. In such a case, recycling of part of the hydrogenFigure 3 Typical layout for olens hydrogenation, using Topse ated gas can solve the problem. hydrogenation catalyst This is illustrated in Figure 3. The

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flow diagram shows actual operating data from a hydrogen plant operating on refinery offgas. The recycle flow is controlled by the temperature measurements in the top part of the catalyst bed since the olefin content in the feed varies from nil to 25 per cent. Another problem, which may arise when operating on various types of feedstocks, is a large variation in sulphur content in the feed. The TK250 catalyst is most active in the sulphide state. If the feed for longer periods is essentially sulphur free, the sulphur on the catalyst will gradually be stripped off and the catalyst activity will decrease. When switching to a feed with high sulphur content, the activity of the catalyst may not be sufficient for converting all the organic sulphur. This problem can be solved by adding small quantities of sulphur to the sulphur-free feed, which will ensure that the CoMo catalyst is kept in sulphide state. The refinery offgases often contain chlorine and in many hydrogen plants it has been necessary to include a chlorine removal step. After the hydrogenation step, chlorine is efficiently picked up on a chlorine guard. HTG-1 catalyst is applicable for this application. It can pick up 18 per cent chlorine on weight basis. The hydrogen sulphide is removed by zinc oxide for which HTZ-3 and HTZ-5 is recommended. Both catalysts consist of more than 99 per cent pure zinc oxide. HTZ-3 is the standard product for sulphur removal. It is especially suited for sulphur removal of hydrocarbon feedstocks containing more than 5ppm of sulphur. It has a capacity of more than 500kg sulphur per m3 of catalyst. HTZ-5 has a higher porosity and higher surface area than HTZ-3. It is recommended for hydrocarbon feedstocks with low sulphur content or for low temperature application. Some plants, however, experience problems with efficient desulphurisation of the feedstock. Reasons for this may be a large variation in sulphur content in the feed, low operating temperature or high CO2 content in the feed. CO2 will react with hydrogen on the TK-250 catalyst according to the reverse shift reaction. The steam formed from this reaction has an impact on the equilibrium H2S leakage from the zinc oxide. For such cases, a Cu-based catalyst, type ST-101, has been developed, which effi-

ciently removes all types of sulphur which may leak from the desulphurization section.

Case study 1
A plant using natural gas as feed experienced sulphur poisoning of the steam reforming catalyst resulting in high tube wall temperatures and high methane leakage. The natural gas had for a long period been essentially free of sulphur and the hydrogenation catalyst had consequently lost activity. When the sulphur content in the feed suddenly increased, organic sulphur slipped through the HDS section and poisoned the reformer catalyst. Topse recommended a regeneration of the steam reforming catalyst and installation of ST101 catalyst in the bottom of the last zinc oxide vessel. Following these measures, the plant has now been operating for four years with the regenerated steam reforming catalyst.

Traditionally, the reforming section has consisted of a tubular reformer only. Today, however, the adiabatic prereformer has become the state of the art in hydrogen plants, because it complies with the demand for flexibility with respect to hydrocarbon feedstock composition and operating conditions. The benefits of an adiabatic prereformer include: Risk of carbon formation in the tubular reformer can be excluded Lower tube skin temperatures in the tubular reformer resulting in a longer lifetime of the tubes compared to operation without prereforming catalyst More than 10 years lifetime of the catalyst in the tubular reformer Possibilities of operating at a steam to carbon ratio down to 1.6 Plant load can be increased if part of revamp Energy consumption can be lowered by reheat of the prereformer exit gas in connection with a plant revamp. In the prereformer, all higher hydrocarbons are converted into hydrogen, carbon oxides and methane. Since carbon formation in the tubular reformer is normally caused by higher hydrocarbons, the prereformer will eliminate this risk. Furthermore, the prereforming catalyst picks up

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Figure 4 Prereforming catalyst operating on naphtha bed temperatures at various catalyst ages

thereby making the initial startup fast and smooth. The prereformer will normally be equipped with several thermocouples, whereby the temperature profile in the catalyst bed can be followed. Based on the temperature profile in the catalyst bed, it is possible to predict the remaining lifetime of the catalyst.

