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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 m(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 cots d'exploitation des installations de dshydratation au glycol sont dans une large mesure dtermins par les cots associs la rgnration et au remplacement du glycol. Dans le monde entier, plus de 50 milliards de tonnes de glycol sont consomms par an pour la dshydratation au glycol. Ruhrgas AG a dploy des efforts considrables pour rduire 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 tre maintenue en dessous de 2 kg par 100.000 m(n). Des pertes excessives de glycol dues la formation de mousse rsultant des boues noires peuvent tre matrises da faon efficace en ayant recours un agent antimousse. Le vieillissement du glycol constitue un autre problme souvent rencontr. L'additif anti-vieillissement dvelopp par Ruhrgas a ici fait ses preuves dans toute une srie d'essais sur site sous diverses conditions; une dure de vie du glycol suprieure 10.000 heures de fonctionnement a t prouve dans un essai pilote. La mthode de filtration au point de trouble, mise au point par Ruhrgas, a galement t teste sur une mini-site; une installation pilote devant tre mise en service en juin 2001. La prsente communication se propose de comparer les nouvelles mthodes avec celles communment employes pour prolonger la dure de vie.

INTRODUCTION Glycol dehydration is one of the most important dehydration processes for natural gas, with some 30,000 units in operation in the USA alone. The basic technology of most old glycol dehydration systems is based on the state of the art of 1970, although significantly improved technologies such as the DRIZO process are now available. The objective of most of the improvements made has been to reduce pollutant emissions. However, the growing cost pressures faced by gas transmission companies now call for improvements to efficiency and reductions in operating expenses. 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. Total glycol consumption for natural gas dehydration is about 30,000 tonnes per year in the USA, and about 10,000 tonnes per year in Russia. Glycol consumption per cubic metre of gas treated is about 22 mg/m(n) in the USA and about 17 mg/m(n) in Russia. The annual cost of glycol consumed throughout the world is probably of the order of at least US$ 35 to 50 million. This paper presents methods which have been tested for the reduction of glycol consumption to values below 5 - 6 mg/m of natural gas treated. The approach adopted consists of three stages: 1. 2. 3. reduction of glycol losses to below 2 mg/m increase in glycol service life to more than 10,000 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. Only evaporation losses, indicated as a function of gas outlet temperature in Fig. 1, are unavoidable. At the plants operated by Ruhrgas, glycol losses are below 0.2 mg per m(n) of gas treated and it should be possible to reach values below 2 kg per 100,000 m(n) even if the values specified by plant manufacturers are higher. If these values are exceeded, problems in the downstream pipework are inevitable in the long term. Causes of Higher Glycol Losses Higher glycol losses may have a number of causes. Firstly, the mist eliminator may be incorrectly installed, fouled or inadequately sized. In this case, glycol mist will not be effectively separated and will be entrained out of the glycol contactor. Secondly, high glycol losses may be caused by acute or chronic foaming. Foam floods the mist eliminator and it is not effectively removed. Foam carried out of the system is normally not converted into mist but results in a bottom or annular flow, depending on the linear flow velocity of the gas. Foaming may also be caused by fouling of the mist eliminator. Glycol losses may also occur on the regeneration side if the temperature at the reboiler column head reaches inadmissibly high values. High-temperature cracking processes convert glycol into smaller molecules which are also carried out of the column head even if the

temperature is sufficiently low. It should be possible to detect these substances by analysis of the waste gas condensate.
1,6 gas phase concentration / mg/m 1,4 1,2 1 0,8

0,6 0,4 0,2



0 10 15 20 25 30 temperature / C 35 40 45 50

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

Fig. 2. a) Schematic diagram of hydraulically adjustable sampling probe. The probe is mounted on a flange and may be inserted into a pressurized pipeline via the bore of a ball valve.

Fig. 2. b) The "Mist Detector" produced by Telegrtner Gertebau detects liquid mists in high-pressure gas pipelines. The optical sensor shown above is connected to an electronic control unit by a fibre-optic cable.

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 substances absorbed are treated, analysed and quantified in the laboratory. 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. Depending on the gas flow velocity, the liquid glycol is carried along the bottom of the pipeline or as a ring or film on the pipe wall. In cooperation with Ruhrgas AG, Telegrtner Gertebau 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. The detector is bolted to an existing nozzle on the pipeline and is connected to a control unit by a fibre-optic cable. The detector is based on laser dispersion measurements. 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. If a waste gas cooler is not installed on the dehydration unit, a defined partial flow of waste gas is routed

