Operating Manual Catalysts for Steam Reforming Natural Gas, Associated Gas & LPG

Page Introduction KATALCOTM 25-series, KATALCO 57-series and KATALCO 23-series catalysts Catalyst storage, handling, charging and discharging Health and safety precautions Start-up Operation Reformer tube appearance Catalyst poisons Nickel carbonyl hazard Shut-down 3 4 6 9 10 15 17 19 21 22

Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at time of going to press, and is given in good faith, but it is for the User to satisfy itself of the suitability of the product for its own particular purpose. Johnson Matthey Catalysts gives no warranty as to the fitness of the Product for any particular purpose and any implied warranty or condition (statutory or otherwise) is excluded except to the extend that exclusion is prevented by law. Johnson Matthey Catalysts accepts no liability for loss or damage (other than that arising from death or personal injury caused by Johnson Matthey Catalysts’ negligence or by a defective Product, if proved), resulting from reliance on this information. Freedom under Patent, Copyright and Designs cannot be assumed.

701JM/103/0AMOG © Johnson Matthey Group 2003

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g. LPG) the catalysts must be promoted with potash or lanthana to resist carbon deposition. This also allows reforming of lights feeds (e. KATALCO 23-series is produced by impregnating a strong alpha alumina support with nickel. KATALCO 57-series and KATALCO 23-series catalysts are unalkalized. The information provided is sufficient for the preparation of the detailed operating instructions which of necessity will be plant-specific. KATALCO 57-series and KATALCO 23-series are produced by impregnating a strong. reformers operate at high pressure to optimize the overall economics of the process. KATALCO 57-series or KATALCO 23-series catalysts can be used successfully. and 1.0 for hydrogen plants.5 – 3. natural gas containing significant proportions of heavier hydrocarbons. 2. Also despite the thermodynamics of the process. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 3 . Johnson Matthey steam reforming catalysts are available in a wide range of types and sizes to suit specific steam reformer designs and feedstocks. off-gas) at steam to carbon ratios lower than the unpromoted natural gas reforming types. Thus combinations of promoted and unpromoted catalysts can be provided for all duties.5 for H2/CO plants. ranging from reforming natural gas with little or no heavier hydrocarbons. Johnson Matthey Catalysts will make appropriate recommendations for the proportions. These catalysts must be reduced before use to convert nickel oxide to the active nickel metal. so that the steam ratio is normally in the range 2. natural gas. porous calcium aluminate support with nickel. The commonest combinations are to use either alkalized KATALCO 25-series catalysts in the top 40-50% of the reformer tube. These techniques provide catalysts with high strength and activity. or even use in plants which are prone to “hot band” formation. With light feeds.. The steam reforming of saturated hydrocarbons can be represented by the three reactions: CnHm + nH2O CO + 3H2 CO + H2O → → → nCO + (n+m/2) H2 CH4 + H2O CO2 + H2 An excess of steam is required to suppress carbon formation and promote the reforming reaction. mid-range feedstocks such as LPG.5-5. with KATALCO 57-series or KATALCO 23-series in the remainder of the tube.6-2. They can handle a wide range of feedstocks from natural gas through LPGs to naphthas with a final boiling point up to 225oC (435oF). combinations of catalysts are usually required. As the hydrocarbon feedstock becomes heavier (e.Introduction Johnson Matthey steam reforming catalysts are designed for operation in all current steam reforming furnaces. This manual discusses the principles of start-up. As feeds become heavier or at lower steam to carbon ratios..5 for ammonia and methanol plants. operation and shut down for the Johnson Matthey catalysts for steam reforming natural gas through to LPG feedstocks.g.

impregnated with nickel oxide.5 2. nickel oxide dispersed on a calcium aluminate ceramic support. Physical properties (typical) Catalyst Form 23-4 23-4M Optimized 4-hole shape 15 11 3 1200 75 23-4G Optimized 4-hole shape 20 19 5.KATALCO 25-series.7 900 56 57-4GQ Optimized Quadralobe 20 16 4. For use with heavier feedstocks.7 950 59 25-4GQ Optimized Quadralobe 20 16 4.5 2.3 1090 68 23-4MQ Optimized Quadralobe 13 10. nickel oxide dispersed on an alpha alumina support.5 900 56 57-4Q Optimized Quadralobe 17.4 760 47 Optimized 4-hole shape 19 Length (mm) 14 OD (mm) 4 Hole ID (mm) Typical charged bulk density 1000 (kg/m3) 62 (lb/ft³) 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 4 . Optimized 4-hole shape 19 Length (mm) 14 OD (mm) 4 Hole ID (mm) Typical charged bulk density 1100 (kg/m3) 70 (lb/ft³) Catalyst Form 25-4 25-4M Optimized 4-hole shape 15 11 3 900 56 25-4G Optimized 4-hole shape 20 19 5. Composition KATALCO 25-series KATALCO 57-series KATALCO 23-series These catalysts can be supplied pre-reduced. or with light hydrocarbon feeds at low steam to carbon ratios.3 850 53 57-4MQ Optimized Quadralobe 13 10. the KATALCO 25-series catalysts are specially promoted with potash.5 13 3. and are available in a range of sizes to allow selection of the optimum for any particular application.5 13 3.4 790 49 Optimized 4-hole shape 19 Length (mm) 14 OD (mm) 4 Hole ID (mm) Typical charged bulk density 1000 (kg/m3) 65 (lb/ft³) Catalyst Form 57-4 57-4M Optimized 4-hole shape 15 11 3 900 56 57-4G Optimized 4-hole shape 20 19 5.7 1140 71 23-4GQ Optimized Quadralobe 20 16 4.4 1050 66 nickel oxide dispersed on a promoted calcium aluminate ceramic support.5 2.5 13 3.5 900 56 25-4Q Optimized Quadralobe 17. KATALCO 57-series.3 870 54 25-4MQ Optimized Quadralobe 13 10. KATALCO 23-series catalysts All the catalysts are based on calcium aluminate or alumina ceramic supports.5 1100 70 23-4Q Optimized Quadralobe 17.

