Purification KATALCO Mar 07
Purification KATALCO Mar 07
Purification KATALCO Mar 07
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 plc (JM) 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. JM accepts no liability for loss or damage (other than that arising from death or personal injury caused by JMs negligence or by a defective Product, if proved), resulting from reliance on this information. Nothing here in should be considered to provide freedom to operate under any Patent.
Contents
Page Introduction Case studies KATALCOJM PERFORMANCE adds value to your plant Advantages of choosing Johnson Matthey purification catalysts and absorbents Additional capability with KATALCOJM PERFORMANCE Catalyst selector Catalyst characteristics 2 3 5 6 9 12 13
Introduction
Feedstock purification is a key unit operation in any synthesis gas plant which employs steam reforming technology. Its importance is often overlooked, however, and the consequences of not installing the correct catalysts and absorbents, or of not monitoring performance appropriately, can have dramatic and costly consequences for downstream catalysts. The key catalysts in synthesis gas plants that may be poisoned by trace components in the feed gas are pre-reforming, steam reforming, low temperature shift and methanol synthesis. The most common catalyst poisons experienced are sulphur compounds present as hydrogen sulphide, COS, mercaptans, organic sulphides and disulphides, and thiophenes. Occasionally halogen compounds are present, usually as hydrogen chloride, but sometimes as organic chlorides. Some plants also experience feedstocks with more unusual poisons such as mercury, arsenic and other metallic species. Very severe poisoning will lead to significant costs. For example, with severe sulphur poisoning incidents the affected steam reforming catalyst may need to be replaced. In addition to downtime, possibly measured in weeks, the catalyst cost must be added. The financial cost of such incidents varies depending on the size and type of the plant, however, for large scale plants (e.g. 100 MMSCFD hydrogen; 2,000 mtpd ammonia; 2,500 mtpd methanol) each day of lost production costs in the order of US$ 350,000 and typical catalyst replacement cost is in the order of US$ 750,000. In comparison, the catalyst and absorbent cost in a typical purification system for plants of a similar scale is around US$ 240,000. Thus, the provision and timely replacement of these materials is a comparatively small investment compared to the potential costs of poisoning the downstream catalysts. In plants with a pre-reformer, sulphur removal is critical to successful operation of the catalyst. A serious sulphur incident usually means immediate catalyst replacement is required. In addition to downtime, the replacement catalyst cost will be significant, approaching that for a steam reformer charge depending on the pre-reformer bed volume. Both sulphur and chlorides severely affect both low temperature shift (LTS) and methanol synthesis catalysts. These copper-based catalysts scavenge both sulphur and chlorides very effectively and are poisoned as a result. For a 2,000 mtpd ammonia plant, the cost in terms of lost LTS life can be of the order of US$ 500,000 per year plus the incremental production loss as water gas shift efficiency decreases. The effect on methanol synthesis catalysts have similar financial consequences. In comparison, the total cost of the catalysts and absorbents in the purification system is significantly less than the cost of the problems that can occur if the purification catalysts are not well maintained.
Case study Correct sampling for poisons eliminates plant operating problems
Sampling and testing for sulphur is not a simple task and there are many issues that have to be addressed. One plant suffered severe hot banding leading to regular steam outs and a loss of tube life. Sampling of the feedstock at the exit of the desulphurization system detected no sulphur and this was therefore ruled out as the cause of the problem. A lengthy investigation was conducted to identify the root cause of the problem but no other potential causes of the hot banding were found. The desulphurization system was then re-investigated. The first issue highlighted was that the sample lines were relatively long and the metal utilized for the sample lines would absorb sulphur. The sample lines were therefore redesigned, reducing the length significantly and using a metallurgy that would not absorb sulphur. The sample bombs were also replaced with a superior metallurgy. Subsequent analysis of the feed gas established that significant levels of sulphur were passing through the desulphurization system to the steam reformer. The installed catalysts and absorbents were then replaced with KATALCOJM products and the steam reformer was steamed a final time to remove the sulphur from the catalyst. As a result of this the tube appearance has now improved and the tube wall temperatures have returned to the normal value.
Following the scan the vessel was discharged with samples of the absorbent taken at intervals down the bed depth. The samples were analysed in the bed and confirmed that from 50% onwards, the bed was unreacted ZnO. The operator only changed out 50% of the absorbent, which saved them US$ 190,000 in turn-around costs.
Chlorides are very difficult to remove from a steam reformer during a steam out and in many cases the primary reformer catalyst will have to be changed out. The total cost for a two week shut-down to replace the catalyst is estimated to be US$ 2.6 million per week, including shut-down, catalyst and lost production costs.
Operational benefits
All Johnson Matthey purification catalysts offer a number of operational benefits: Flexible operating conditions KATALCOJM and PURASPECJM catalysts and absorbents can be operated over a wide range of temperatures, pressures and feedstocks. For example, HDS catalysts and zinc oxide absorbents have operated continuously in systems designed to run at temperatures as low as 250C (482F) and pressure as high as 50 bar (725 psi). Our purification catalysts are proven to be effective on a wide range of feedstocks, from light natural gases, through LPGs, light naphthas to heavy naphthas containing 20% aromatics. Long lives High activity and excellent absorption capacity mean that, with appropriate product selection, the purification catalysts lives will be maximized while extending the life of the downstream catalysts.
