FUEL PROCESSING TECHNOLOGY

ELSEVIER
Fuel Processing Technology 42 (1995) 85-107

Tubular reforming and autothermal reforming of natural gas - an overview of available processes
Ib Dybkjax*
Haldor Topwe A/S, Nymallevej 55, DK-2800 Lyngby, Denmark

Received 7 February 1994; accepted in revised form 12 July 1994

Abstract

Tubular reforming and autothermal or secondary reforming of natural gas are the most important process steps in the production of synthesis gas. The paper reviews the state-of-theart of the technologies with emphasis on new developments in equipment design, especially relating to the tubular reformer furnace and to the burner for the autothermal or secondary reformer. The chemical reactions are briefly described, and the various steam reforming processes - tubular, fired reforming, heat exchange reforming, and adiabatic pre-reforming - are reviewed. The difference between autothermal and secondary reforming and new developments in these process technologies are highlighted.

1.

Introduction

Natural gas is the most important raw material for, production of ammonia, methanol, hydrogen, carbon monoxide, and many other important products. In almost all cases it is converted catalytically by reaction with steam and/or oxygencontaining gases, i.e. air, enriched air, or oxygen. The related technologies, i.e. the various versions and combinations of steam reforming and autothermal or secondary reforming, are thus key technologies in the petrochemical and fertilizer industries today. The technologies have been known and applied in the industry for more than 50 years and must today be considered quite mature. However, important new developments are constantly being made, both in equipment design and in the related catalysts. The purpose of the present paper is to review the state-of-the-art and to describe recent developments for tubular reforming and autothermal and secondary reforming with emphasis on process concepts and design of critical items.

* Tel.: + 45 45 27 29 99. Fax: + 45 45 27 20 00. 0378-3820/95/%09.50 0 1995 Elsevier Science B.V. All rights reserved SSDI 0378-3820(94)00099-9

86

I. DybkjmlFuel

Processing

Technology 42 (1995) 85-107

The conversion of natural gas may be done by several different processes or combinations of processes. The most important options are: (i) tubular, fired reforming; (ii) heat exchange reforming; (iii) adiabatic pre-reforming; (iv) autothermal and secondary reforming. In the following, a short introduction is given to the relevant chemical reactions. After this follows a description of each of the processes, in particular the tubular reformer furnace and the burner for secondary/autothermal reformers.

2. The reactions A number of chemical reactions are of interest for the discussion of reforming technology. In the following the stoichiometry and the thermodynamics are briefly discussed for the most important reactions. Methane may react with steam by the methane steam reforming reaction and the shift reaction: CH4 + Hz0 = CO + 3H2, CO + Hz0 = CO2 + Hz, Higher hydrocarbons a similar way: AH = + 49 kcal/mol AH = - 10 kcal/mol (1) (2) will react in

in natural gas, LPG or liquid hydrocarbons

C,H, + nHzO = nC0 + (n + m/2)Hz,

Endothermic

(3)

Steam may be replaced by carbon dioxide, which gives a more favourable hydrogen to carbon monoxide ratio for many syntheses: CH4 + COz = 2C0 + 2Hz, AH = + 59 kcal/mol (4)

Reactions (l)-(4) require a catalyst, typically supported nickel. Methane may also be converted by means of oxygen into synthesis gas by partial oxidation, represented e.g. by: CH4 + +O, + CO + 2Hz, AH = - 9 kcal/mol (5)

This reaction may be non-catalytic or use a catalyst, typically supported nickel. The methane reforming reaction (1) and the water gas shift reaction (2) are reversible at reforming temperatures, while reaction (3) is irreversible and proceeds to full conversion of the higher hydrocarbons. Reaction (4) is the difference between reaction (1) and reaction (2). It is evident, from the principle of Le Chatelier, that at higher temperatures less methane and more carbon monoxide are present in the equilibrium gas, and that methane content increases with pressure and decreases with increasing ratio of steam to carbon. This is illustrated in Fig. 1 [l].

it is possible to carry out the process without external heating. The product gas composition from a reformer can be estimated from thermodynamic calculations because it will in most cases be close to that of the equilibrated gas. and the overall reaction becomes strongly endothermic.g. in an ‘ adiabatic pre-reformer’ However. depending on the process conditions. “C Fig. 1. At low steam to carbon ratios and at low catalyst exit temperatures. Carbon formation is discussed in detail in [Z-4]. Equilibrium composition (dry gas). higher hydrocarbons may react in parallel to reaction (3) by thermal cracking (pyrolysis or “steam cracking”) into olefins which may easily form coke via reaction (9): C.41 kcal/mol AH = + 18 kcal/mol (6) (7) (8) CH4 = C + 2Hz. The conversion of hydrocarbons with oxygen is done in the catalytic autothermal or secondary reforming processes and also in the non-catalytic partial oxidation processes. (9) Reactions (6) and (7) are reversible. + olefins + polymers + coke. for the production of gases with lower methane . The overall heat of reactions (l)-(3) may be positive. Pressure 30 bar. the overall reaction is only slightly endothermic or even exothermic. C. AH = . whereas (8) and (9) are irreversible for n > 1. A list of equilibrium constants may be found in [2]. a high catalyst outlet temperature is required. This is caused by methanation of carbon monoxide formed by reaction (3) and reflected by a high content of methane in the product gas.I. Dry Mole % 100 80 60 40 400 600 800 1000 TemDerature. Reactions (1) and (3) may be accompanied by the following reactions forming carbon: 2co = c + coz. if the feed contains high concentrations of higher hydrocarbons. atures (above about 65o”C). In such cases. Steam reforming of methane. contents such as synthesis gas and hydrogen. steam-carbon ratio = 4. Due to the internal combustion these processes are exothermic and takes place in adiabatic reactors. zero.0.H. DybkjmlFuel Processing Technology 42 (1995) 85-107 87 Composition. In such cases. heat must be supplied to the reaction. or negative. -+ nC + m/2Hz Reaction (6) is normally referred to as the ‘ Boudouard reaction’ At high temper. .H. e. which then takes place in a tubular reformer.