Case study 2
poisons in the feed and thus protects the catalyst in the tubular reformer as well as the shift catalyst(s). This results in lower tube wall temperatures and thus a longer lifetime of the tubes. Further, the lifetime of the catalysts in the tubular reformer and shift converter(s) is prolonged. The prereformer catalyst will be poisoned by sulphur but due to the relatively low operating temperature, carbon formation will not take place. The operating temperature is typically around 500C. With a prereformer, it is possible to operate at a low steam to carbon ratio. This is especially of interest for hydrogen plants using a PSA unit for purification of the hydrogen. In existing hydrogen plants, the plant capacity can normally be increased by installation of a prereformer. The exit gas from the prereformer can be reheated to 650C in a coil in the convection section before being routed to the tubular reformer. The higher inlet temperature to the tubular reformer will reduce the required duty in the reformer or, alternatively, the feed flow can be increased at unchanged reformer duty. The reheat of the prereformer effluent gas may lower the energy consumption. For the prereformer, the nickel based catalyst RKNGR can operate on feedstocks ranging from natural gas to heavy naphtha. Furthermore, it can operate on naphtha at a steam to carbon ratio down to 1.6. This allows a very high flexibility with respect to operating conditions when designing new plants or revamping existing hydrogen plants. The RKNGR catalyst is delivered prereduced, In 1992, a 72500Nm3/h Topse hydrogen plant operating on naphtha was commissioned. It was one of the first hydrogen plants designed with a prereformer and being operated at a steam to carbon ratio of 2.5. In Figure 4, the temperature profile from the prereformer has been plotted at various catalyst ages. The plant has been operating for seven years without replacing prereforming, tubular reforming or shift catalyst. The temperature profile in the prereformer indicates that the catalyst can operate for at least another four years.
Tubular reformer

The tubular reformer is the most critical and most expensive unit in the hydrogen plant. In older hydrogen plants using methanation for final purification of the hydrogen, there is little flexibility with respect to modification of operating conditions. This is mainly due to design limitations in the tubular reformer. In these plants, the best way to cut costs is related to the feedstock; ie using refinery offgases or any other cheap feedstock available. In newer hydrogen plants using PSA for final purification of the hydrogen, there is more flexibility with respect to optimising operating conditions. In particular, the new types of alloys for the reformer tubes make it possible to design for exit temperatures of more than 900C. This means that the hydrogen plant can be designed for a low steam to carbon ratio, and the methane leakage from the reformer can be chosen to give the minimum overall production cost for the hydrogen. The desired methane leakage will

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mainly depend on availability of low cost fuel for the reformer. Since the tubular reformer is an expensive unit, it is desirable to minimise its size, ie increase the heat flux. In naphtha-based plants, the heat flux is limited by the risk for carbon formation. However, if a prereformer is installed, the risk of carbon formation can be excluded and the heat flux of the tubular reformer will only be limited by the tube wall temperatures which depend on heat transfer and catalyst activity. Furthermore, if the effluent gas from the prereformer is reheated, the size of the tubular reformer can be reduced further. In the high heat flux tubular reformer, the demand for catalyst activity is high. The company produces a high activity R-67-7H catalyst for tubular reformers operating on natural gas or on prereformed gas. It is delivered in the form of cylinders penetrated by seven holes. This shape of the catalyst particle leads to higher activity and lower pressure drop compared to ringformed catalyst. The catalyst is based on a magnesium/aluminium-spinel structure, which has an unmatched high thermal stability. For tubular reformers operating on naphtha, there is an MgO-based nickel catalyst, type RKNR. This catalyst can operate on feedstocks ranging from natural gas or refinery offgases to heavy naphtha or any mixture hereof. The high alloy tubes in the tubular reformer are very expensive. The lifetime of the tubes will depend very much on the actual tube wall temperature. Normally, the tubes are designed for a lifetime of 100000 hours but if the actual tube wall temperatures exceed the design temperature due to low catalyst activity or due to carbon formation in the tubes, the lifetime of the tubes may be reduced considerably. Typically, the lifetime will be reduced from 100000 hours to 25000 hours if the tubes are operated 30C above design. Since replacement of the reformer tubes is very costly, the tube wall temperature is a very important operating parameter and normally plant operators monitor the tube wall temperature every day.
High temperature shift

