ADAPT SILICA GEL ADSORPTION TECHNOLOGY: REASONS FOR SELECTION ON GAS CONDITIONING PLANTS.

Antony Kane, GL Noble Denton Lorenzo Micucci, Siirtec Nigi SpA Luciano Grisanti, Siirtec Nigi SpA

1 Abstract The choice of technology for both dehydration and hydrocarbon dewpointing is crucial for the smooth operation and economic success of gas conditioning plants. Several process technologies are available to designers including adsorption of water and heavy hydrocarbons on silica gel. ADAPT uses this technology to combine the dehydration and hydrocarbon dewpoint control unit operations into a single process plant. This avoids the need for multiple gas treating units that are usually associated with high energy demands and the installation of complex rotating machinery. This paper describes the technology and the technical reasons for its choice as the gas conditioning plant with a particular emphasis on underground gas storage facilities and long pipeline gas transportation schemes.

2 Introduction In the last few decades, the consumption of natural gas has been steadily increasing worldwide. The growth of the demand of this resource in the period between 1970 and 2004 has been 1.4 times faster than the growth in primary energy. The resultant growth of exports of the natural gas from producing country to consumers via pipelines is linked to the increasing of transportation distances, which can be as much as 3750 km for the transportation pipelines in Russia. Due to the head loss through the pipeline, it is necessary to compress again the gas when its pressure falls to a critical pressure, typically around 55-60 bar g. For networks having linear configuration, the distance between two compression stations is typically 150-200 km. These compressors need continuous maintenance and labour. In such cases it is required the water content of the natural gas is in the range of 4-7 lb/MMSCF and the hydrocarbon dew point -10C at 55 bar g. The increasing length of the transportation via pipelines raises the issue of the reduction of the compression costs, in particular when the pipelines have to cross marine areas as it the case of Blue Stream and Nord Stream projects. In such situations, the natural gas flows through regions with a wide variety of environmental conditions that could lead to formation of solid hydrates and condensed liquids. Both are detrimental for the operation due to blockage, erosion, corrosion, clogging of fittings and mechanical stresses they can cause to the pipeline system.

Thus, due to stringent specification for gas required by long distance transportation, special care must be paid to the conceptualization of the gas treatment plant upstream the transportation system in order to prepare the natural gas for the long trip toward the market. On the market side, the natural gas demand features a high seasonal variability, in cold countries the ratio of the winter/summer consumptions may be as much as 3:1, on the other hand the production and transportation systems of the gas require steady conditions. Thus, to conjugate the stability of the supply with the variability of the demand it is necessary to provide in between a suitable storage capacity. For this reason, during the summer period the excess supply is accumulated in underground (geological) storage while during the winter period is withdrawn to meet extra demand. When exhausted oil & gas fields are used as storage, the extracted natural gas may not match the pipeline specification due to the absorption of water and gasolines contained in the porous geological substrate used as storage. In such cases, the extracted natural gas needs to be re-conditioned before being added to the energy network. In the current NG industry, the gas conditioning includes the water removal and the hydrocarbon dewpointing. The former can be achieved by means of a dehydration process based on glycol, usually triethylene glycol (TEG). The latter can be achieved with gas expansion lowtemperature separation processes or by direct refrigeration. In the overall, if the C6+ content of the natural gas is below 0.25 % v as might be the case of gases from conventional and semi-conventional underground storage or the export gas from local distribution networks, the gas treatment plant may be expensive because it should include multiple process facilities fitted with heavy-duty machinery (turbo-expanders and compressors). Furthermore, for international natural gas export, the TEG process and the low-temperature processes or direct refrigeration are not able to achieve stringent specification for the treated natural gas . Therefore alternative processes have to be implemented in order to cost-effectively remove the NG contaminants. This paper will show how the ADAPT adsorption technology combines multiple process facilities into one single unit achieving stringent natural gas specification while assuring cost effective projects and the reasons why it should be selected for gas conditioning plant. 3 ADAPT Technology The ADAPT technology is a separation process based on the principles of surface chemistry, more specifically on physi-sorption consisting of chemical species (adsorbates) adsorption on the active sites distributed throughout the surface of a solid media, silica gel. The silica gel is a mesoporous adsorbent, in the form of beads, obtained through a sol-gel process consisting of: i) Preparation of a silicic acid, a concentrated dispersion of finely divided particles of SiO2 (silica hydrosol), by mixing a sodium silicate solution, for example, with a mineral acid (HCl): Na2SiO3 + 2HCl + nH2O 2NaCl + SiO2*nH2O + H2O