The tubes. DybQzrlFuel Processing Technology 42 (1995) 85-107 3. are arranged in a single row.1. Mechanical design A Topsere reformer furnace is shown in Fig. 2 [S]. which are filled with catalyst.88 I. fired reforming 3. Tubular. 2. Reformer furnace designed by Topwe for high outlet temperature. and burners are placed in the furnace walls at Fig. .

:. 3. allowing expansion of the tube.. and the heat is utilized in the flue gas waste heat section.. Reformer outlet systems. Process gas from the outlet of the reformer tubes passes through the transition joint outside the furnace to the refractory-lined outlet collector. _. The two outlet systems are illustrated in Fig. In order to reduce the load on the refractory-lined collector and to eliminate any risk of tube bending. Feed gas passes from a distribution header through the inlet hairpins to the tubes. In other applications. The tubes are supported at the bottom and expand upwards through the furnace. most of the tube weight is supported by a spring arrangement connected to the top flange of the tube. Lk Catalyst TUbe . it is possible to adjust and control the heat input along the length of the tube.. In this case the inlet hairpin is connected to the side of the reformer tube. an alternative outlet system with hairpins and hot collector is used. 3 [S].I. . . With this arrangement. DybkjazrlFuel Processing Technology 42 (I 995) 85-107 89 four to six levels.: Cold Collector Catalyst Tube - Pigtail V fractow Lined Transfer Line 1 Hot Subcollector and Cold Transfer Line Fig.I :.::. The inlet hairpin is flexible. Hot flue gas leaves the radiant chamber through a refractorylined duct. allowing higher preheat temperature. thus ensuring an optimum temperature profile at all operating conditions.

In Figs. Therefore it is essential to consider the steam reformer not only as a furnace but also as a chemical reactor.90 I.6 bar. Hydrogen to carbon monoxide ratio in reformer exit gas as function of steam-carbon ratio (s/c) and outlet temperature. 4 and 5 [S] the gas composition at the reformer outlet is shown as a function of steam to carbon ratio and outlet temperature for a case where the feedstock is naphtha. however. (iii) outlet temperature. A low steam to carbon ratio. results in high methane content. pressure 21. and extra carbon dioxide may be imported when available. “ C Fig. 840 8&l 880 960 9io 9kl 9bo 9tio Temperature. the reformer outlet temperature can be increased. A high outlet temperature also changes the equilibrium of the shift reaction towards carbon monoxide. . Maximum conversion to carbon monoxide by the reverse shift reaction (2) is favoured by a low steam to carbon ratio.2. (iv) outlet pressure. In such cases the carbon dioxide from the outlet of the reformer is recycled. Gas composition The gas composition at the outlet of the reformer is strongly influenced by the process conditions. In order to compensate for this. In some cases it is also advantageous to add carbon dioxide at the inlet of the reformer in order to save hydrocarbon feedstock and decrease the hydrogen to carbon monoxide ratio in the product gas. (ii) inlet steam to carbon ratio. 4. Feed: naphtha. Dybkjter/Fuel Processing Technology 42 (1995) 85-107 3. The feed to the reformer can be any hydrocarbon ranging from a hydrogen-rich off-gas or natural gas to heavy naphtha. The most important variables are: (i) hydrocarbon feed characteristics.

is the enthalpy difference between the exit and the inlet gas. 5. The other half of the fired duty is available in the hot flue gas and recovered in the waste heat section of the reformer for preheat . the use of sulphur passivated reforming [7]. The development of new highly active steam reforming catalysts including noble metal based catalysts [6]. Normally. membrane units or cryogenic units.0. Feed: naphtha. DybkjmJFuel 25 Processing Technology 42 (1995) 85-107 Of 760 I 780 I 800 I 820 I 840 I 860 Temperature. the highest acceptable pressure is chosen so that compression downstream the reformer is avoided or minimized. 880 “C I 900 I 920 I 940 I 960 I 980 Fig. Heat balance and tube design The heat input required by the reformer. In other cases the pressure is dictated by the requirements of downstream separation or purification processes. 3.g. An increase in pressure results in high methane content. the steam to carbon ratio in reformers was relatively high due to the risk of carbon formation.6 bar. and it can easily be calculated from enthalpy tables. The outlet pressure strongly affects reaction (1) while reaction (2) is not affected.3. pressure 21. PSA units. In a typical tubular reformer furnace. the reformer duty. e. about 50% of the heat produced by combustion in the burners is transferred through the reformer tube walls and absorbed by the process gas (in an ammonia plant: 60% for reaction. and the installation of adiabatic pre-reformers [8] make it possible to reduce the steam to carbon ratio to below 1. 40% for temperature increase). The duty consists of heat of reaction as well as heat required to raise the temperature to the level of the reformer exit. ratio (s/c) and outlet Traditionally.I. Methane content (dry) in reformer exit gas as function of steam-carbon temperature.