Chloride removal
Where chloride species are present in hydrocarbon feeds, the level is usually low. After these species are converted to hydrogen chloride over the HDS catalyst, they are present as hydrogen chloride and must be removed upstream of the zinc oxide absorbent. Zinc oxide reacts with chlorides to form zinc chloride and this adversely affects the porosity of the zinc oxide bed. This in turn impairs its sulphur absorption capacity and reduces the absorbent life. In addition, at normal operating temperatures, zinc chloride may migrate causing potential poisoning, corrosion and metallurgy issues downstream. The low chloride level means that the volume of absorbent required is usually small as long as it has a good chloride capacity. Consequently, it is usually included in the same reactor(s) as the zinc oxide as a thin top layer. The low contact time necessitates a fast efficient reaction between the HCl and its absorbent to effectively remove chloride to extremely low levels needed for protection of downstream catalysts. KATALCOJM 59-3 is formulated to provide fast reaction times and to have a high capacity for chloride removal. It contains a highly reactive alkali phase, sodium aluminate, dispersed on an alumina substrate. The gas phase reaction between HCl and sodium aluminate locks up the chloride as sodium chloride. Where higher chloride levels are encountered, the high reactivity of KATALCOJM 59-3 allows spikes of HCl to be removed effectively without compromising plant operation.
Ultra-purification
Ultra-purification or sulphur polishing absorbents are appropriate in some specific plant circumstances where the downstream catalysts are more susceptible to poisoning even by low sulphur levels. Analysis indicates that the total sulphur level exiting the zinc oxide absorbent is typically a few tens of ppb comprising of H2S, COS and traces of organo-sulphur species. The precise levels and mix vary as a function of the feedstock composition, operating conditions and effectiveness of the purification products installed. This low level of sulphur may still have a negative impact, for example, if the plant has a pre-reformer or a highly stressed top fired reformer since these are both particularly sensitive to sulphur poisoning. Thus, to maximize the life of these absorbents, Johnson Matthey Catalysts recommends the use of an ultra-purification catalyst, PURASPECJM 2084, as a final stage in the purification system. This reacts with and removes most of the trace sulphur compounds typically to levels below 10 ppbv.
Catalyst probe
The TRACERCO catalyst probe allows insertion of a sample of catalyst into a process stream. By selecting an appropriate absorbent/catalyst it is possible to check for the presence of poisons within a stream and thereby determine the root cause of downstream problems. Intermittent slugs of poisons can be identified using the sample probe whereas such random levels of poisons will be almost impossible to identify with spot sampling of the process stream, but yet can cause severe plant problems.
10
This figure illustrates typical locations for installation of the catalyst probe. A probe installed upstream of the purification system will pick up and allow identification of the poisons in the feed gas. A probe installed downstream of the purification system will allow pick up and identification of any poisons that have slipped through the purification system.
1 1
Catalyst selector
KATALCOJM and PURASPECJM purification catalysts are suitable for the full range of feeds to synthesis gas plants, whether an off gas, a natural gas, LPG or naphtha. Typical recommendations for our standard purification products are given below, however, Johnson Matthey Catalysts will provide specific recommendations to suit particular plant conditions depending on the feedstock composition, poisons present and vessel configuration. Johnson Matthey Catalysts are experts in difficult and unusual purification requirements and for these applications offer the PURASPECJM product range for a wide range of trace impurity removal. These include HDS catalyst and ZnO absorbents for low temperature applications, as well as products to remove the less usual poisons such as mercury and arsenic compounds. Pre-sulphided HDS catalysts may be recommended in the following circumstances: very high sulphur feeds high olefin feeds high carbon oxide feeds very low sulphur feeds very high hydrogen feeds fully active immediately fully active immediately avoid methanation avoid possible over reduction avoid possible over reduction
Pre-sulphiding can be achieved in situ by injection of a sulphiding agent with hydrogen at defined conditions. Alternatively, Johnson Matthey Catalysts can deliver the catalyst in the pre-sulphided form. PURASPECJM products may be recommended for removal of the less usual poisons. The most frequently offered products are summarised. Operating situation mercury arsenic low temperature HDS low temperature ZnO PURASPECJM product recommendation 156/ PURASPECJM 1 PURASPECJM 6156 152/ PURASPECJM 1 PURASPECJM 5152 KATALCOJM 61-2T PURASPECJM 2020
Feedstock impurity/ operating situation organic sulphur olefins saturation high COx content halide removal low sulphur content (single bed) moderate sulphur content (single bed) high sulphur content (lead lag beds) downstream pre-reformer long reformer catalyst cycle times
KATALCOJM product recommendation 41-6T 61-1T 61-1T 59-3 32-4 32-5 & 32-4 32-5 PURASPECJM 2084 PURASPECJM 2084
12
Catalyst characteristics
KATALCOJM 41-6T KATALCOJM 61-1T KATALCOJM 59-3 KATALCOJM 32-4 KATALCOJM 32-5 PURASPEC 2084
Composition
KATALCOJM 41-6T KATALCOJM 61-1T KATALCOJM 59-3 KATALCOJM 32-4 KATALCOJM 32-5 cobalt oxide/molybdenum oxide/alumina nickel oxide/molybdenum oxide/alumina sodium aluminate/alumina zinc oxide zinc oxide
590 37
560 35
860 54
1 140 71
1350 84
870 54
13
For further information on Johnson Matthey Catalysts, contact your local sales office or visit our website at www.jmcatalysts.com KATALCO, PURASPEC, STREAMLINE and TRACERCO are trademarks of the Johnson Matthey group of companies. PO Box 1 Belasis Avenue Billingham Cleveland TS23 1LB UK Tel +44 (0)1642 553601 Fax +44 (0)1642 522542 Oakbrook Terrace Two Transam Plaza Drive Chicago Illinois 60181 USA Tel +1 630 268 6300 Fax +1 630 268 9797
www.jmcatalysts.com