ii) Dispersion of the obtained hydrosol into a hot oil where the silicic acid undergoes to a polymerization condensation through which a high molecular weight polysilicate forming a 3-D

porous network filled with water molecules (hydrogel) having hydroxyl groups distributed on both the inner surface of pores and the outer surface of the beads. iii) Recovery of the obtained beads, drying and calcinating in order to produce beads with the targeted properties. The hydroxyl groups scattered on the surfaces of beads constitutes the active sites of the adsorbent material. Thus hydrogen bonds and van der Waals interactions are the major types of bonding for the adsorption of water and hydrocarbons.

Being an amorphous material with mesopores of about 20 , the pores of the silica gel is also the locus of capillary condensation. This is because the shape of the cavities are irregular. The adsorption of molecular layers of adsorbates molecule will coat the surface as indicate in the second sketch of the side figure. At the tip, the size of the pores is comparable with the size of the molecules, however the presence of active sites magnifies the level of van der Waals interactions so that the multilayer adsorption on the surface causes the formation of a meniscus separating the gas phase from the liquid phase (third sketch). In such situation, the adsorbed species vapour pressure is lower than the corresponding partial pressure of the same species in the gas phase and the condensation occurs inside the pores. Thus, the silica gel allows the easy separation of natural gas components even at their very low partial pressure. This phenomenon provides the rationale for the advantages of the use of silica gel over other systems based on the low temperature separation of hydrocarbons.

Increasing the temperature, the hydrogen bonding and the van der Waals interactions loosen due to the increased kinetic energy of the adsorbates making the adsorption a reversible process. Thus, once saturated the adsorption bed can be regenerated simply by providing heat to strip away water and hydrocarbons.

The separation by means of silica gel is a dynamic process. In a single component adsorption process, when the gas contacts the adsorbent bed, the upper part of the silica gel becomes saturated with the adsorbates (the dark part of tower in the following drawing) whilst the lower part remains fresh. Due to the saturation of the silica gel, the concentration of the key species in the gas remains unchanged throughout the saturation zone of the bed, then it decreases according to the S curve to zero as shown in the following figure. The bed depth where the gas concentration of the adsorbates changes is referred to as the mass transfer zone (MTZ). Thus, at any given time, in the adsorption bed three distinct layers can be spotted: the saturated zone featuring a constant gas concentration, the MTZ and the fresh bed where the content of the adsorbate concentration in the gas is zero. In time, the MTZ moves downward, as illustrated in the following diagram, at a rate characteristic of the adsorbates until it breaks into the outlet stream at the breakthrough time, defined by the gas specification. The breakthrough marks the end of the adsorption process. The saturated bed thus has to be taken off line and regenerated to repeat the adsorption cycle.

In multi-component adsorption processes, as is the case for the natural gas conditioning, the process is a little bit more complex because each natural gas components has a different affinity with the adsorbent bed depending upon the molecular structure. Silica gel preferentially adsorbs polar species and high molecular weight hydrocarbons according to the following order of adsorption: H2O > RSH > C8+ > C7 > C6 > C5 > Light Ends Thus methane breaks out practically instantaneously followed by ethane and propane, in the meantime water is retained by the silica gel so it is found at the top of the adsorbent bed, the other components being distributed