Even a slight increase in the maximum tube wall temperature may result in a serious decline of the expected tube lifetime.. and reformer duty. whereas the dimensions of the furnace box remain’ roughly constant. The pressure drop over the reformer also decreases. The stress value in the tubes is strongly influenced by the maximum tube wall temperature and by the maximum heat flux. Basically there are four types of reformers as illustrated in Fig. These parameters are interrelated. The catalyst volume. feed flow. independent of the number of tubes: qay = d. The use of a thin tube wall improves the tube lifetime by increasing the tolerance of the tube to thermal cycling and thermal shock [9]. It can be shown by a total heat balance and by assuming constant inlet and outlet conditions that. however. also decreasing the number of inlet and outlet hairpins. the tube length is limited by the risk of tube bending and by restrictions in pressure drop across the catalyst. The furnace appr0aches.a counter-current design resulting in high metal temperatures at the outlet. 6 [Z]. The new materials which have superior creep rupture characteristics. and the space velocity. increases linearly with d. and it has the highest heat flux where the metal temperature is at its . The tube geometry has a complex influence on the reformer design. For a given tube length. Recent developments in metallurgy have allowed safe designs with exit gas temperatures exceeding 950°C corresponding to tube wall temperatures up to 1050°C. allow a design with a considerable reduction in tube wall thickness. However. qav. The top fired reformer is characterized by a peak in the tube wall temperature in the upper part of the reformer.5) 85-107 duties and for steam production. Increasing the length of the tubes is more economical than increasing the number of tubes. SV. * sv. (reduced SV. In this way. the number of tubes decreases. (10) This means that only two of these three parameters can be selected freely. Tube wall temperature and heat JIux projile Tubular reformers are designed with a variety of tube and burner arrangements. The bottom fired type has an almost constant heat flux profile along the length of the tube. (lo)). increases. the average heat flux. Eq. d. and the total weight of the tubes increases more than proportional to d. Llybkjar/Fuel Processing Technology 42 (199. The balance between heat input through the reformer tube walls and heat consumption in the endothermic reforming reaction is the central problem in steam reforming. the number of tubes is determined by the selected tube diameter. due to increased tube wall thickness above a minimum diameter below which the tube wall thickness must be kept constant for other reasons.4. the overall thermal efficiency of the reformer may approach 95%.92 I. The terrace wall fired reformer is a modification of the bottom fired type. having slightly lower tube wall temperatures. because more tubes mean more complex inlet and outlet systems. 3. If qav is constant and d.

.000 kcsl/m’ /h / / lOOO-. typically below 50 ppm for reformers without combustion air preheat. The side wall fired design thus offers more flexibility in design and operation. 7 for start of run. Typical configurations of reformer furnace. As an added advantage. 7. whereas the highest heat flux is at a relatively low temperature. The side wall fired furnace allows adjustment and control of the tube wall temperature. Start of run.1.000 kcal/m’ /h loo 600 - 1 I I 20 40 60 80 100 Tube Length. The maximum temperature is at the outlet of the tube. Typical tube wall temperature and heat flux profiles for top. Side and top fired reformers. Tube wall temperature and heat flux profiles. Top Fired Reformer Average Heat Flux: 65. % Fig. levels in the flue gas. the short residence time in the flames in the side wall fired furnace ensure very low NO.120 \/ \ Y\ Side Fired Reformer Average Heat Flux: 75.’ / /-\ . and higher average heat flux and more severe operating conditions are possible.and side fired reformers operating at the same conditions are shown in Fig. 6. DybkjmlFuel Processing Technology 42 (1995) 85-107 93 maximum. The Bottom Fired Top Fired Terrace Wall Side Fired Fig.

In the top fired reformer this means that the maximum tube wall temperature increases correspondingly. The reduced activity means that less reaction takes place here. Even in this case. Furthermore. there is no distinct maximum. since the maximum temperature is in the top of the tube. The heat flux profiles are calculated on the basis of the temperature profiles using computer models. therefore. provided the required heat is made available. whereby the temperatures increase as indicated by the dotted lines because less heat is consumed. Comparisons based on the same average heat flux are. well-defined area. This means that also for the same maximum heat flux. which is determined by the conditions . There is. since reduction of the total firing is the only possible way to reduce the heat input in the top of the tube.the conversion is determined by the heat transfer.g.94 I. by sulphur. A further point of considerable interest is the ‘ response’ of the furnace to changes in catalyst activity. a significant effect on the tube wall temperatures in the upper part of the tube as shown in Fig. Also. The tubes must therefore be designed with a considerable margin above the start-of-run maximum temperature. the heat transfer from the furnace to and through the tube. The heat flux profile of the top fired reformer shows a sharp maximum in the top of the tube . temperatures in a narrow. In the side fired reformer the temperature in the top can increase significantly without approaching the design temperature. the tubes in the side fired reformer are subject to lower stresses and thus can be designed with thinner wall (at same diameter) or larger diameter (at same wall thickness). DybkjmlFuel Processing Technology 42 (1995) 85-107 temperature profiles are based on measured data from operating reformers. alternatively. Reformers of all types normally contain ample catalyst activity . In the side fired reformer. the capacity of the unit must be reduced. there is a risk of carbon formation on the hot tube wall. the tube wall temperature increases at a controlled rate to a maximum value at the outlet of the tube. the heat flux profile is much flatter. however. and the highest local heat flux is much lower that in the top fired reformer. It is seen that the tube wall temperature profile for the top fired reformer shows a flat maximum approximately one third down the tube. or. but they are misleading for different types. which will aggravate the problems and lead to so-called ‘ hot banding’ very high tube wall .g. This means that a significant loss of activity can be accommodated without any loss of conversion and with only modest increase in the temperatures in the lower end of the tube. It is thus evident that the side fired concept allows a much higher average heat flux than the top fired concept. which take into account both the geometry of the furnace chamber. unrealistic. and the heat transfer and catalytic reactions inside the tube. in comparisons of side and top fired reformers. In the side fired reformer. Such changes are inevitable due to ageing of the catalyst and possibly due to poisoning. 8. A more relevant comparison would be based on maximum local heat flux. e. although the average heat flux is higher. e.at a location where the tube wall temperature is relatively high. They may be relevant for comparison of reformers of the same type. the conditions on the tube would be more severe in the top fired reformer concept because of higher temperature at the peak in the heat flux. the tube temperature at the point where the heat flux is highest is much lower in the side fired reformer than in the top fired reformer.

