R. Forster Ruhrgas AG, Essen, Germany ABSTRACT The operating costs of glycol dehydration units are very largely determined by the cost of glycol replenishment and replacement. Over 50,000 mty of glycol are consumed worldwide for natural gas dehydration. Ruhrgas AG has made considerable efforts to minimize glycol consumption within the company's own plants and as a service rendered for other companies. Without extensive effort, glycol losses can be kept below 2 kg per 100,000 m³(n) of gas. Excessive glycol losses caused by foaming, a result of black sludge, can be effectively controlled by a defoamer. Glycol ageing is another commonly encountered problem. The Ruhrgas-Anti-Ageing Additive has proven its effectiveness in a series of field tests under a variety of conditions; a glycol life of > 10,000 operating hours has been demonstrated in pilot tests. The cloud-point filtration process developed by Ruhrgas has been successfully tested on a mini-plant scale; a pilot plant will be in service in June 2001. In this paper these methods are compared with common lifetime extension methods. RESUME Les coûts d'exploitation des installations de déshydratation au glycol sont dans une large mesure déterminés par les coûts associés à la régénération et au remplacement du glycol. Dans le monde entier, plus de 50 milliards de tonnes de glycol sont consommés par an pour la déshydratation au glycol. Ruhrgas AG a déployé des efforts considérables pour réduire la consommation de glycol aussi bien dans ses propres installations que dans celles de tiers auxquels elle offre ses services. Avec peu d'effort, la perte de glycol peut être maintenue en dessous de 2 kg par 100.000 m³(n). Des pertes excessives de glycol dues à la formation de mousse résultant des boues noires peuvent être maîtrisées da façon efficace en ayant recours à un agent antimousse. Le vieillissement du glycol constitue un autre problème souvent rencontré. L'additif anti-vieillissement développé par Ruhrgas a ici fait ses preuves dans toute une série d'essais sur site sous diverses conditions; une durée de vie du glycol supérieure à 10.000 heures de fonctionnement a été prouvée dans un essai pilote. La méthode de filtration au point de trouble, mise au point par Ruhrgas, a également été testée sur une mini-site; une installation pilote devant être mise en service en juin 2001. La présente communication se propose de comparer les nouvelles méthodes avec celles communément employées pour prolonger la durée de vie.

with some 30. Foam floods the mist eliminator and it is not effectively removed. Causes of Higher Glycol Losses Higher glycol losses may have a number of causes. However. Glycol treatment and the replacement of glycol losses and spent glycol account for a large part of the operating expenses of a glycol dehydration system. high glycol losses may be caused by acute or chronic foaming. 1.000 units in operation in the USA alone.000 operating hours cost-effective processing of spent glycol AVOIDANCE OF GLYCOL LOSSES The most important prerequisite for the cost effective operation of a glycol dehydration unit is the avoidance of glycol losses. reduction of glycol losses to below 2 mg/m³ increase in glycol service life to more than 10.6 mg/m³ of natural gas treated. Foam carried out of the system is normally not converted into mist but results in a bottom or annular flow. Only evaporation losses. Firstly. In this case. The approach adopted consists of three stages: 1. At the plants operated by Ruhrgas.2 mg per m³(n) of gas treated and it should be possible to reach values below 2 kg per 100. although significantly improved technologies such as the DRIZO process are now available. the mist eliminator may be incorrectly installed. problems in the downstream pipework are inevitable in the long term. glycol losses are below 0. indicated as a function of gas outlet temperature in Fig. The basic technology of most old glycol dehydration systems is based on the state of the art of 1970. glycol mist will not be effectively separated and will be entrained out of the glycol contactor. depending on the linear flow velocity of the gas. The objective of most of the improvements made has been to reduce pollutant emissions. 2. 3. the growing cost pressures faced by gas transmission companies now call for improvements to efficiency and reductions in operating expenses. Glycol consumption per cubic metre of gas treated is about 22 mg/m³(n) in the USA and about 17 mg/m³(n) in Russia. Total glycol consumption for natural gas dehydration is about 30. Foaming may also be caused by fouling of the mist eliminator. This paper presents methods which have been tested for the reduction of glycol consumption to values below 5 .000 tonnes per year in Russia. The annual cost of glycol consumed throughout the world is probably of the order of at least US$ 35 to 50 million. and about 10. Secondly.INTRODUCTION Glycol dehydration is one of the most important dehydration processes for natural gas.000 m³(n) even if the values specified by plant manufacturers are higher. Glycol losses may also occur on the regeneration side if the temperature at the reboiler column head reaches inadmissibly high values. are unavoidable.000 tonnes per year in the USA. If these values are exceeded. High-temperature cracking processes convert glycol into smaller molecules which are also carried out of the column head even if the . fouled or inadequately sized.