along the axis of the vessel depending upon the affinity towards the adsorbent. At a certain time, in the same token of a chromatograph, a number of MTZ can be spotted on the silica gel bed. As time passes by, these MTZs move downwards and the species having the most affinity will displace and replace in their location the weaker held components. Typically within 1-3 hours, depending upon the design, the C6+ breaks through. At this point most of the C6+ is loaded on the solid adsorbent along with 60-80% of C5+. For the design of the adsorption plant, depending upon the NG specification, the designer has to determine the hydrocarbon cut which corresponds to the desired dew point and thus has to define the plant design to assure the continuity of the operation. This is the most crucial step of the project, requiring expertise and deep knowledge of the technology, from which the success of the process depends on. The adsorption is based on physi-sorption process where the bonds between the adsorbent and the surfaces are weak being based on hydrogen bonds and van der Waals interactions. Heating the bed will cause the desorption of the adsorbates which can be easily recovered downstream, typically by cooling to condense them. In this way the adsorption capability of the adsorbent material is restored and the production cycle can be repeated. The regeneration of the silica gel is achieved in two steps: heating by blowing a hot regeneration gas through the loaded bed for a certain period of time and cooling the hot, regenerated bed back to the operating conditions. Typically, the same wet natural gas is used as the regeneration media with the co-current arrangement for the flow pattern. In some cases, where very tight specifications are required, the treated gas (dry) is used for the regeneration. Thus a slipstream of the produced gas is withdrawn from the dried natural gas and recycled back to the tower to be regenerated by means of a compressor. This process configuration offers the advantage of more efficient operation for the regeneration due to the use of a dry gas. However this benefit bears the burden of extra expenditure and reduced reliability due to the rotating machinery and the compression energy. For pipeline transportation and underground storage facilities, the process configuration based on the raw gas (wet) is preferred. In this case a control valve, which imposes a pressure drop to the fluid, is installed at the facility battery limit and the regeneration gas is taken upstream of the said valve so that it has enough pressure to pass through the regeneration circuit and re-enter into the raw gas downstream of the control valve. This option allows for a reduction of the Capex because the recycle compressor is not needed and the pressure drop across the control valve is typically only around 1.5 bar.

In both cases, the heat for the regeneration is usually provided by a fired heater. During the cooling step of the regeneration, the fired heater is on pilots and being by-passed.

The ADAPT technology implements the regeneration technique termed heat pulse. In this case the heating-cooling steps are sequenced on a single bed by interrupting the bed heating, not when

the entire bed is brought to the regeneration temperature, but only when a part of the bed is heated to the desired temperature. Feeding the cooling gas to the top (hot) part of the bed causes the shifting downward of the heat accumulated in upper part of the adsorbent bed to the lower part. While the upper end of the bed cools down, the temperature of the lower end rises and the adsorbates are stripped away from the adsorbent surface in the bottom part of the regeneration tower which thus is completely regenerated. The heat pulse technique concentrating the two regeneration steps only on one individual adsorbent bed allows the saving of a second regenerating tower needed by some schemes. Because the adsorption towers are also equipped with costly cycling valves, the saving of a tower turns into a significant reduction in investment cost. The heat pulse technique allows the regenerated bed to be placed on standby until it is required when the product gas hydrocarbon dewpoint is approached. The use of the standby reduces the plant Opex by reducing fuel gas consumption and also extending adsorbent service life. It also allows improved operational flexibility by providing the opportunity for variable cycle times and higher regeneration cooling flowrates if required. This flexibility is beneficial when the plant duty is reduced such as in cases of lower throughput and leaner feed gas and also allows optimisation for fresher silica gel that exhibits higher capacity. The ADAPT technology, implementing the heat pulse technique for the regeneration turns out to be the technology of choice for the simultaneous water removal and hydrocarbon dewpoint control.