or premature catalyst change can thus be avoided. 100 Fig. Side and top fired reformer. at the lower part of the tube. 8.5. tube damage by hot banding. the firing can be adjusted if the tube wall temperatures approach the design temperature. % I 20 1 40 1 60 I 80 . The furnace has radiant wall burners at six levels on two opposite walls in the furnace box. The demonstration unit consists of one inter-changeable full-size reformer catalyst tube placed in a rectangular furnace (Fig. Furthermore. USA. Gas samples are taken continuously from the inlet and the outlet of the tube and from different positions in the catalyst bed so that the degree of conversion in the reaction can be followed. “C) lOOO- 95 600- Start of Run ----End df Run Tube Length. This configuration is particularly appropriate as it allows simulation of almost any kind of outer tube wall temperature profile by variation of the firing pattern. 3. Furthermore. LlybkjazrlFuel Processing Technology 42 (1995) M-107 Tube Wall Temperature (Outside. Tube wall temperature profiles at start and end of run. For this purpose Topsse has built a full-scale process demonstration unit at the pilot facilities in Houston. the outer tube wall temperature is measured very accurately by pyrometry. and thermocouples.I. but the complicated heat and mass transfer characteristics in a reformer furnace must be studied in industrial size units. infrared camera. Texas. and loss of capacity. . Thermocouples are positioned inside the reformer tubes for measuring axial and radial temperature profiles. Process demonstration unit It is relatively simple to produce an equilibrated gas over a nickel catalyst in the laboratory. 9).

s . Topsee’ process demonstration unit in Houston. USA. 9. Dybl@r/Fuel Processing Technology 42 (1995) 85-107 Fig. Texas.96 I.

An alternative design better suited for high pressure applications and for larger capacities is the convection reformer. This is in contrast to the conventional ‘ tubular reforming’ where all heat is supplied by external combustion. Heat exchange reforming In heat exchange reforming. but also by the reformer gas flowing upwards through the bayonet. production of carbon monoxide and carbon monoxide-rich synthesis gas: [17. 163. Space will not permit a discussion of s all these areas.alone or in combination with other reforming steps such as adiabatic pre-reforming or secondary reforming . and to secondary or autothermal reforming. and good load following characteristics are essential. axial and radial catalyst bed temperature profiles. part or all of the heat required for the reforming reaction is supplied by heat exchange with process gas. high efficiency. With the purpose of optimizing the heat transfer. This ensures that the . town’ gas. production of hydrogen: [15. etc. Properties such as physical strength. axial conversion profiles. 3.5]. Applications of tubular reforming Tubular reforming is used . The capacity range for the HER is 504000 N m3/h of hydrogen for fuel cell operating conditions (low pressure). and intrinsic activity give important information about risk of carbon formation and expected catalyst life and thus about the suitability of the tested catalyst for a given process. pore volume distribution. where the heat is supplied by internal combustion. The convection reformer is designed with a number of bayonet reformer tubes. At the hot end.14]. the reformer tube is inherently protected against overheating by means of a patented convection control device. and for parameter estimation in reaction kinetic models and in heat transfer and pressure drop correlations. a sleeve has been installed around the cold end of the reformer tube. It is heated mainly by the flue gas flowing upwards on the outside of the reformer tubes. production of methanol synthesis gas: [13. hydrogen. 4. The catalyst is examined in the laboratory after a certain operating period. carbon monoxide. One mechanical concept of these units is known as the heat exchange reformer (HER) [18]. A number of heat exchange reformers have been designed for hydrogen production in fuel cell plants. A full-scale process demonstration unit with a capacity of 840 Nm3/h hydrogen has been operated at Topsoe’ Houston pilot s facilities for more than 2000 h.in the majority of installations for conversion of light hydrocarbon feedstocks to synthesis gas. and pressure drops. carbon content.6. This information is then used for evaluation of the conditions to which the catalyst and tube have been exposed during the experiment. Some relevant references are: production of ammonia synthesis gas: [l&12]. sulphur capacity. where the requirements with respect to compactness. reducing gas. Dybkjmrl Fuel Processing Technology 42 (I 995) 85-107 91 The information obtained from the experiments is in the form of outer tube wall temperature profiles.I.

98 I. This is straightforward in production of hydrogen and methanol synthesis gas. tubular reforming step is supplied by heat exchange with the exit gas from a second. 10 illustrates temperature profiles from the process demonstration unit. and the process concept is of interest only in certain situations [25. simplifying the design and control of the unit. and that it is almost insensitive to variations in operating conditions. Temperature profiles from the process demonstration unit. but in production of ammonia synthesis gas with air-fired secondary reforming there is a poor correspondence between the heat available and the heat required. It is clearly seen how the tube wall temperature is controlled in the lower part of the tube. A special problem in these process concepts and in other situations where carbon monoxide-rich gases contact metals at high temperature is metal dusting corrosion. The corresponding figure in a fired tubular reformer is around 50%. this means that about 80% of the fired duty is utilized in the process. Other types of heat exchange reformers have also been proposed [ 19-24.or oxygen-fired step which can either be a catalytic. the reaction may be catalyzed by hot .A given gas will have potential for carbon formation by the (exothermic) Boudouard reaction (6) below a certain temperature.151. The convection reformer combines in one relatively small piece of equipment the radiant chamber with tubes and burners and the hot part of the convection section. 11. the Boudouard temperature. Fig. When the Boudouard temperature is high. The Topsse convection reformer has a single burner. maximum metal temperature is kept below a predetermined value even at high conversion. at which the reaction is at equilibrium. The exit temperature from the reformer is for both process gas and flue gas reduced by heat exchange to about 600°C. when the partial pressure of carbon monoxide is high. The burner chamber is separated from the reformer tube section. secondary reformer or a non-catalytic partial oxidation [23]. air. i. thus avoiding the energy surplus inherent in conventional plants. . These references all describe two-step processes where heat for the first.e. In plants using the convection reformer it is possible to balance the duty required by the reformer to match the heat available in the PSA off-gas. Dybkja?rlFuel Processing Technology 42 (1995) 85-107 Tube Length Fig. 10. Topsee convection reformer.