Germany) is equipped with a replaceable nozzle which is inserted against the direction of gas flow. 1. an isokinetic splitter is used to allow independent adjustment of the sample gas flow. the first stage is to draw up a balance sheet of glycol losses on the basis of the records available. The first step in reducing glycol losses is to determine the cause. Witten. temperature (p = 1 bar). diethylene glycol (DEG) and triethylene glycol (TEG) vs. experience indicates that incorrectly low readings are not to be expected.8 EG 0. Foaming probably affects 5 to 10 % of all dehydration units.4 0. It should be possible to detect these substances by analysis of the waste gas condensate. Equilibrium gas phase concentration of ethylene glycol (EG). The probe (produced by Marquis. a hydraulically adjustable sampling probe is inserted into the pipeline. An increase in glycol losses over the course of time may for example indicate a faulty mist eliminator. After gas has been allowed to flow through the measurement system for a few hours.2 DEG TEG 0 10 15 20 25 30 temperature / °C 35 40 45 50 Fig. The probe is inserted into the pipeline up to the point where the tip is in the center third of the line. 1. Measurement Systems In troubleshooting.temperature is sufficiently low. The Ruhrgas central laboratory has developed a number of test procedures for effective troubleshooting in the case of glycol losses. In our experience. preferably directly downstream from the glycol contactor.6 gas phase concentration / mg/m 1. A flow controller sets the sample gas flow to obtain isokinetic conditions at the probe inlet. the splitter is heated to reduce wall absorption.4 1. For this purpose. excessive glycol losses are frequently caused by foaming. Glycol contactor losses can be assessed on the basis of the glycol concentration in the treated gas.2 1 0.6 0. Glycol contactor and reboiler losses are then measured. The sampling system is described in [2]. . Like all the other sampling pipework. the balance sheet should preferably cover a period of several years. If necessary.

2. analysed and quantified in the laboratory. In cooperation with Ruhrgas AG. The substances absorbed are treated. The sample gas is fed through pipework filled with a suitable absorbent which traps the glycol and higher hydrocarbons entrained by the gas flow. The detector is bolted to an existing nozzle on the pipeline and is connected to a control unit by a fibre-optic cable. If a waste gas cooler is not installed on the dehydration unit. the liquid glycol is carried along the bottom of the pipeline or as a ring or film on the pipe wall. b) The "Mist Detector" produced by Telegärtner Gerätebau detects liquid mists in high-pressure gas pipelines. Glycol losses in the reboiler can be assessed by measuring the quantity of water entrained out of the system and determining the concentration of glycol in the water by analysis. The optical sensor shown above is connected to an electronic control unit by a fibre-optic cable. Depending on the gas flow velocity. Telegärtner Gerätebau has developed a mist detector suitable for use in explosion hazard areas which allows the continuous remote monitoring of glycol and oil mists in transmission pipelines. a) Schematic diagram of hydraulically adjustable sampling probe. 2. The probe is mounted on a flange and may be inserted into a pressurized pipeline via the bore of a ball valve.Fig. This method detects glycol mist entrained by the flowing gas but not glycol which has already separated out from the gas flow as a liquid. The detector is based on laser dispersion measurements. a defined partial flow of waste gas is routed . Fig.