ciency. The shift section may consist of either a one step or two step conversion (see Figures 1 and 2). In the latter, the section will normally have a high temperature shift converter and low temperature shift converter. Over the years, the high temperature shift catalysts have been operated under conditions that are increasingly severe. In particular, the reduction of the steam to carbon ratio increases the strain on the catalyst. To meet the demand for todays high temperature shift catalyst, there is the SK-201-2, which is a copper-promoted catalyst. This catalyst prevents the formation of iron carbide formation at low steam to carbon ratios, which weaken the catalyst and may eventually lead to its disintegration. The copper content of SK-201-2 further inhibits the formation of Fischer-Tropsch byproduct, such as hydrocarbons and oxygenates, thereby saving valuable hydrogen. The SK-201-2 catalyst possesses an activity that is 50 per cent higher than that of previous generation of high temperature shift catalysts. The higher activity may also allow the operating temperatures to be reduced significantly, thus leading to a lower CO slip. Another feature of SK-201-2 is that it is essentially free of hexavalent chromium. The initial startup therefore becomes smooth and easy and it eliminates chromium-containing condensate during this operation. The sulphur content is also very low and the time-consuming desulphurisation before the catalyst is being put on stream for the first time can thus be eliminated. Some plants experience pressure drop problems due to deposition of foreign material on top of the bed. Such material may originate from the upstream equipment like refractory in the reformer outlet system. TK-20 is a special topping material combining high porosity and high void, thus preventing crust formation.

Case study 3
A plant operated a charge of the classical high temperature shift catalyst for five years. In 1990, the plant installed Topses copper promoted high temperature shift catalyst SK-201. The new charge was a short-loading with a catalyst volume of 80 per cent of the catalyst volume of the classical high temperature shift catalyst. Furthermore, the plant throughput was raised

The shift section converts the high level of carbon monoxide in the process gas stream into hydrogen. An effectively working shift section is thus important in order to obtain high plant effi-

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skimmed in order to reduce the pressure drop. After experiencing a few cycles with pressure drop build-up, the plant decided to install the inert TK topping material on top of the catalyst bed. Since then, the pressure drop has remained stable at 0.5kg/cm2 without any tendency to increase.
Low temperature shift

The low temperature shift catalyst is an important cataFigure 5 High temperature shift outlet CO slip lyst as it has to ensure the final CO conversion to a low by 50 per cent. So far, the catalyst has been in level and thereby directly affect the plant effiservice for eight years and, as seen from Figure ciency. The low temperature shift catalyst may to 5, the SK-201 has still not reached the CO leak- some extent compensate for an increasing CO age experienced at the end-of-run with the slip at the outlet of a high temperature shift classical high temperature shift catalyst. converter. The high temperature shift catalyst, however, cannot make up for a badly performing Case study 4 low temperature shift catalyst. A user of Topse high temperature shift catalyst The requirement of the low temperature shift experienced pressure drop problems with an catalyst is that it has a high and stable activity. otherwise satisfactorily performing catalyst. At The low temperature shift catalyst LK-821-2 the beginning, the pressure drop was 0.5kg/cm2. possesses an inherently high and stable activity. After a couple of years, the pressure drop had Furthermore, the catalyst acts as its own sulphur risen to 1.5kg/cm2 and the plant had to inspect guard as it has a very high capacity for sulphur. the catalyst bed. The low temperature shift catalyst charge is It was determined that deposits on top of the normally delivered as a combination charge. A catalyst bed caused the pressure drop problem. small layer of LSK is installed on top of the LKAccordingly, the top of the catalyst bed was 821-2. The LSK is a special catalyst. It has a very strong affinity for absorbing chlorine, thereby retaining this severe poison in the very top of the bed. Further, LSK will not weaken or disintegrate if exposed to steam condensate. The composite loading of LSK and LK-821-2 thus ensures that the low temperature shift catalyst has a high and stable activity, high resistance to poisoning and excellent mechanical stability. The increasing environmental focus has in some areas led to strict local emission regulaFigure 6 Methanol formation at low temperature shift conditions tions. For hydrogen plant