and variations in feedstock. if this film is destroyed.g. the duty of the tubular reformer will not change. this can be done during a scheduled shutdown. The installation of an adiabatic pre-reformer upstream a steam reformer gives a number of benefits: . In the pre-reformer. giving a completely sulphur-free feed to the tubular reformer. However. the catalyst outlet temperature will always be above Boudouard temperature (because carbon would otherwise be formed on the catalyst). and it will facilitate changes in operating conditions. Fe-Ni-Cr alloys are protected against carburization by an oxide layer. bring the product gas below the Boudouard temperature. A temperature drop in the reformer outlet system or in the cooling channels of the heat exchange reformer could. 5. The corrosion starts by pointwise attack. and no new preheat coils are installed. probably by carburization at defects in the oxide layer.I. However. By reheating the pre-reformer effluent to 650°C the required heat duty in the tubular reformer is decreased by up to 25%. For heavier feedstocks such as naphtha the overall process is exothermic or thermoneutral. The reactor is loaded with a highly active reforming catalyst. In an operating reformer. the overall process is endothermic. the pre-reformer will act as a guard for the tubular reformer. Dybkjcw/Fuel Processing Technology 42 (1995) M-107 99 metal surfaces. The corrosion products can easily be eroded and holes are formed in the material similar to pitting.27]. e.e. a catastrophic corrosion can occur [26. the equilibrium for chemisorption of sulphur on the Ni-based catalyst is favourable. but close to Boudouard temperature. 11 shows the preferred solution for debottlenecking or revamp of existing plants and the most common process lay-out in new plants. At most conditions. Fig. It is thus important that a gas with a high Boudouard temperature does not come into contact with a metal surface with a temperature below. hydrogen and methane. Adiabatic pre-reforming Adiabatic pre-reforming is used for reforming of hydrocarbon feedstocks ranging from natural gas to heavy naphtha with final boiling points above 200°C and aromatics content above 30%. If the feedstock is natural gas. i. however. Tr ace s of sulphur leaking from the desulphurization section are quantitatively removed from the feed gas. into an area where carbon may be formed on the metal surface. reduction of steam to carbon ratio. The installation of a pre-reformer in an existing plant is very simple since there is no change in the hot end of the tubular reformer. resulting in a temperature drop. If no modifications of existing coils are made. Since the operating temperature of the pre-reforming catalyst is relatively low. Fundamentals of the process are discussed in [28]. The process is carried out in a fixed bed adiabatic reactor upstream the tubular reformer. If a new coil is to be installed in the flue gas waste heat section. higher hydrocarbons are completely converted into a mixture of carbon oxides. Most of the new equipment can be installed while the plant is in operation.

. By installing an extra preheat coil or heater between the pre-reformer and the tubular steam reformer. is a stand-alone process in which the entire hydrocarbon conversion is carried out in one reactor aided by internal . Process concepts Autothermal reforming. natural gas reforming catalyst may be used in the tubular reformer. .The production capacity of the plant can be increased. Preferred lay-out. town’ gas plants. ammonia plants.All higher hydrocarbons are completely converted to carbon oxides and methane. Installation of pre-reformer. the risk of hot banding or hot spots is reduced. i. _ The sensitivity of the tubular steam reformer to variations in steam to carbon ratio and feedstock composition is practically eliminated. hydrogen plants.The benefits can be achieved in all plants having a tubular steam reformer. Even in plants based on naphtha. 6. increasing the lifetime of the tubular steam reforming catalyst and low temperature shift catalysts. Autothermal reforming and secondary reforming 6. . Dyb&zr/Fuel Processing Technology 42 (1995) 85-107 Tubular Reformer Steam Hvdrocarbon Feed Flue Gas Channel Fuel I .100 I. 29). oxogas/carbon monoxide plants. To Heat Recovery Fig. as described in this paper. I. the load on the reformer is decreased. methanol plants.All traces of sulphur from the desulphurization unit are removed. Use of pre-reforming is discussed in s [&lo-12. 11.Since there is no sulphur poisoning of the top layer of catalyst in the tubular reformer. This can be utilized either as a capacity increase or as a decrease in firing with unchanged capacity. . and reducing gas plants. .e.

This lay-out features Carbon Dioxide Boikr Feed Water Fig. Production of synthesis gas with . Desulphurization is normally not required if the feed is natural gas with low sulphur content. Therefore. The flowsheet in Fig.I. 13 illustrates ‘ state-of-the-art’ technology for production of ammonia synthesis gas by primary reforming and air-fired secondary reforming [25]. The concentration of combustibles in the feed to the autothermal reformers is higher than in the feed to the secondary reformers. DybkjwlFuel Processing Technology 42 (1995) 85-107 101 combustion with oxygen. for production of ammonia synthesis gas. Similar schemes can be used for large-scale production of methanol synthesis gas. Fig. 12 [30]. Secondary reforming is a process in which partially converted process gas form a primary (tubular) reformer is further converted by internal combustion. comprises a feed preheat section. This concept is normally not used in natural gas-based ammonia plants. The secondary reformer in ammonia plants will typically be air-blown while in methanol plants it will be oxygen-blown.0 suitable for synthetic fuel. with enriched air with properly adjusted composition. a reactor. hydrogen or. the heat release. and a gas separation unit. it is mainly of interest in cases where steam production must be minimized. Typical hydrogen-carbon process flow diagram monoxide ratio 2. The lay-out of a ‘ two-step’ reforming process for production of methanol synthesis gas is shown in Fig. 12. for autothermal reforming. flow conditions.0. as illustrated in Fig. 12 illustrates the use of autothermal reforming for synthesis gas production of hydrogen/carbon monoxide = 2. 14 [13]. Secondary reforming is mainly used in production of synthesis gas for ammonia and methanol. The scheme shown also includes an adiabatic pre-reformer. and the risk of soot formation are different in the autothermal and secondary reformers resulting in different requirements to burner and reactor design. a heat recovery section. This plant lay-out contains much less equipment that conventional steam reforming plants. A typical autothermal reforming process scheme.

