i sifayosan Use molecular sieves to remove water, sulfur and other contaminants A.M, Aitani, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia he ability to remove moisture and sulfur com- ‘pounds in a single-step operation makes molecular sieves uniquely suited for drying sour natural gases. They have an ordered erystal structure resulting in a.uniform pore size, determined by the crystal’s unique structure and chemistry. ‘© Many plants now use molecular sieves for gas drying “sécause they can remove water to very low levels. The phenomena occurring in a molecular sieve dryer is simul- taneous H,S adsorption and rate-limited, adsorbent eat- alyzed reaction of HS to earbonyl sulfide, Special acid-resistant molecular sieves ean maintain their ‘dehydration capabilities over long periods of onstream use ‘without undesirable side effects, With the increasing value of natural gas, many previously uneconomical acd gas fields are now considered for processing by acid-esistant molecular sieves. Molecular sieves are attractive for gas drying since no precooling is required as with glycol dehydrators, Com- mercially proven molecular sieve technology produces prod- uct gas steams containing less than 0.1 ppmv water. Appli- ‘able pressure ranges are from subatmospheric to mare than 100 atm and temperature ranges from below zero to 200°C. Design technology inclides mass transfer rate information asa function of temperature, pressure, mass flowrate, vis- cosity, water content and carrier composition. sur gas. Drying natural gas is a growing problem for ~# industrial world. Sweet gas is no problem, But many wells in areas such as Saudi Arabia produce a gas con- taminated by: * Heavy hydrocarbons (propane and butane) C0; HS * Mercaptans. With the increasing value of natural gas, the HPI needed acid-resistant molecular sieves that could main- tain dehydration capacities over long onstream periods exposed to these contaminants. For Saudi Arabia, the importarice of natural gas to the petrochemical industry is revealed by the master gas sys- tem. It can process more than 118 million md (4 billion £8/a) of raw natural gas.! The system includes three gas processing plants and two NGL fractionation facilities (at ‘Yanbu and Juaymah). Gas is collected with crude from onshore and offshore fields and deep nonassociated “dry gas" from various Saul fields. However, the gas contains constituents other than metifane. Therefore, a knowledge ofthe occurrence and concentration ofthese constituents in the gas is needed to properly handle processing. natural gas dn % Support -beam Sample top Ils ogy & thermowel Fig. 1. Dyers spectcations—dyer relocated between the stp- potand docthanizor!® Natural gases containing HaS are “sour” whereas H,S- free natural gases are “sweet.” Water removal from natu- ral gas is necessary to prevent condensation and formation of ce or gas hydrates, Water in the liquid phase eauses corrosion or erosion problems in pipelines and equipment, particularly when CO, and HS are present in the gas. ‘Water is also removed to meet a water dew point require- ment of a sales gas contract? Natural gas dehydration using solid adsorbents (molecular sieves, alumina and sil- ica gel) is one of the convenient water removal options Other options use cooling (refrigeration or cryogenic sep- aration) and hygroscopic liquids (di or triethylene glyco Molecular sieves are usually used for gas dehydration ahead of cryogenic plants because they consistently dry gas toless than 0.1 ppmv Natural gas drying. One of the first industry-accepted gas purification applications for molecular sieves was natu- ral gas dehydration ™’ They ean also remove specific con- taminants in addition to water. A valuable specific appli- cation is water removal from natural gas streams containing high percentages of acid gases (HaS and CO») ‘Many existing dehydration plants that used alumina or silica gel to obtain pipeline quality gas have switched to molecular sieves to increase capacity of existing equip- ment, obtain longer adsorbent life, reduce hydrocarbon liquid losses or decrease dew points.”# Molecular sieve properties. Molecular sieves are crys- talline alkali metal alumino silicates with a three-dim: sional interconnecting network of silica and alumina tetra- HYDROCARBON PROCESSING! APRIL 1953. 67Fig. 2. Reaction and equilbrium of COS formation hedra. The resulting structure is a honeycombed array of cavities interconnected by uniform pores ranging from about 3 to 10 A in diameter depending on molecular sieve type.” Pores are formed by driving off water of crystallization thatis present in the hydrated material as synthesized. To be adsorbed, impurities must diffuse through these pore ‘openings tothe internal surface area ofthe cavity. As used in process industries, molecular sieves are commonly sup- plied in the form of Yin. diameter pellets or beads. The large internal surface area of these materials is used with ‘maximum efficiency because of their unique characteris- tics of selectivity based on molecular size and configuration, and polar forces. Compared with other adsorbents, such as silica gel and alumina, molecular sieves offer highor adsorption design loadings, greater resistance to fouling and coking, more ‘complete removal of impurities from the process stream, and uniquely selective adsorption based on molecular size! In commercial operation, these properties result in minimum adso:bent inventory lower pressure