In such cases. With structured packages. A complex coalescer filter is of little effect in eliminating liquid flowing along the wall of a pipe and a separator cannot trap mists. Choice of a Defoamer Acute foaming problems can be effectively solved by adding a suitable defoamer. the effectiveness of these systems is often limited because they attempt to tackle the wrong problem. If filters are flooded or soaked. glycol can absorb a volume of gas which is many times higher than the physical solubility of gas in glycol. glycol mists are difficult to coalesce and separate. In general. the flash gas flow rate may even reach 30 to 50 times the value in normal operation. Vane and mesh-pad mist eliminators. it is recommended to install a gas flow meter in the flash gas line and to monitor the flow reading regularly. Gas bubbles are bound to the sludge and lose their buoyancy. . A considerable increase in flash gas flow gives a clear indication of foaming. In this case. Where foaming is suspected. multicyclones and coalescer filters are highly effective in removing glycol mist but of limited effect when film flow or foam is present. the volume of the gas bubbles increases and the gas is released.through a highly effective gas cooler where the condensables components are separated out. However. The volume of foam formed in the glycol contactor is a function of the ratio of gas velocity to glycol recirculation flow. Filters must not be oversized. This also applies to chronic foaming caused by glycol with a high concentration of black sludge. extensive foaming is also observed in structured packages. unstable glycol release from the column is the result. It is therefore necessary to investigate the underlying problem thoroughly before taking any action. which is normally the case. the tendency to foaming is normally significantly less pronounced than with bubble trays. However. Foaming is produced by intensive contact between the liquid and gas phases in the glycol contactor. the larger the foam volume formed in the glycol contactor. if glycol is not effectively distributed through the structured package as a result of blocked holes in the distributor tray. In this case. it is more effective to combat the foaming problem itself than to invest in filters. glycol losses cannot be reduced using filters. In this way. Glycol ageing products and unavoidable impurities combine to form an emulsion known as black sludge. otherwise the coalescing effect is weakened. glycol flow through the package will be uneven and partial flooding may possibly be the result. In the case of foaming. The mechanism of foaming is dealt with in [1]. complex equipment is installed to retain the glycol or to separate it from the gas flow in the pipeline. Glycol Foaming Foaming is always caused by impurities in the glycol. their efficiency is also reduced. Frequently. Troubleshooting on Mist Eliminators and Glycol Separators Operators of plants with high glycol losses are well aware of the problem and have often taken a variety of action to combat it. If the foam reaches the bottom of the glycol contactor. During subsequent depressurization in the flash tanks. The higher the gas velocity and the lower the glycol recirculation flow. This is one of the reasons why TEG is used to create an artificial mist. The condensate is then analysed in the laboratory.

Over the course of time. maintaining its purity and significantly extending its service life. Methyldiethanolamine (MDEA) proved to be more stable than TEA. A few weeks later. These aldehydes are primary products of glycol cracking. As low pH values result in plant corrosion.5 m³/h. are used. greater . The defoamer was injected directly into the bottom of the glycol contactor. Tests carried out with various types of activated carbon showed that low-cost regenerated carbon may be more effective than costly new carbon. Further investigations were made and it was found that the filtration effectiveness of activated carbon is determined to a large extent by its ion exchange capacity. This observation was supported by the finding that a higher water content. An effective defoamer should meet the following requirements: • • • • • • • • • immediate defoaming effects excellent spreading very low dosing silicone-free high storage stability and low tendency to separation adequately low viscosity at low temperatures no adverse impact of long-term use chemical compatibility with glycols low ash content The defoamer used by Ruhrgas was initially tested in various dehydration units. 100 m³/h to 20 m³/h. problems occurred with increased flash gas flow and unstable glycol discharge from the contactor bottom.e. For this reason. Tests of the behaviour of various amines in glycol showed that the problem of heat stable salt (HSS) formation already familiar from amine plants also occurs in glycol. resulting in significant black sludge formation. The reason for this phenomenon is the formation of a number of carboxylic acids from aldehydes in Cannizzaro reactions. Normally. higher hydrocarbons entrained into the glycol react with glycol decomposition products. At one plant. Diethanolamine (DEA) was also found to be stable but cannot be recommended for other reasons. the flash gas flow fell from approx. following by continuous follow-up dosing of approx. 50 ml/h was used. As a result. it is recommended to skim off any oil at regular intervals. follow-up dosing was no longer required and the flash gas flow rate remained stable. An initial dose of 2 litres.Comprehensive laboratory tests were carried out on various proprietary defoamers recommended for glycol. bases are added to increase the pH. In other words. It was found that the defoamer must be injected directly at the point where it is intended to combat foaming.000 m³(n)/h at 60 bar and a constant glycol circulation rate of 3. It was not found that the defoamer had any detrimental impact on dehydration performance. i. Activated Carbon Filtration Activated carbon filtration can be used to remove a variety of impurities from glycol. The plant concerned is operated with a gas flow of 450. tertiary alkanolamines with a high boiling point such as triethanolamine (TEA). EXTENDING THE SERVICE LIFE OF GLYCOL Regular Maintenance The pH of glycol normally falls over the course of its service life. the carbon must be capable of absorbing the carboxylic acids present in the glycol.