However. . A similar process is described in [31]. ‘ Two-step’ reforming for production of methanol synthesis gas.mixture of oxygen (generated in a package air separation plant) and steam. a relatively small primary reformer operating at mild conditions followed by a secondary reformer using a. 13. ‘ State-of-the-art’ reforming section for production of ammonia synthesis gas.102 I. 14. in this case part of the hydrocarbon feed by-passed the primary reformer and is added direct to the oxygenfired secondary reformer. Process Steam Oxrw HP Steam to Turbines Boiler Feed Water Make-up Gas Natural Gas _ I I I Heat Recovey (mm Methanol Synthesis Fig. DybkjcerlFuel Processing Technology 42 (1995) 85-307 HDS Process Air Prereformer Primary Reformer Secondary Reformer < Process Steam Natural Gas Feed t Stack Air < 11:” Recycle Gas Combustion Fuel Gas J To Waste Heat Recovery and Shih Fig.

DybkjmlFuel Processing Technology 42 (1995) 85-107 103 6.55-0. the catalytic zone. The flame core has a very high temperature. The combustion proceeds as a substoichiometric process with an overall oxygen to hydrocarbon ratio of 0. but various pyrolysis reactions involving higher hydrocarbons also take place. The chemical reactions taking place are combinations of combustion and steam reforming reactions dividing the reactor space into three reaction zones.6. The main reactions are thermal methane reforming (1) and water-gas shift reaction (2). as illustrated in Fig. a combustion chamber and a catalyst bed. a burner design based on the understanding of the fluid dynamic principles of the mixing and combustion processes is necessary to obtain a safe operation and a satisfactory burner lifetime. i. the principle of ‘ mixed-isburnt’ can be assumed.2. but in a simplified model it can be considered as one molecular reaction. Hence. The burner provides the mixing of the feedstreams in a turbulent diffusion flame. because the exothermic combustion reactions consuming oxygen are very fast reactions.e. Reactor design The autothermal reformer reactor and the secondary reformer are very similar. Thermal Zone Catalyst Bed Fig. Both consist of a compact refractory-lined pressure vessel with a burner. the highly exothermic combustion of methane to carbon monoxide and water with an oxygen to methane ratio of 1. The combustion of methane takes place through numerous radial reactions. The catalyst will destroy any soot precursors formed in the combustion and thermal zones.5. 15 [30]. The so-called thermal zone is the part of the combustion chamber where further conversion of the hydrocarbons proceeds by homogeneous gas phase reactions. Reaction I Catalvtic Zone zones in autothermal reforming. 15.and transfer of heat back to the burner from the flame core by radiation and by recirculation of hot gas must be minimized. . Normally. The combustion zone is the turbulent diffusion flame where the hydrocarbon and the oxygen are gradually mixed and combusted. in which the final hydrocarbon conversion takes place through heterogeneous catalytic reactions.I. Excess methane will be present at the combustion zone exit after all the oxygen has been converted. The combustion chamber is followed by a fixed catalyst bed. The burner is the key element of the autothermal and secondary reforming technology. At the exit of the catalytic zone the synthesis gas will be in equilibrium with respect to the methane reforming (1) and shift reactions (2). Combustion of higher hydrocarbons can be simplified by similar reactions. often above 2OOo”C.

The CTS burner design is patent-pending in countries worldwide. Pilot plant testing also provides the advantages that development of the combustion equipment (burner. 6. and high thermal stability of the catalyst and the carrier system is required. In practice the catalyst volume is determined by optimal flow distribution and pressure drop in the reactor. 6. The performance of various burner models was predicted by CFD calculations and verified in the pilot plant. The calculations were supported by isothermal physical modelling experiments with acid and alkali simulating the mixing in the flame. A new generation within the burner technology. Pilot plant A pilot plant was built for testing and demonstration of new process and reaction engineering developments in the autothermal reforming technology. Mixtures of natural gas and butane are also applied as feedstocks. Development of burner and combustion chamber Although autothermal reformer burners of conventional design are operating industrially with satisfactory lifetime. at high equilibrium temperatures. and recent tests have shown that trouble-free operation is possible at very low steam to carbon ratios. A nickel catalyst supported by a magnesia-alumina spine1 carrier has shown high stability and activity for operation in autothermal and secondary reformers. (ii) isothermal physical modelling (hydraulic modelling). The scale of the pilot plant was chosen in order to enable reliable adiabatic tests of the highly exothermic combustion process. (iii) pilot plant testing. LIybkjwlFuel Processing Technology 42 (1995) 85-107 The top of the catalyst bed is exposed to the process gas leaving the combustion chamber at temperatures of llOO-14OO”C.0 have been produced [30]. the CTS burner [32]. the pilot testing revealed that for production of carbon monoxide-rich synthesis gas a more resistant burner design was required. Synthesis gases with a hydrogen to carbon monoxide ratio below 1. The plant was designed for operation on natural gas and pure oxygen at a capacity corresponding to 100 Nm3/h natural gas producing synthesis gas (carbon monoxide + hydrogen) in the range of 250-300 N m3/h. In laboratory-scale equipment it is difficult to carry out adiabatic as well as isothermal experiments on methane oxidation. The pilot plant has been in operation for three years. combustion chamber and refractory) can be made at realistic conditions which is required for the scale-up to larger industrial plants. and the results were used to optimize the burner design into the new CTS burner technology. was developed using the following tools: (i) computational fluid dynamics (CFD). the region near the burner nozzles and the whole combustion chamber were made with the LCFDSFLOW3D program.3. as well as at high addition of carbon dioxide feed. The reactions are mainly controlled by film diffusion at the outer catalyst pellet surface. The CFD calculations of the flame.4. meaning that the process can be carried out at very high space velocities.104 I. .