loading technique etc. Depending on reformer type. actual achieved density may be different from these values. Important Note The charged density values are typical values. the catalysts may also be supplied as Raschig rings in which case the instructions below may be applied and further product information will be supplied on request.By special arrangement. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 5 .

The stabilization layer will break down at temperatures in excess of 100oC (210oF). and the lower drums can be crushed due to the weight of the drums above them. then the catalyst should be redrummed without delay. If the drum lid cannot be replaced. All drums should be inspected when they first arrive on site. If any contamination occurs it is difficult to assess the extent of any damage without full examination of the catalyst. If prolonged storage is expected. discharging and handling steam reforming catalysts any potential risk to health during these activities should be assessed and appropriate precautions taken. Taller stacks tend to be unstable and there is the risk that the top drums may fall off the stack. charging and discharging Before charging. Any catalyst in damaged drums should be repacked in clean. If there is any doubt about the state of the catalyst it is best not to charge it to the reactor. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 6 . The metal drums are usually suitable for outside storage for a few months but should be protected against rain and standing water. The lids should be left on the drums until just before the catalyst is to be charged. Drum storage Steam reforming catalyst is generally supplied in mild steel drums fitted with polythene liners. The catalyst drums must be kept cool. Catalyst that is supplied pre-socked will be contained in wooden crates. dry lined steel drums and sealed to restrict access to air and protect the catalyst from moisture. Pre-reduced catalyst storage Pre-reduced catalysts will be supplied in mild-steel drums as described above. dry and away from direct sunlight and sources of heat. Storage guidelines are similar to drum storage. Catalyst 25-4/57-4 25-4G/57-4G 25-4M/57-4M 23-4 23-4G 23-4M 25-4Q/57-4Q 25-4GQ/57-4GQ 25-4MQ/57-4MQ 23-4Q 23-4GQ 23-4MQ Net weight (kg) 155 155 175 200 200 200 145 145 170 200 200 200 Tare (kg) 18 18 18 18 18 18 18 18 18 18 18 18 Drum dimensions (cm) 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia 88 height x 59 dia Drums must not be stacked on their sides or stacked more than four drums high. The temperatures generated can exceed 1000oC (1830oF). If the lids are removed it is important that they should be replaced as soon as possible. handling. so that contamination of the catalyst is avoided. the heat generated will accelerate the breakdown. With adequate access to air. even when held on pallets. In addition the Johnson Matthey brochure on “Catalyst Handling” should be consulted. having the following packaging details. they should be kept under cover and away from damp walls and floors.Catalyst storage. These parameters may change but precise information will be recorded in the documentation covering the goods.