oil entering the unit was emulsified very rapidly.500 operating hours without the additive. Following the successful completion of the field tests. As expected. Field Test of the Ruhrgas Anti-Ageing Additive The Ruhrgas Anti-Ageing Additive was already presented at IGRC 1998 [1]. led to more effective filtration. the glycol is still fit for use and achieves the specified dehydration performance. The objective was to investigate the effect of the additive at typical conditions found in aquifer and cavern storage facilities and pipeline compressor stations. by catalytic reactions on steel surfaces and corrosion products. the service life of glycol at the station was limited by severe black sludge formation with associated foaming. Following 10. Further investigations of the underlying chemical processes showed that the mechanism of effective activated carbon filtration is very similar to that of cloud point filtration described below. The formation of carboxylic acids by Cannizzaro reactions is also significantly reduced. Any oil entering the system could be skimmed off easily in the surge tank. the tendency to black sludge formation was significantly reduced with the additive. However. the Ruhrgas Anti-Ageing Additive is to be introduced successively at all the plants operated by Ruhrgas. Glycol with additive will be filled in during glycol replacement in combination with thorough cleaning of the entire unit. glycol service life with the additive has reached more than 10. the dehydration unit acts as an oil separator.500 and 4.000 operating hours. Epe and Waidhaus. In some sense. At the Waidhaus pipeline compressor station. Emulsification did not take place. A further field test at a production plant in the permafrost zone is already under preparation in cooperation with OOO Gazprom. At the two other stations.dissociation of the weak carboxylic acids. Previously. compared with the previous figure of between 2. No further action was required to maintain the purity of the glycol. it is already clear that the additive has significantly reduced black sludge formation at these stations compared with previous experience. .000 hours. which is operated on a continuous basis. It slows down the decomposition of glycol into compounds of lower molecular mass (for example. In addition. the additive impedes the formation of glycol gums. Field tests with the Anti-Ageing Additive were carried out at the Ruhrgas stations at Bierwang. After one year of operation. which act as emulsifiers in the formation of black sludge. about 200 litres of glycol were added to top up the system. including the elements of neutral exchange. The additive is added to the glycol at a concentration of 1 % to prevent the thermal cracking of the glycol or the thermo-oxidative decomposition. triethylene glycol is cracked into ethylene and diethylene glycol). Activated carbon filters should therefore always be installed on the rich glycol side. the glycol purity was still 96 %. such high operating hours have not yet been reached as these stations are only operated during withdrawal from storage. Black sludge formation was caused by the large volume of machine oil which is not retained by upstream separators. After 10. It is therefore to be expected that slow filters with a dwell time of at least 1 hour will give the best results. Previously. black sludge flocculation and deep bed filtration.000 operating hours.

the load on the sand bed filter (2) has been reduced and the backflushing times have been increased. was already presented at the last IGRC. Glycols processed by two different companies were tested. TeEG and high-boiling impurities comprising triethanol amine and higher hydrocarbons) is then separated from nonvolatile components in the thin film evaporator. Under these conditions. Furthermore. The process is suitable for the regeneration even of severely contaminated glycols which have been in service for 4. were significantly worse than those of fresh glycols. The quality of the processed glycols was to specification of technical grade TEG. only the low-boiling components (EG and DEG) are boiled off.000 to 5. This water is collected in the condensate tank of the dehydration unit. the distillation residue (TEG. which gives an indication that the surfactants have not been properly removed. The residue is then rectified under reflux. It was found that the wetting properties of the processed glycols.000 hours. In the meantime. In some cases. The purity was in excess of 95 %. The wetting properties of this distilled glycol were also inferior to those of fresh glycol. the water content of the rich and regenerated glycol falls. . At that time. the water is distilled off the glycol in a thin-film evaporator. the surface tension of the reclaimed glycols was found to be lower than expected. In addition. One problem in connection with the system is the disposal of the backflush water which is so severely contaminated with hydrocarbons and other organic substances that it cannot be fed to the public wastewater system. this was indicated by a slight yellow tinge in the processed glycol. The distilled TEG was inferior in quality to unused glycol. Poorer wetting properties have an adverse effect on mass exchange and therefore also on dehydration performance. the process has been tested and development has continued using a continuously operated mini-plant. The mode of operation of the cloud point filtration system has already been discussed elsewhere [1]. A pilot plant is currently being constructed and is scheduled for commissioning in June 2001. the principle of the process had been tested and developed on the laboratory scale. Initially. In laboratory tests. a glycol purification process patented by Ruhrgas. used glycol was purified by fractional distillation in vacuum using a 40 cm Vigreux column. which collects the liquids separated at the glycol contactor inlet. but all the samples had a more or less pronounced yellowish discoloration. Experience with the use of the pilot plant will be presented at the conference. further laboratory-scale tests were then carried out. Only minor changes have been made to the schematic design presented in that paper. and fed to the waste gas incineration system.Treatment Processes Distillation und Rectification A number of companies offer the regeneration of spent glycols from gas dehydration processes by vacuum rectification. assessed on the basis of the edge angle. It is therefore not necessary to install the cloud point filtration system on a permanent basis and the pilot plant has been designed for mobile service. A settle tank heated to 60 °C is installed downstream from the resin bed filter (1) for the separation of flocculated impurities. Cloud Point Filtration Cloud point filtration.