g. CTS burners have been used in recent revamps of existing autothermal reformers. i. In all cases formation of carbon dioxide and water is reported. for shift conversion (2). these experiments showed only partial methane conversion and high consumption of oxygen. Use of autothermal reforming is discussed in [30. Alternative processes Recently. Industrially. for boosting the production capacity. A more detailed discussion of this is given in [30]. In a modified version the CTS burner may be used also in secondary reformers. e. the following reaction engineering aspects are of general importance: (i) effective mixing at the burner nozzles. and accordingly it was possible to obtain a product gas with a lower hydrogen to carbon monoxide ratio than predicted at equilibrium. demonstrating that the catalysts are active for methane reforming (l). The experiments described in [35] showed that carbon monoxide and hydrogen were the primary products. Some degree of complete combustion has taken place as the oxygen conversion is higher than that corresponding to partial oxidation. the catalyst particles being hotter than the gas due to testing at low Reynolds number. and also for complete oxidation to carbon dioxide. claiming high selectivity [34-361. However. The CTS burner technology can be used both for new plants and for revamp of existing plants. In order to be economically attractive. Recirculation of the reacted gas from the thermal zone back to the burner can protect the refractory and the burner from the hot flame core and ensure a homogeneous gas and temperature distribution at the entrance to the catalyst bed. 7. So far no catalyst has shown selectivity for methane oxidation to carbon monoxide and hydrogen at industrial conditions yielding less carbon dioxide than predicted by equilibrium. 331. In [34] is reported high yields of carbon monoxide and hydrogen at reactor temperatures as low as 3OO”C. It showed no sign of wear or corrosion indicating much improved burner performance and extended burner lifetime. DybkjmlFuel Processing Technology 42 (I 995) 85-I 07 105 In the design of the burner and the combustion chamber. (ii) low metal temperatures of the burner. (iv) homogeneous gas and temperature distribution at the entrance to the catalyst bed.e. catalytic methane oxidation must be carried out . The data reported in [36] correspond to the chemical equilibrium at the measured temperature. taking both methane reforming and shift conversion into account. The apparent selectivity for partial oxidation (5) can be explained by the equilibrium for the methane reforming and the shift reactions favouring formation of carbon monoxide and hydrogen at atmospheric pressure and temperature above 800°C.but investigations of the reported data have shown that these apparently high activities at low temperature can be explained by catalyst over-temperatures. (v) protection of the refractory from the hot flame core. After 1 year in operation the CTS burner at one of the plants was inspected. investigations at atmospheric pressure on catalytic methane oxidation to carbon monoxide and hydrogen through mild exothermic partial oxidation (5) have been published. (iii) soot-free combustion.I.

Steam reforming. J. opportunities and limits of the technology. [3] Alstrup. (Eds. Kluwer Academic Press. R. 249-281. J.S. 32: 122-128. Sulfur-passivated nickel catalysts for carbon-free steam reforming of methane. and Christiansen. Takemura. et al (Eds. S. J. J.. J. A model explaining carbon filament growth on nickel. pp.. The problems related to such processes were discussed in some detail in [l].. Catal. C. I.. 109: 241-251.J. Catalysis. 1993.. L. Catal. oxidative conversion of methane may well be exciting. 33: 86100. LlybkjwlFuel Processing Technology 42 (1995) 85-107 at elevated pressure and at high methane conversion. Copenhagen. 85: 31-43. Antwerp. Today.. 1992. Stub Nielsen. pp.106 I. 1993.. pp. Belgium.. J. Springer. J.-H.R. l-130. [S] Vannby.. pp 97-113. K. Irrespective of whether a thermal burner or a catalytic burner. In: de Lasa. 1993. Important new developments with respect to both process and equipment design have recently been introduced to the industry. l-10. and reference is made to that paper. Catal.L. Operating experience in advanced steam reforming. 91. 1984a. T. J. Chemical Reactor Technology for Environmentally Safe Reactors and Products.. In: Proceedings of Nitrogen ‘ British Sulphur Conference. whether a fixed or a fluidized catalyst bed is used.R. Dybkjrer. and Boudart. Ammonia Plant Sat. and Bak Hansen. [9] Mohri.R. L. 1991. [lo] Storgaard.). Production of synthesis gas.. October 12-14. 19: 305-324. I. CO1-reforming of methane over transition metals. Berlin.. Paper presented at the Symposium on Large Chemical Plants. The conclusion is that the chemistry of the direct. 1988. Ammonia Plant Saf. and Shibasaki. and Kim. 1993.. 8. [7] Rostrup-Nielsen. Process options in natural gas steam reforming and evaluation of catalyst performance. [2] Rostrup-Nielsen. Catalytic steam reforming. In: Anderson. but have not yet been developed to a point where they are of industrial interest. M. but the process engineering requirements still represent severe obstacles before these routes may become economic alternatives to the indirect processes via synthesis gas. Dordrecht. [8] Vannby. the composition of the product exit gas will be determined by the thermodynamic equilibrium at the exit temperature which is determined by the adiabatic heat balance.R..). J. 144: 38-49. iron and Ni-Cu alloy catalysts. Adiabatic pre-reforming. H.. I. and Winter-Madsen. Alternative processes such as selective oxidation of methane to carbon monoxide and hydrogen and direct conversion of methane to products such as methanol or ethylene are widely discussed... Another process route which has attracted much interest is direct. J. Science and Technology. [6] Rostrup-Nielsen.R. 1992. oxidative conversion of natural gas into useful products such as methanol or ethylene. J. Conclusions Steam reforming and autothermal reforming are the most important technologies for production of synthesis gas. References [l] Rostrup-Nielsen.R. R. . 1984. Application of advanced materials for catalyst tubes for steam reformers. Catal.J.E. [4] Rostrup-Nielsen.