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

Comprehensive laboratory tests were carried out on various proprietary defoamers recommended for glycol. 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. It was found that the defoamer must be injected directly at the point where it is intended to combat foaming. At one plant, problems occurred with increased flash gas flow and unstable glycol discharge from the contactor bottom. The defoamer was injected directly into the bottom of the glycol contactor. An initial dose of 2 litres, following by continuous follow-up dosing of approx. 50 ml/h was used. As a result, the flash gas flow fell from approx. 100 m/h to 20 m/h. A few weeks later, follow-up dosing was no longer required and the flash gas flow rate remained stable. It was not found that the defoamer had any detrimental impact on dehydration performance. The plant concerned is operated with a gas flow of 450,000 m(n)/h at 60 bar and a constant glycol circulation rate of 3.5 m/h. EXTENDING THE SERVICE LIFE OF GLYCOL Regular Maintenance The pH of glycol normally falls over the course of its service life. The reason for this phenomenon is the formation of a number of carboxylic acids from aldehydes in Cannizzaro reactions. These aldehydes are primary products of glycol cracking. As low pH values result in plant corrosion, bases are added to increase the pH. Normally, tertiary alkanolamines with a high boiling point such as triethanolamine (TEA), are used. 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. Methyldiethanolamine (MDEA) proved to be more stable than TEA. Diethanolamine (DEA) was also found to be stable but cannot be recommended for other reasons. Over the course of time, higher hydrocarbons entrained into the glycol react with glycol decomposition products, resulting in significant black sludge formation. For this reason, it is recommended to skim off any oil at regular intervals. Activated Carbon Filtration Activated carbon filtration can be used to remove a variety of impurities from glycol, maintaining its purity and significantly extending its service life. 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. In other words, the carbon must be capable of absorbing the carboxylic acids present in the glycol. This observation was supported by the finding that a higher water content, i.e. greater

dissociation of the weak carboxylic acids, led to more effective filtration. Activated carbon filters should therefore always be installed on the rich glycol side. 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, including the elements of neutral exchange, black sludge flocculation and deep bed filtration. It is therefore to be expected that slow filters with a dwell time of at least 1 hour will give the best results. Field Test of the Ruhrgas Anti-Ageing Additive The Ruhrgas Anti-Ageing Additive was already presented at IGRC 1998 [1]. 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. It slows down the decomposition of glycol into compounds of lower molecular mass (for example, triethylene glycol is cracked into ethylene and diethylene glycol). The formation of carboxylic acids by Cannizzaro reactions is also significantly reduced. In addition, the additive impedes the formation of glycol gums, which act as emulsifiers in the formation of black sludge, by catalytic reactions on steel surfaces and corrosion products. Field tests with the Anti-Ageing Additive were carried out at the Ruhrgas stations at Bierwang, Epe and Waidhaus. The objective was to investigate the effect of the additive at typical conditions found in aquifer and cavern storage facilities and pipeline compressor stations. A further field test at a production plant in the permafrost zone is already under preparation in cooperation with OOO Gazprom. At the Waidhaus pipeline compressor station, which is operated on a continuous basis, glycol service life with the additive has reached more than 10,000 operating hours, compared with the previous figure of between 2,500 and 4,500 operating hours without the additive. After 10,000 hours, the glycol is still fit for use and achieves the specified dehydration performance. Previously, the service life of glycol at the station was limited by severe black sludge formation with associated foaming. Black sludge formation was caused by the large volume of machine oil which is not retained by upstream separators. In some sense, the dehydration unit acts as an oil separator. Previously, oil entering the unit was emulsified very rapidly. As expected, the tendency to black sludge formation was significantly reduced with the additive. Any oil entering the system could be skimmed off easily in the surge tank. Emulsification did not take place. Following 10,000 operating hours, the glycol purity was still 96 %. After one year of operation, about 200 litres of glycol were added to top up the system. No further action was required to maintain the purity of the glycol. At the two other stations, such high operating hours have not yet been reached as these stations are only operated during withdrawal from storage. However, it is already clear that the additive has significantly reduced black sludge formation at these stations compared with previous experience. Following the successful completion of the field tests, 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.

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

In the mini-plant, the cloud point filtration process was tested with a number of glycol samples from a wide variety of plants. Purification was successfully completed in all cases. One of these glycols was severely contaminated with amines which had already been converted into heat stable salts to a very large extent. 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). The cationic impurities of the HSS were removed in the cation exchanger in bed (4). There was no reduction in the capacity of the selected ion exchange materials even after three months of continuous operation in the mini-plant. In view of the high load, ion exchange resins can therefore be expected to reach a service life of two years. A viability analysis is given in Table 1. 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, wastegas incineration required No plant hold-up No separation of low-boiling glycols, 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, no separation of glycol ethers with similar boiling point Inferior wetting properties of regenerated glycol, higher edge angle Incomplete separation of heat stable salts 100 % separation of hydrocarbon contaminants not always possible

Table 1. Viability analysis for a mobile cloud point filtration unit with a treatment capacity of 300 lb/h. The base case is based on 85 % capacity utilization in three-shift operation. The unit is adequately sized for dehydration plants with up to 15 tonnes of glycol.
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 $36,364 $7,273 $5,818 $7,000 $56,455 US Dollars $3,636 $2,727 $6,364 US Cents/lb 3.1 2.4 0.1 0.6 0.6 0.4 1.0 8.1

CONCLUSIONS It was shown that it is feasible to reduce glycol consumption to 5 of 6 mg/m of treated natural gas by taking relatively simple action. 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 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. Practical experience with cloud point filtration is presented in the paper. The cloud point filtration process and the anti-ageing additive are being marketed by the German-Russian joint venture Zapsibruhrgas-Engineering. REFERENCES [1] [2] Forster, R., Extending Glycol Life in Natural Gas Dehydration Systems, paper presented at the 1998 International Gas Research Conference Altfeld, K., Forster, R. and Kaesler, H., Metallspurenanalysen im Erdgas, gwf GasErdgas 140 (1999), pp. 799-802