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operators, the methanol byproduct Results of LK-821 chemical analyses formation across the low temperature shift catalyst has been the subject of Sample Catalyst Sulphur,ppm Chlorine,ppm Silicon,ppm increasing concern. 3ft LSK 1700 3500 1500 The methanol partly ends up in the 4ft LK-821 7300 1000 410 6ft LK-821 8600 730 Not available process condensate where it may be 8ft LK-821 4300 970 Not available recycled back to the reformer section 10ft LK-821 3200 Not available Not available or stripped in a process condensate 12ft LK-821 2500 Not available Not available stripper. The rest of the methanol ends 14ft LK-821 4200 Not available Not available up in the process gas going to the CO2 removal system, exiting the plant with Table 1 the CO2 from the CO2 stripper. Apart from this emission problem, Example of LK-811 performance other concerns are that methanol may react to form amines and give odour Hydrocarbon feedstock: Naphtha problems, may affect the quality of the Catalyst age SOR 6 years process condensate, and in the CO2 Plant rate, % 102 96 may affect downstream processes if the S/C ratio inlet tubular reformer 2.6 2.5 MTS performance Inlet Exit Inlet Exit CO2 is not vented. Formation of methaGas analyses, mole% dry nol also consumes valuable hydrogen. H2 66.1 70.2 66.7 70.8 In order to overcome the problem with CO 16.4 1.4 16.4 1.9 methanol byproduct formation, Topse CO2 9.8 22.5 9.6 20.8 CH4 7.7 6.1 7.4 6.4 has introduced a low methanol, low Temperature, C 205 309 205 306 temperature shift catalyst LK-823. This is a caesium-promoted catalyst that has all the salient features of LK-821-2, Table 2 described above, as well as a significantly improved selectivity, resulting in a comply with the new regulations. The alternative reduction in the methanol byproduct formation to LK-823 was to engineer and install methanol removal equipment at an estimated cost close to by nearly an order of magnitude. Figure 6 shows the methanol formation of LK- US$2 million. 823 and LK-821-2 under low temperature shift Medium temperature shift operating conditions. The medium temperature shift catalyst LK-811 Case study 5 has been developed to cover a wide range of A hydrogen plant operated a charge of LSK/LK- operating conditions. LK-811 is more flexible 821 for six years experiencing a very satisfactory than a traditional, high temperature shift catalyst performance. Upon unloading of the spent cata- and may therefore be used as a replacement for lyst, samples were collected for chemical analysis. the standard, high temperature shift catalyst in Table 1 shows the results of the analyses, illus- hydrogen plants operating at very low steam to trating how the combined LSK and LK-821 carbon ratios. loading provides an excellent protection for the In new hydrogen plants, the LK-811 may active catalyst below the poisoning zone. replace both the high and low temperature shift catalysts in which case the medium temperature Case study 6 shift exit gas after the CO2 removal may be sent In 1997, a hydrogen plant located in an area with directly to a PSA unit (see Figure 2). already strict environmental regulations had to Alternatively, the medium temperature shift exit comply with new government legislation as well gas may be sent to a low temperature shift unit as even stricter local regulations aiming at limit- where the CO is reduced further. ing methanol emissions. The Topse medium temperature shift catalyst The plant decided to install LK-823 in the low LK-811 is a copper/chromium/ zinc catalyst temperature shift converter which enabled it to which is normally operated in the temperature

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range 190330C. Since the LK-811 contains no iron, operation at steam to carbon ratios as low as 2.5 or even lower is possible.

Case study 7
Table 2 gives an example of the performance of LK-811 in a hydrogen plant operating at a steam to carbon ratio of around 2.5 illustrating that even at a very low steam to carbon ratio and with a heavy hydrocarbon feedstock, it is possible to obtain a low CO leakage in a single step. Even after six years of operation the catalyst is still giving good performance at a low inlet temperature, and no replacement is planned yet.

Topse has therefore introduced the prereduced methanation catalyst PK-7R in order to accommodate the increased demand for low temperature operation. The PK-7R is a nickel type catalyst on an alumina carrier reduced under controlled and optimal conditions. This catalyst displays a much higher activity than conventional methanation catalysts, especially in the low temperature range and in fact, it is possible to operate continuously at an inlet temperature of 190C.

Case study 8
A hydrogen plant which has always had problems with very high CO and CO2 slip (typically 10002000ppm), because it is unable to increase the inlet temperature above 250260C, decided to go for PK-7R methanation catalyst because of the catalysts characteristics. This catalyst has now been in service for four years and is operated at an inlet temperature as low as 204C. The plant reports that CO and CO2 concentration is below 1ppm or not detectable at all.
Leif Storgaard is product manager, Reforming Catalysts, and Hans Christian Nielsen is marketing manager, Syngas, with Haldor Topse A/S, Lyngby, Denmark.

Methanation is the last reaction step in the traditional hydrogen plant. The process gas is at this stage normally free of poisons. Furthermore, operating conditions are not as demanding as is the case for the reforming and shift catalysts. The lifetimes of the methanation catalysts are thus commonly in the area of 10 years or more. However, the improvements in shift catalysts and efficiency of CO2 removal systems have significantly reduced the content of carbon oxides in the methanation feed gas. The consequence has been lower methanation temperatures and many plants have experienced deteriorating methanation catalyst performance. To alleviate this problem, an increased preheat of the methanation feed stream may be implemented. This, however, is at the expense of valuable heat that could be used in other parts of the plant.

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