One of these glycols was severely contaminated with amines which had already been converted into heat stable salts to a very large extent. Purification was successfully completed in all cases. no separation of glycol ethers with similar boiling point Inferior wetting properties of regenerated glycol. A viability analysis is given in Table 1.In the mini-plant. In view of the high load. higher edge angle Incomplete separation of heat stable salts 100 % separation of hydrocarbon contaminants not always possible . ion exchange resins can therefore be expected to reach a service life of two years. wastegas incineration required No plant hold-up No separation of low-boiling glycols. the cloud point filtration process was tested with a number of glycol samples from a wide variety of plants. Weak acids were also effectively separated in the resin bed filter (1) and impurities were effectively flocculated and separated in the settle tank (2) and the sand bed filter (3). In comparison with vacuum rectification at a central plant. the differences are as follows: Cloud point filtration Possible on site with a mobile plant Dehydration unit remains in operation Disposal of backflush water difficult. antiageing additive required Regenerated product with superior surface and wetting properties Almost complete separation of heat stable salts 100 % separation of hydrocarbon contaminants Vacuum rectification Logistics of central processing Dehydration unit normally needs to be shut down Disposal of plant hold-up required Plant hold-up unavoidable Excellent separation of low-boiling glycols. There was no reduction in the capacity of the selected ion exchange materials even after three months of continuous operation in the mini-plant. The cationic impurities of the HSS were removed in the cation exchanger in bed (4).

R.4 1.1 2. R.818 $7.1 CONCLUSIONS It was shown that it is feasible to reduce glycol consumption to 5 of 6 mg/m³ of treated natural gas by taking relatively simple action. pp.6 0.4 0.Table 1. The cloud point filtration process and the anti-ageing additive are being marketed by the German-Russian joint venture Zapsibruhrgas-Engineering.273 $5.455 US Dollars $3. Extending Glycol Life in Natural Gas Dehydration Systems.636 $2. Glycol cost can already be reduced by 60 % by reducing glycol losses and using the anti-ageing additive: the cost of this action can be recouped immediately. The unit is adequately sized for dehydration plants with up to 15 tonnes of glycol. paper presented at the 1998 International Gas Research Conference Altfeld.0 8. The base case is based on 85 % capacity utilization in three-shift operation.364 US Cents/lb 3. The additional investment in a mobile cloud point filtration unit can be recouped after about 9 months if the quantity of glycol for regeneration is 100 tonnes per year. Forster... REFERENCES [1] [2] Forster..1 0.000 $56. Viability analysis for a mobile cloud point filtration unit with a treatment capacity of 300 lb/h. 799-802 . Practical experience with cloud point filtration is presented in the paper. Fixed Costs Purchased equipment Working capital (20 % of capital cost) Startup Materials Total Fixed annual costs Maintenance & repairs (10 % of equipment costs) Shipping costs Total Variable costs Natural gas Tap water Electricity Chemicals Materials Service Supervisor Total US Dollars $36.6 0.364 $7.727 $6. K. Metallspurenanalysen im Erdgas. H. gwf GasErdgas 140 (1999). and Kaesler.

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