The catalyst is then allowed to spill out of the sock by applying a short jerk to the rope to which the sock is attached. these catalysts should be stored away from combustible materials. eliminates the need to use socks. The most common one in use today is UNIDENSETM loading licensed from Norsk Hydro. the catalyst can be purchased pre-socked. which is licensed by Johnson Matthey Catalysts. hence the strict requirement to keep the catalyst dry especially during catalyst loading and storage. but requires suitable fork-lift trucks and a paved area to handle the pallets. suitable fork-lift trucks must be provided at the reception point. Charging reformer tubes The target in all steam reforming charging operations is to ensure that each tube has an identical pressure drop such that the process flow down each tube is uniform across the whole reformer. It is important not to use standard forks to lift the drums under the rolling hoops. It is also important that the catalyst pellets must not be allowed to form bridges across the tubes as this leads to empty regions in the tubes and overheating during operation. Catalyst drums are often supplied on pallets. Pre-charging checks Before charging begins. To save time at site with filling the socks with catalyst. Drum handling Catalyst drums should be handled as carefully as possible.The stabilization layer can also be broken down by contact with specific chemicals. Catalyst discharge 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 7 . again. More even tube loading has been shown to give less temperature variation at the tube exits. the support grids must be checked and both the inlet and exit connections should be tested to ensure that they are clear. They must not be rolled. as damage to the drums and catalyst is almost inevitable. The fork-lift truck to be used for dismantling the pallets should be fitted with rim or body clamps to avoid damage to the drums. In charging. The UNIDENSE technique uses steel springs or brushes in the tubes to prevent excessive free fall of the catalyst that might otherwise cause damage. A useful check for obstructions in the inlet and exit connections can be made with a pressure drop device which is described in the Johnson Matthey “Catalyst Handling” brochure. An alternative loading method is the use of polythene or canvas socks. Experience with the UNIDENSE loading technology has found the process to be quicker and to give more even loading of the tubes. it is important to ensure that the catalyst is not dropped by more than 50 cm (20 ins) as this can lead to damage of the catalyst pellets. resulting in better overall reformer performance. which reduces the likelihood of damage in transit. This method is described in more detail in the Johnson Matthey Catalysts brochure on “Catalyst Handling”. Water is the greatest risk here. which allow the catalyst to be lowered slowly down the tube until there is only a short free-fall height for the catalyst. There is a variety of established reforming catalyst charging techniques. The patented technique. When the support grid is clear the tube top should be covered to prevent debris from dropping in. It is common practice to blow each tube with air and then to carry out a visual inspection using a boroscope. The use of containers for either catalyst drums or palleted drums eases shipment and further reduces the likelihood of damage in transit but. Given the potential to generate heat.

Johnson Matthey offers the environmentally safe disposal of their complete product range.The catalyst is usually discharged from the reforming tubes with vacuum extraction units. In some instances the design allows gravity discharge. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 8 . Disposal of discharged catalyst Through the “Catalyst Care” Programme.

eyes and respiratory system. in particular. Over-exposure can give rise to more serious effects. then respiratory protection should be used. Operators who handle catalyst must wear suitable protective body clothing. Ergonomics Physical hazards arise from the handling of drums. Dust exposure Short-term exposure to the metals and metal oxides used in catalysts may give rise to irritation of the skin. discharging and handling steam reforming catalysts any potential risk to health during these activities should be assessed and appropriate precautions taken. materials and lifting equipment. Catalysts should be handled as far as possible in well-ventilated areas and in a way that avoids the excessive formation of dust. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 9 . Product safety data sheets should be consulted for information. Under no circumstances should personnel be allowed to walk over the catalyst until it has been fully stabilized. Inhalation of dust should be avoided. Transport of such catalyst should only be in metal skips or metal-sided trucks. and the appropriate occupational exposure limits should be strictly observed. Note: The European Union has decided that it is prudent to classify all insoluble nickel compounds as Category 1 carcinogens. Discharged pyrophoric catalysts Catalysts discharged in the pyrophoric state must be kept separate from flammable materials. Appropriate information is contained in the Material Safety Data Sheet sent with all orders. Everyone involved in the handling operation should clean up afterwards and. Personnel should be aware of these and appropriate precautions taken. If these limits are likely to be exceeded.Health and safety precautions Before charging. gloves and goggles. and more frequently if contamination is heavy. Clothing should be changed at the end of each shift. High temperatures can build up in heaps and it is a prudent precaution to spread the catalyst thinly over the ground until the oxidation is complete. Dumps of the catalyst should be within reach of water hoses so that any overheating that occurs can be controlled. must wash before eating.

The effects of rapid temperature rise on plant equipment must be known before the appropriate warm-up rate can be selected. The appearance of the tubes. Minimum thermal stress is favoured by a low rate of temperature rise while. Throughout the start-up. regular visual checks must be made on the furnace. It is virtually impossible to provide sufficient instrumentation for start-up conditions that will give a true measure of the process conditions during start up and shut downs and other similar transient operations. Nitrogen circulation may be stopped at any convenient time after steam has been added and before hydrocarbon feedstock is introduced. This will achieve maximum catalyst activity. Traditionally. if the constraints on plant equipment allow. particularly at the tube inlet where the temperature is lowest. The reduction of the nickel oxide content in a steam reforming catalyst charged to a steam reformer is possible using either hydrogen. For most seam reformers. whenever the throughput is increased. warm-up rates as high as 150-170oC (270-305oF) per hour can be used to minimize energy consumption. of course. Consequently. natural gas. and heat the reformer above the condensation temperature while still circulating nitrogen. reforming tube tensioners and refractory linings.Start-up When the steam reformer is commissioned. 1 Purge the plant free of oxygen using nitrogen. freshly charged catalyst may be heated in air during the initial reformer warm-up period. Steam may be added as soon as possible after the temperature of the exit header is at least 50oC (90oF) above the condensation temperature of steam. flames and refractory lining is the best guide to the actual furnace conditions during start-up. the furnace designer’s instructions should be observed. As a general rule. because the instrumentation provided to monitor furnace performance is designed primarily for operation under normal running conditions. however. ammonia or methanol. Johnson Matthey reforming catalysts can however. the catalyst should preferably be reduced in the presence of hydrogen before feedstock is introduced. or above. Warm-up rate The warm-up rate is determined by the need to minimize both the thermal stresses on plant equipment as well as the energy consumption during start-up. Note. Care should be taken to maintain safe conditions in the heat recovery section because mechanical failures are often a major cause of delay during the start-up period. Particular attention should be given to the thermal expansion of inlet/exit pipes. LPG’s. the design value. Although details will vary from plant to plant. Instructions concerning the burner pattern and the rate at which the firing is increased should be followed. off-gases containing hydrogen. the general procedure described will be sufficient for most modern plants. especially those concerning the rate of increase of temperature and the heating procedure. that this is not recommended for catalyst which has previously been reduced. or been supplied in a pre-reduced form. Excessive delays should be avoided before starting the catalyst reduction. As an alternative. If no hydrogen is available then natural gas or other alternates may be used. withstand a more rapid rate of heating. a warm-up rate of 50oC (90oF) per hour has provided a reasonable compromise between the two objectives. 2 3 4 The steam flow should be increased to 40-50% of the design rate as soon as possible to allow even firing of the furnace. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 10 . As soon as the exit header is 50oC (90oF) above the condensation temperature the plant must always be purged free of oxygen with steam. the change in steam flow should always precede the change in hydrocarbon flow to ensure that the steam to carbon ratio is always held at. minimum energy consumption is favoured by rapid heating of the reformer.