4 Reasons for selecting the ADAPT technology As mentioned earlier, the characteristics of silica gel that differentiate it from other adsorbent materials are the distribution of active sites on both the inner surface of pores and the outer surface of the beads. These give rise to relatively intense interaction fields attracting polar and polarisable molecules. Furthermore, the asymmetrical shape of the pores causing the capillary condensation of the heavy hydrocarbon adds adsorption capability of the silica gel. Those peculiarities make possible the extraction of adsorbate species from a gas mixture even when their partial pressures are lower than their vapour pressure at the operating conditions. Consequently, the adoption of the ADAPT process is advantageous for the conditioning of lean natural gas at lower pressures. In general, the technology selection of the gas treatment plant pivots around three major variables: the feed stream pressure, the differential pressure available between the feed and the treated gas and the feed composition. The C5+ hydrocarbon load on silica gel in dynamic applications is typically around 10-20 % wt/wt of adsorbent, thus for rich gases (with more than about 0.75 % v of C5+), the silica gel process may not be the optimum solution due to amount of adsorbent the process would require. In case of lean natural gas, typically with C6+ < 0.2% v, the cost effectiveness of the choice depends upon the feed gas pressure and the allowed differential pressure for the overall process plant. At lower pressures (<80 bar g) and low differential pressure, ADAPT is the technology of choice. As a matter of fact, the alternate gas expansion low temperature separation process based on constant-

enthalpy processes (J-T process) or constant-entropy (gas expansion in turboexpander) processes requires high pressure drop to attain the specified dewpoint. Thus, these alternate processes need to be complemented with expensive booster compressors at the plant outlet in order to restore the pressure. At high feed gas pressure, if the allowed differential pressure is less than 5 bar, as is the case of gas conditioning plants upstream of the compression stations feeding the backbones of gas transmission system, the ADAPT process is advantageous. UGS is concerned with the storage of transmission quanlity gas that requires re-conditioning when the gas is extracted. In the case of gas storage in depleted oil and gas reservoirs, the extracted gas requires dehydration and hydrocarbon dewpointing to remove water and heavy hydrocarbon components that have contaminated the stored gas. ADAPT technology is advantageous on UGS sites because it can operate at variable pressure, can achieve high turndown, can handle variable feed gas compositions and exhibits rapid start-up and shut-down characteristics. The above concepts have been extensively implemented in several important projects. Here below the Case History outlines how the ADAPT technology has been translated into industrial practice.

5 Case History, the Portovaya Gas Treatment Plant for the Nord Stream project An important example of use of the ADAPT process for NG treatment is the Portovaya GTP recently realized by Siirtec-Nigi in Russia, treating a large stream of NG (~ 170 MMsm3/d) fed to the Nord Stream subsea pipelines and then delivered to Europe. Operation of Nord Stream pipelines is quite challenging due to the amount of transported NG and the considerable length of subsea pipelines, (about 1224 km) without intermediate recompression, leading to unusually high pressure drops and Joule-Thomson cooling across pipelines. This requires very stringent NG specifications to ensure a safe and stable transport through the pipelines, with a HC dew point < -20 C (@22 bar) and a water dew point < -30 C (@22 bar), much lower than what required for transport on the European NG distribution grid.

NORD STREAM

Raw feed at Portovaya GTP is a stream of high pressure lean NG contaminated with both water and heavy hydrocarbon (80 bar, 95% methane plus 0,1 % as C5+); lean composition and high pressure along with the very low treated gas HC dew point increases the complexity of process selection. Due to vapour-liquid equilibrium constraints of treated gas, the adoption of a conventional processing scheme would require a complex arrangement with a mol sieve dehydration followed by gas expansion (turbo-expander plus auxiliary cooling) to achieve cooling at nearly cryogenic level, this arrangement is not only complex but also associated with undesirably high pressure losses, as the GTP is located just upstream the main Compression Station (CS) this would require either and additional booster compressor or an enlargement of main CS. Conventional processing is therefore characterized by both higher investment costs and energy consumptions.

Instead, energy consumption and investment cost for Portovaya GTP have been optimized by adoption of silica gel ADAPT process, able to achieve the required water and HC dew points in a single process unit without cryogenic processing and with minimum pressure losses, allowing considerably lower energy consumptions and also a lower investment cost.

As a reference, for the given conditions, the energy consumption for the conventional arrangement based on mol sieves & gas expansion is about 500% higher than for ADAPT, while investment cost for ADAPT arrangement is about 30% lower than for the conventional; to be also noted that differences in energy consumptions between the two options equals to about 160 MMsm3/y of equivalent NG, net saving achieved with use of ADAPT equals to about 0,3% of the overall amount of transported NG and could pay back the investment cost for Portovaya GTP well within the project life of 25 years.