44: 89-97.. 138: 267-281.R. Kitchen.J. 1992. Fertilizer Association of India Seminar. J. Ammonia Plant Saf. Rajput. 1993. Hydrogen.I.. paper SII-1. I. pp 145. and Wang. Nitrogen.L.D.. [16] TOPSOE TOPICS. Modern ammonia technology: Where have we got to..R. [24] Sosna. A. 33: 1088122. 1992. A. and Udengaard. [31] Farina. New Delhi. Rostrup-Nielsen. K. 91. A. H. I... A. J. Werkstoffe und Korrosion.J. J. Proceedings of World Meths anol Conference.. G. and Grotz. Choose optimal syngas route. and Schmidt. I.. Cheetham. Mater.-H.C. Cat. Tosaka.S. March: 39-46. L. L. I. Selective oxidation of methane to synthesis gas using transition metal catalysts. pp l-10. [12] Appl. Dybkjrer. October 1994. Improve syngas production using autothermal reforming.M. Advanced in reforming system design. Primdahl. Sci. Review of Topsee’ methanol technology.I.. Ammonia Plant Saf. In: Fuel Cell Seminar. [35] Hickman. T..T.. [14] Schneider. pp l-18. 1992.R. In: Proceedings of Nitrogen ‘ British Sulphur Conference... A heat-exchanger type steam reformer for ammonia production.J.. C. W.S. Haldor Topsne A/S. [36] Ashcroft... 195: 22-36. 71(3): 51-57. Carburization and oxidation.. Lett. and Primdahl. 1990.D. N. 1990. and Primdahl.A. particularly Ammonia-Synthesis Gas. Denmark. 1989.H. 33: 165-170. J.. 1990. and Suzuki... H. 1993.. pp. Grey. S. 1984.. Hydrocarbon Process. pp 83-95. Paper presented at second Nordic Symposium on Catalysis.. [15] Johansen. [27] Grabke. 1992. Hansen. Hydrocarbon Process. and Thiagarajan.. 39. Metal dusting of high temperature alloys. Reforming the front end. H..M.I. M. Foord. R. R. pp l-15. J. 344: 319-321..V. [lS] Stahl. Experience with a prereformer. Ammonia Plant Saf.. USA.S. Low temperature oxidative conversion of methane to syngas over NiO-CaO catalyst.. P. I. Nature.. and Supp.. T. A.. Hydrocarbon Process. D. 15: 363-370.. [25] Dybkjar.I. Denmark. Oil and Gas J.-I. 83-88 [19] Topsae.. and Hackett. and Vernon. T. Meeting. Hanson.. [ZS] Christensen. 1994. Synthesis gas formation by direct oxidation of methane over Pt Monoliths. Fundamentals in design of adiabatic preconverters for steam reforming of hydrocarbons.-H.. Burners for secondary and autothermal reforming ~ design and industrial performance. Kawai. T.. P. T.. [30] Christensen. J. Raghuraman. Lyngby. Trends in hydrogen plant design.. Orlando. Sulfur passivated reforming process lowers syngas Hz/CO ratio. [17] Stal. Danish Pat. 1987. 1992. where are we going? Nitrogen. III.S. B. paper No. A. [34] Choudhary. AIChE Ammonia Safety Symposium. DC. 71(8): 119-127.D. 1994. Gunko. A. N. Catal. Murrell.. I. 1993.. Produce syngas for methanol. H. Preparation of synthesis gas. Tucson.K. High efficiency heat exchange reformer.. R. Krajak.J. Hydrocarbon Process. . History of development of the Tandem reforming process.R. Bak Hansen.. 148882. [26] Grabke. B. 87: 23-33.S. New Delhi. 1993. 1993. Green.. D. L. paper SIII-2.F. paper 2a. [29] Verduijn. and Udengaard.. and Prabhakar.. pp l-7. M. and Miiller-Lorenz. CAR demonstration unit on stream. and Bak Hansen.. I.R. Jr. Copenhagen. 1992. Paper 106A presented at AIChE Spring Natl. Fertilizer Association of India Seminar. B. pp l-20. III and Le Blanc.. 1979. pp l-l 1. [21] Elkins. M. [13] Sogaard-Andersen. Orlando. 25: 6468. E. [33] Lowson. J.J. Vancouver. D.A.. 1991 The ICI gas heated reformer (GHR) system. N. K.A.. V. T. [23] March.. Smith. Eng. E. 90(10): 62-67. [22] Schneider.. and Pinto.D. XVII. Arizona. and Wolf.. Houston. H. 1989. 1992. Lyngby. 71(3): 77-79.P. 199: 5675.L. I.. Advances in ammonia production technology. DybkjwlFuel Processing Technology 42 (1995) 85-107 107 [ll] Nitrogen 1992. 1990. AIChE Ammonia Safety Meeting. S.V. 1985. [20] Miyasugi. Bondar.. [32] Christensen. Jeffery.

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