once the reformer has reached the design exit temperature. KATALCO 25-series and KATALCO 57-series catalysts. level. the catalyst reduction will be virtually complete and there will be no need to maintain reducing conditions for more than two hours unless the steam to hydrogen ratio has been outside the appropriate limit during the warm-up. For KATALCO 23-series. the minimum steam to carbon ratio should be at least 10:1. This may be done before the hydrogen concentration has attained the required level. During catalyst reduction. The firing rate should be adjusted to maintain the design exit temperature as the reforming reaction begins. The steam rate should always be increase before increasing the feed rate such that the steam to carbon ratio is always higher than 5:1 and therefore the potential for carbon formation is minimized. If the methane concentration increases or the tubes show hot zones. The natural gas rate should be increased to 25% design rate as quickly as possible. KATALCO 25-series and KATALCO 57-series. check the methane concentrations of exit gas after each change in rate to ensure that it reaches a low steady level. Again. steaming for more than 24 hours before proceeding with the reduction is not recommended. the steam to hydrogen ratio for reduction is in the range 6-8 to 1. At all critical stages during reduction it must be emphasised that the temperatures referred to are those at the actual tube exit. The steam to hydrogen ratio should be controlled in the range for reducing conditions and additional hydrogen should be supplied to maintain this ratio throughout the reduction period. it is recommended that the hydrocarbon flow be increased more slowly in stages during a period of at least three hours until the design steam to carbon ratio is reached. Increase the flow of natural gas until the design steam to carbon ratio is reached. Temperatures indicated by control room instruments are inevitably lower than the true value because of heat losses and allowance must be made for any discrepancy. For KATALCO 23-series. indicated values may be 25-100oC (45-180oF) lower than actual temperatures. KATALCO 25-series and KATALCO 57-series catalysts.For KATALCO 23-series. The steam to carbon ratio must be at least 5:1 and the steam rate should be increased as necessary to maintain this condition as the natural gas rate is increased. Increase the reformer exit temperature to the design value. if available. Hydrogen must always be free of catalyst poisons. With higher molecular weight gaseous hydrocarbon feedstocks. steady. With higher molecular weight gaseous hydrocarbon feedstocks. If the methane concentration increases or the tubes show hot zones. Reduction with hydrogen 1 Hydrogen or hydrogen-rich gas may be added at any time after the plant has been purged of oxygen. Introduce natural gas. restore reduction conditions with hydrogen for 1-2 hours. Depending on the location of the thermocouples. Hydrogen addition should continue. then restore reduction conditions with hydrogen for 1-2 hours. or increase the steam to carbon ratio to 7:1 and hold the decreased natural gas flow steady for 2-3 hours before increasing the rate once again. until the hydrogen recycle loop to the desulphurizer can be established. Check the methane concentration of the exit gas during this period to ensure that it reaches a low. the tube inlet temperature should be as high as possible to promote maximum reduction at the inlet of the tubes. or increase the 2 3 4 5a 5b 6a 6b 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 11 . Regular visual checks on the tubes should be conducted to ensure that the reformer tubes are not being overheated.