The resulting arrangement of Portovaya GTP based on ADAPT is simple: silica gel is packed in adsorber vessels working cyclically and switching in phases of adsorption and regeneration. During regeneration, realized using a slip stream of feed gas, silica bed is heated up to about 250 C to complete desorption and then it is cooled down to recover the adsorption capacity, heating is realized by the highly optimized heat pulse procedure, allowing to decrease the number of installed adsorbers as well as the number of switching valves and piping with additional advantages on investment cost compared with conventional silica gel processing. Due to constraints related to the transportability of the equipments, Portovaya GTP has been arranged in four parallel process trains, each one sized for about 42,5 MMsm3/d. Each train includes 5 adsorber towers (within the 5 m diameter x 10 m tan-tan length maximum allowable sizes), a complete regeneration circuit and high efficiency filtration systems to improve silica gel life. Operation of each train is ensured by 22 automatic switching valves in synchronized operation to switch adsorbers between production and regeneration circuits. A total of 2120 tons of silica gel is required in 20 Adsorbers making Portovaya GTP the worlds largest silica gel based dew point control plant based on treated NG flowrate, number of adsorber towers and installed silica gel amount.

About some of the technical issues related with ADAPT process it is to be noted that unit arrangement is simple but characterized by pronounced transient conditions mainly due to the short regeneration time which is in the range of 90 100 minutes, much lower that typical times seen in similar solid bed processing units such as the mol sieves, characterized by longer regeneration times (6 8 hr) leading to smoother transients.

One example is the quite pronounced HC desorption peak during silica gel bed regeneration, or the cyclic and sharp fluctuations of temperatures during regeneration inducing cyclic stress on equipment and piping that needs to be accounted for a correct mechanical design (by means of dedicated finite element numerical approach). To be also mentioned that short regeneration time requires adsorbers be lined with internally refractory to avoid excessive heat dispersions in massive adsorbers wall, operation is not complex but lengthy adding additional constrains to delivery time for adsorbers which are the critical items for ADAPT units. Siirtec-Nigi was awarded the contract for the supply of the Portovaya GTP in early 2009 and the overall project schedule has been tuned based on the Nord Stream schedule. One of the key points setting project timing was the long delivery time of the adsorber towers requiring very early placement of orders which was possible thanks to the excellent cooperation between Siirtec-Nigi and GL Noble Denton. Construction and start up of first two process trains at Portovaya GTP has been completed in November 2011 in conjunction with the start of the first Nord Stream subsea pipeline, achieving excellent results in terms of treated gas quality. Remaining two process trains of Portovaya GTP are currently under pre-commissioning activities and the start -up is foreseen in the second half of 2012.

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As a final note, when Portovaya GTP will be at full capacity about 25% of the overall Russian NG export (according to 2011 forecast) will be treated by means of ADAPT process, demonstrating the key role of this technology for NG treatment.

6 Conclusions The full understanding of the properties of the silica gel adsorbent made ADAPT the technology of choice in the market segment of NG transportation via pipeline and underground storage facilities until recently dominated by mechanical refrigeration and gas expansion low temperature separation plants. The Blue Stream project, launched on August 2000 for the exportation of 47 MMsm3/d of Russian gas to Turkey by crossing the Black sea via 360 km deep submarine pipeline, marked the inception of the silica gel as the viable alternative to the more traditional and expensive cryogenic plants. The tight collaboration between GLND and SINI started with the Burullus Gas projects in Egypt, provided the valuable plant feedbacks needed for lowering the position on the learning curve and thus, to improve the design and operation of silica gel technology that now can be custom-tailored to maximise the benefits it can offer in terms of cost savings while meeting tight process specification. There are currently 11 ADAPT plants in operation or under construction with an overall capacity of 475 MMsm3/d and the technology has been proven in service for over 25 years. The application to the Nord Stream Project, currently the worlds biggest silica gel plant, has once again proved that the silica gel process is the technology of choice when the NG has to be treated to be transported for long distance via pipelines.

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