The reduction procedure described for hydrogen should then be followed except that the reformer exit temperature should preferably be as high as 800oC (1470oF) to achieve maximum ammonia cracking. and at the stage where there is no nitrogen circulation but with 40-50% design rate steam flow. 7 Throughput may now be increased to the design level in regular stages that depend on the overall plant commissioning schedule. Reduction with ammonia Ammonia can be used as a source of hydrogen by cracking it to a hydrogen/nitrogen mixture in a conventional ammonia cracker or in the steam reformer tubes. then additional checks have to be made since these carbon oxides can methanate across the hydrodesulphurisation catalyst. Always increase the steam flow before the hydrocarbon flow to maintain the steam to carbon ratio at or above the design value. If the hydrogen source contains hydrocarbons. if possible. When it is introduced before the feedstock heater. be bypassed. Cracked gas should not be recycled because of the possible methanation of carbon oxides. Reduction with natural gas 1 After following the recommended warm-up procedure. For KATALCO 23-series. The start-up procedure may well include a recycle through the desulphurization system and thus a similar limit to carbon oxides applies or bypass of the hydrodesulphurizer is required. or by cracking ammonia or methanol. KATALCO 25-series and KATALCO 57series catalysts. Johnson Matthey will provide more detailed advice on the procedure on request. increase the temperature to 750oC (1380oF). If the hydrogen source contains carbon oxides. At temperatures above 250-300oC (480-570oF) any carbon oxides could methanate over the unsulphided cobalt molybdate or nickel molybdate catalyst in the hydrodesulphurizer. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 12 . increase the reformer exit temperature. usually before the process steam superheater. causing an excessive temperature rise.steam to carbon ratio to 7:1 and hold the hydrocarbon flow steady for 3-4 hours before increasing the rate once again. Attention must also be paid to the nature of any hydrocarbons in the hydrogen source and the composition of these hydrocarbons. The source of hydrogen must be free of poisons such as sulphur and chlorine. The flow of liquid methanol should be regulated to give a steam to hydrogen ratio between 6:1 and 8:1 at the reformer exit. Hydrogen source Hydrogen or hydrogen-rich gas needed for catalyst reduction is supplied from either high pressure cylinders. Johnson Matthey will provide more detailed advice on the procedure on request. then these will be converted to carbon oxides in the reformer. Liquid ammonia should be injected upstream of the primary reformer. Reduction with methanol Methanol will decompose in the primary reformer to give a mixture of hydrogen and carbon monoxide and can also be used as the source of hydrogen during catalyst reduction. the desulphurizer should. it is advisable to bypass the hydrodesulphurizer. from another plant. If the hydrogen contains more than 3% (vol) of carbon monoxide or more than 13% (vol) of carbon dioxide.

but great care is required as the risk of carbon formation is very high. These conditions should be held. For KATALCO 23-series. Reduction with hydrogen and hydrocarbon mixtures When the reforming catalyst is required to be reduced with hydrogen/hydrocarbon mixtures (e. For KATALCO 23-series. Increase the gas rate to give the required steam to carbon ratio during a period of 2-3 hours. However. maintain the tube inlet temperature as high as possible to ensure catalyst reduction at the tube inlet. more methane will be reformed. the purification unit must be at a sufficient temperature to desulphurize the feed. continue the reduction for a further period at a steam to carbon ratio of 6-7:1. and then hold this ratio for the specified period. While the natural gas rate is being increased to this level. For the required steam to carbon ratio. The heat requirement in the furnace will increase as the endothermic steam reforming reaction begins. the reformer exit temperature should be increased to the design level. and it is essential that instrumentation is capable of monitoring the correct steam and hydrocarbon flow during the catalyst reduction (e. KATALCO 25-series and KATALCO 57-series catalysts. As the catalyst gradually reduces. low flows etc). the general use of hydrogen addition to the hydrocarbon feed will greatly assist the reduction process and help prevent carbon formation. the procedure described for reduction with natural gas should be used but the hydrocarbon flow during reduction should be controlled in the range 8-10:1.g. then some hydrogen is required for complete hydrodesulphurization. For KATALCO 23-series. but there is an increased risk of carbon formation. usually for 4-8 hours. this will cause a reduction in the reformer exit temperature and therefore the furnace firing should be increased to maintain the necessary exit temperature.2 Introduce desulphurized natural gas at about 5% design rate. KATALCO 25-series and KATALCO 57-series catalysts. Check the methane concentration in the reformer exit gas after each change to ensure that it stays at a low steady value. Increase the throughput in stages to the design level depending on the overall plant restart schedule. until reduction is complete which can be checked for by monitoring the methane slip. Always increase the steam rate before the natural gas rate to maintain the steam to carbon ratio at or above the design value. consideration should be given to both the steam to hydrogen ratio as well as the steam to carbon ratio. a steam flow of about 40-50% of the design value usually corresponds to a natural gas flow rate of 20-25% design. low pressure.. Always increase the steam rate before the natural gas rate to maintain the steam to carbon ratio at or above the design value. During this stage the exit methane concentration should be checked at hourly intervals. the steam to carbon ratio should be 7:1. Reduction should be complete when the exit methane concentration reaches a low steady value. If organic sulphur species are likely to be present. Ethane. KATALCO 25-series 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 13 . increase the flow of natural gas in stages until the design steam to carbon ratio is reached. other than methane or light refinery gases may be used as an alternative hydrogen source for catalyst reduction. 5 6 Reduction with other hydrocarbons Hydrocarbons.g. If the methane concentration increases or the tubes show hot zones. refinery off-gas feeds). In addition. 3 4 During the reduction period. before once again increasing the natural gas flow to the design steam to carbon ratio. propane or butane streams could be used. When the catalyst reduction is complete.

or upset. then it is essential that the catalyst should be dried out slowly. by holding the temperature just below or at the condensation temperature until the catalyst is dry. Pre-reduced catalyst As pre-reduced catalyst is used in conjunction with oxidized catalyst. re-reduction will be required to restore full activity. Re-start When catalyst has been steamed during a plant shut-down. Alternatively. in some circumstances.and KATALCO 57-series the steam to hydrogen ratio should not be less than 6:1 and the steam to carbon ratio should not be less than 7:1. This drying process should preferably be carried out using nitrogen. When reducing with hydrogen. and held at constant temperature for a period of one hour. leading to break-up of the catalyst. However. The procedure is the same as for new catalyst except that for KATALCO 23-series. This is to avoid the risk of rapid vaporization of water in the catalyst pores. Catalyst wetting If the catalyst has been subjected to severe wetting (for example. due to condensation of steam during start-up or shut-down). 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 14 . before commencing the start-up procedure. To ensure complete and thorough drying. use of prereduced catalyst can significantly reduce the reduction time. KATALCO 25-series and KATALCO 57-series catalysts the reduction procedure is faster. it is recommended that the catalyst is then heated to 500oC (930oF). the catalyst activity will be recovered as soon as the appropriate operating temperature is reached. air may be used. On re-heating. but only with a fresh charge of catalyst which has not previously been reduced. the holding period on steam only should not exceed 72 hours. When reducing with natural gas however full catalyst activity will normally be achieved in less than two hours after reaching the operating tube exit temperature. the catalyst reduction procedure described above still applies.

the resistance to flow is so great that it is impossible to steam the catalyst and complete catalyst replacement will then be required.3:1. Significantly lower settings are possible with the use of KATALCO 25-series catalysts. and the trip at 2. During this time the exit temperature should be kept as high as possible – preferably around 7500oC (1380oF). can cause complete physical disintegration and must be avoided by the choice of suitable operating conditions. will result in massive deposition of carbon and a rapid increase in pressure drop. it is typical therefore the steam to carbon ratio or hydrogen recycle is increased once carbon formation starts to occur. the surface layers can fall off giving an eroded appearance. and the concentration of air in steam should not exceed 2%. This will weaken the surface so that when the carbon is removed. The downstream high temperature shift catalyst should normally be bypassed to prevent oxidation if air is to be used. To protect the catalyst from carbon erosion caused by operating at low steam to carbon ratio. Carbon formation Under normal conditions. In the worst gas. it is possible to regenerate the catalyst by steaming. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 15 . For larger amounts of carbon on reforming catalysts.8. by steaming. To prevent this from occurs. then the effluent from the reformer should be vented prior to the LTS bed to prevent sulphur poisoning of the LTS bed. Any variation in these two major operating conditions will eventually lead to loss of catalyst activity and overheating of the tubes. Addition of a small constant flow of nitrogen into the steam assists the measurement of carbon oxides when taking dry gas samples. the rate of carbon gasification is greater than the rate of carbon formation and therefore the overall rate of carbon formation is essentially zero. The progress of carbon removal can be monitored during the regeneration procedure by measuring the concentration of carbon dioxide and methane at the reformer tube exit.Operation Johnson Matthey steam reforming catalysts operate successfully over a wide range of plant conditions and withstand most minor plant upsets. The choice of setting will depend on the design of the plant. This can be done by shutting off the flow of hydrocarbon feed whilst maintaining the flow of steam. This can cause increased pressure drop and lead to higher than normal tube temperatures that will often give a patchy tube wall appearance. the nature of the feedstock. and the operating conditions. Complete loss of reaction steam during plant incidents.5. operation with a small steam deficiency or a slightly reduced catalyst activity can result in slow carbon deposition. If the plant has an LTS bed downstream of the primary reformer. the type of catalyst used. it may be necessary to add a small quantity of air to the steam. Carbon deposition in the pores of a catalyst. Catalyst life will however be affected by a large number of factors related to the purity of feedstock and the ability to maintain sufficient steam to prevent carbon deposition. normal operation may be at a steam to carbon ratio of 3. as a result of unfavourable equilibrium (thermodynamic carbon). Between these extremes. it is important that the operating conditions are such that net carbon formation is prevented. reformers have alarm settings and trip systems connected to the steam to carbon ratio controller. Carbon deposition from cracking reactions usually forms on the catalyst surface. Plant operation is mainly concerned with the maintenance of approved conditions to avoid catalyst poisoning and/or carbon formation. For a typical top-fired reformer running on natural gas with KATALCO 23-series or KATALCO 57-series catalysts. This must be done under carefully controlled conditions. however. Regeneration When small amounts of carbon have been deposited on the catalyst in the tubes so that hot spots or hot bands have developed and the pressure drop has increased. with the alarm set at 2.

that sufficient heat must be provided to the reforming furnace to satisfy the requirements of the heat recovery system within the fluegas duct and hence the overall plant steam balance. Operation at temperatures below the design level is normally attractive because of reduced fuel consumption but also because of the increased reformer tube life. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 16 . however. Occasionally. the reforming catalyst may be severely poisoned by sulphur. due to changes in feedstock or mal-operation of the purification system etc. It is possible to remove most of the sulphur by steaming the catalyst as described under regeneration. The catalyst will be reoxidized during regeneration and to restore full activity the catalyst should be reduced before further operation.Considerable care should be taken to ensure that the oxidation reaction does not proceed too quickly and cause overheating of the catalyst. Temperature of operation For many duties. For any operating condition. It should be remembered. Sulphur poisoning Under normal conditions. the feedstock purification system will remove sulphur from the feed such that the sulphur slip to the reforming catalyst has minimal impact on the life of the catalyst. Temperatures should be kept as high as possible and the progress of sulphur stripping can be monitored by measurement of hydrogen sulphide (H2S) in the reformer effluent gas. it will be found that the design methane concentration at the tube exit can be achieved with the reformer operating at temperatures lower than the design level for most of the catalyst life. As with measurement of carbon oxides. an addition of a small constant flow of nitrogen into the steam assists the measurement of H2S when taking dry gas samples. the furnace firing should be adjusted to give an even tube wall temperature for all the tubes.

Channelling can be caused by pockets of broken catalyst and dust. Catalyst may be too old for further use. Hot bands may often be removed by steaming. Catalyst in hot tubes should be discharged at the next opportunity and replaced. the tube should be discharged and refilled at the earliest opportunity. Hammering with a rubber mallet is possible during plant operation but does involve some risk which could make the problem worse. it is possible that the charge has not been properly reduced or that temperature indications are inaccurate. It may be possible to remove carbon in such tubes by steaming but this is usually ineffective because of preferential flow through the unaffected tubes. Several typical forms of overheated tubes are: Tiger tailing Clear. It should therefore be replaced. Tubes will look hot when the steam reforming reaction is inhibited and they cannot absorb the heat input from the furnace. The deactivation may be caused by a general decrease in catalyst activity either because the catalyst is past its useful life. Care is essential. Some guidance in assessing the cause of problems can be obtained from the tube appearance. During normal operation the tube wall temperature profile of all the tubes should be similar. If vibration or careful hammering does not remove the voids. but if this has no effect the catalyst in the affected tubes should be discharged and replaced with new catalyst when a suitable opportunity is available. and are often associated with bridging in the catalyst as a result of improper charging. • Hot tubes Where extensive carbon deposition or catalyst breakdown restricts the flow of gas a whole tube can become overheated. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 17 . If so the proper corrective actions should be taken.Reformer tube appearance Visual inspection of steam reformer tubes and temperature measurements with pyrometers provide a good guide to the performance of the catalyst inside the tubes. These indicate voids in the catalyst packing. well defined. Giraffe necking These are random hot zones or patches which can occur for three main reasons: • • An extreme form of the hot band problem which is caused by extensive deactivation from catalyst poisoning or a surface deposit. When all tubes are hotter than expected with no obvious flow restriction. has been poisoned or if the catalyst surface becomes coated by a thin layer of carbon or some other deposit. so that part may be falling below the minimum required activity level. Hot bands These are not so well defined as the hot zones of ‘Tiger Tailing’ and are generally the result of catalyst deactivation. hot rings alternating with cooler rings which develop at random on individual tubes are known as ‘Tiger Tailing’. or by accumulation of carbon. Channelling through the catalyst. This cools the tube where the gas is still reacting and overheats the tube where the flow of gas is impeded.

Tube appearance Hot band Tiger tailing Giraffe necking Hot tube 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 18 .

irreversible and in severe cases catalyst must be discharged and replaced. the methane concentrations of reformer exit gas may increase. arsenic and in addition for the steam naphtha reforming catalysts.Catalyst poisons The most common poisons for steam reforming catalysts are sulphur. . however. cracking of the hydrocarbons will take place near the top of reformer tubes. Use of cleaning fluids that contain chlorides should be avoided in any part of the plant. This procedure will also remove any carbon which has been formed as a result of the sulphur poisoning. The recommended maximum chloride content in the dry process feed is 0.1 ppmv. Levels as low as 5 ppb can cause problems over prolonged periods. by steaming and re-reduction. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 19 . All arsenic should therefore be excluded from the steam reformer. Reformer tubes and any other pipework which have also been contaminated with arsenic should be carefully cleaned to remove all traces and prevent further contamination of new catalyst. it is recommended that they be removed by pre-treatment with an absorbent material provided by Johnson Matthey. The hot patchy appearance of the reformer tubes will also give an indication of decreased catalyst activity. Lead poisoning is. The effect of sulphur poisoning is reversible and normal activity can be restored once sulphur has been removed from the feedstock. With severe catalyst poisoning. chlorine. When chlorides are known to be present in feedstocks. lead.1 ppmv. The carbon deposited can block the catalyst surface and cause a further increase in tube temperature. is a poison for all steam reforming catalysts. usually present as hydrogen chloride (HCl) or organic chlorides. Sulphur Sulphur. Poisoned catalyst should be discharged and replaced. When the catalyst activity has been sufficiently decreased. Special care should be taken to avoid contamination of boiler feedwater with carbon dioxide removal liquor that contains arsenic. In cases of severe sulphur poisoning it will be necessary to remove the sulphur from the catalyst. Lead Lead is sometimes found in liquid reformer feedstocks transported in tankers previously used for leaded petrol. however. occasionally. less easily removed by steaming than sulphur. which is present in hydrocarbon feedstocks. The amounts involved are generally small enough to be absorbed by the hydrodesulphurization catalyst. to restore normal catalyst activity. For very severe cases of chlorine poisoning it may be more economic to change the catalyst rather than to embark on a protracted programme of steaming and re-reduction. Standard Johnson Matthey desulphurization systems will reduce the sulphur content of feedstock to well below the acceptable level of 0. Chlorine Chlorine poisoning of steam reforming catalysts is also reversible. Large quantities of chlorine in the catalyst are. Arsenic Arsenic in very small quantities will irreversibly destroy the activity of all hydrocarbon reforming catalysts.

Mercury is best removed at ambient temperatures using a specialized absorbent provided by Johnson Matthey Catalysts. the contaminated catalyst can be replaced with an equivalent volume of new catalyst. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 20 . Silica Silica and other typical solids carried into the reformer and deposited onto the catalyst have no severe poisoning effect but can block the pores of the catalyst when present in large enough quantities. If necessary. and an increase in pressure drop. This may lead to a partial loss of activity. can be found in a wide range of feedstocks from natural gas to naphthas.Mercury Mercury is also a severe poison and although not too common. iron. Other poisons Impurities such as copper. affect catalyst performance. phosphate etc will accumulate at the top of the reformer tubes and may in extreme cases.

Catalysts used in the steam reforming process normally operate well above this temperature. Nickel carbonyl formation and variation with temperature and pressure 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 21 . odourless gas which is stable at low temperature. Ni(CO)4 an extremely toxic. Observation of this rule avoids the risk of the formation of nickel carbonyl.Nickel carbonyl hazard Catalysts containing metallic nickel must not be exposed to gases containing carbon monoxide at temperatures below 200oC (390oF). During a plant shutdown the catalysts are normally steamed and are usually in the oxidized state when they pass through the critical temperature regime. If this is not the case and nickel metal is present then stringent precautions must be observed so that there is no risk to personnel.

When natural gas has been used in the final cooling stage. Refer to the section on catalyst wetting. Decrease the steam reformer exit temperature at a rate of up to 100oC (180oF) per hour until it reaches about 550oC (1020oF). It is usual to isolate the steam supply before condensation is possible to avoid the inconvenience of liquid water in the steam reformer. Decrease the hydrocarbon and steam rates in stages to about one third of the design values. If nitrogen is not available and natural gas is to be used in the final cooling stage. Always decrease the hydrocarbon flow before the steam flow to maintain the steam to carbon ratio at or above the design level. After a wet shutdown. The steam flow may now be shut off and a flow of nitrogen introduced before cooling is continued. 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 22 . The catalyst may be discharged (if desired) as soon as the temperature reaches 50oC (120oF). Pressure may be reduced at any time during the process of shutting down. the temperature should be decreased below 200oC (390oF) and the burners turned off before the natural gas is added. 3 4 5 6 7 If the catalyst has been caked either with carbon or as a result of physical breakdown. Special methods are available for the extraction of catalyst in these circumstances and Johnson Matthey will give advice on request. The exit temperature should be maintained at about 750oC (1380oF) until the system is free of hydrocarbons. special care should be taken to ensure that the catalyst is cool enough for the methane to be purged safely with air before the reformer is opened to the atmosphere. Frequent visual checks of the steam reformer are recommended at all stages of the shutdown procedure. Keep the steam flow constant and shut off the hydrocarbon feed. The furnace firing should also be adjusted throughout this operation to maintain the tube exit temperature at about 750oC (1380oF). In an ammonia plant the secondary reformer is normally taken offline when the tube exit temperatures are about 700oC (1290oF). This eliminates any possibility of carbon formation due to thermal cracking. care is needed to dry the catalyst thoroughly and prevent any water refluxing in tubes during the restart. 1 2 Decrease the fuel rate to the furnace so that the tube exit temperatures fall to about 750oC (1380oF). extraction can be a lengthy operation. as this can lead to breakdown and caking of catalyst.Shut-down It is important to avoid overheating of either the reformer tubes or the catalyst when bringing a steam reformer off-line. adjusting the furnace firing to compensate for the decreasing heat demand.

UNIDENSE is a trademark of Norsk Hydro. Catalyst Care is a servicemark of the Johnson Matthey Group of companies 701JM/103/0AMOG © Johnson Matthey Group 2003 Page 23 .