drop, elim- {nation of product loss due to coadsorption, longer adsor- bent life and a more réliable and uniform performance. ‘Table 1 summarizes typical desiccant properties However, the life of a particular molecular sieve bed depends largely on the degree of contamination occurring in the system. Even if contamination is avoided, all des- iccants decline in adsorptive capacity with use, because of the cyclic heating, cooling and wetting of the adsorbent, ‘Capacity decay is most conveniently related to the number of regenerations applied to the system. The most dramatic Table 1. Summary of typical desiccant properties’? Property Silica gel Alumina Molecular sjeves (aAto 5A) Surface area, mfg 750-890 210 ‘850-800 Pore volume, emY/g 040-045 021 027 Pore diameter, A aes 26 * Buikdensity kgm? 731 sot=Ba1 68-721 ‘Apparent speci gravity 1.2 18 WW Specificheat,kikg "CS -092 0.24 02 Particle shape Granular_Granular _Cylincical pallets “pes ypnot mols Soccer cas 74 Rind wit cl oping 2 Aina oui Set aeoter. 68 HYDROCARBON PROCESSING APRIL 3959 2 decay rates occur during the first few months of aps tion, after which the system levels off to a steady decline lasting over the rest of the useful life of the sieve. Molecular sieves with high silica content are usually selected for dehydration of sour natural gas because of their tolerance to H,S. The two types of zeolites, A and X, are of particular interest for adsorptive separation.” Type 4, the most common one, has a uniform, effective pore opening of about 0.4 nm (4 A) and adsorbs molecules with critical diameters ofless than O< nm. The crystal stractare of type X results in an effective pore opening in the range £08 to LO nm @ to 10.A. In the presence of H,0, HeS ‘and COs, a sieve ean be selected (type BA) that adsorbs only water, because HyS and CO, cannot enter the pores of the adsorbent. Table 2 presents some basic characteris tics of selected molecular sieves. ‘The selection of a suitable desiccant is primerily an economic exercise. Aluminas are the cheapest but require larger towers for a given water load, which increases capital cost and heat load. Molecular sieves are selected for sour gases, high inlet gas temperature and low outlet dow points. € ‘The drying process. Drying is a batch process. Two (or mare) vessels operate with part of the dehydrators on-line removing water while others are regenerated for use after the beds switch.” As the gas enters a dry desiccant bed, all the adsorbable components are adsorbed at different rates. After the process has proceeded for a very short period of time, a series of adsorption zones will appear. These zones represent the length of tower involved in the adsorption of ‘any component. These zones form and move down through the desiceant bed. Water would be the last zone formed. On all materials except carbon, it will displace the hydrocar- ‘bons if enough time is allowed to do so. ‘The force that holds the individual molecules is strictly physical and, depending on the desiccant, it may be sim- ple surface condensation, capillary condensation, van der ‘Waal’s forces or some other complex physical attraction. For any system of mixed molecules, such as that of natu- ral gas, in contact with desiccant, equilibrium can be estab- Map i ws he come ode molec} 4 adsorbed will be a function of their physical properti ‘These properties include polarity, molecular weight and thé relative eoncentratién of various molecules in the fluid phase outside the desiccant pores.? Ina typical NGL plant, beds of desiccant never actu- ally establish a state of total equilibrium, that is, they never completely fill all the pores with water. This is ‘because the system is operated cyclically, with only a por- tion of the cycle devoted to adsorption, while the remain- der of the cycle time is occupied by regeneration. A total (of 36 hr is needed for a complete eycle—24 hr of adsorption and 12 hr of regeneration. The adsorbent bed is cycled for regeneration before complete adsorption equilibrium is reached. This is why these processes are called dynamic adsorption systems. Gas dehydrator behavior is a good example of the dynamic adsorption process." Tf wet gas continues to flow, the equilibrium zone will extend further into the bed and the active zone will dimin- ish until there is no longer any desiccant that has not adsorbed any water. This point in the adsorption cycle is referred to as breakthrough. However, most commercial adsorbers are operated 50 that the flow is stopped prior toalae a dryer description. [n' 44 plant dryers are located | stripper and deethianizer. ‘They are fed with wet gases coming from the stripper and other columhé. ©" In one plant,® the wet gas contains about 110 Ib of water/MMsef of gas and flows at a nominal rate of 90 to 180 MMsefd, 27 atm and 50°C to 60°C temperature. The moigture content of this gas is reduced to less than‘or equal to 5 ppm before it is fed ‘to the deethanizer.® ‘The three drying beds consist of molecular sieves (Mein. pellets). Each bed is 6 m in diameter, 16m high, and con- tains 75,000 kg of molecular sieve, The beds are supported by structural beams. The molecular sieve is placed on top of ¥-in, alumina balls (approximately 280 ft) and Yin. ceramic balls (approximately 60 ft*), A 20 mesh stainless steel screen is placed on the structural bed supports to 2vent the molecular sieve or ceramic balls from gravi- sating along with the feed gas stream. This gravitation’ ‘is promoted by the cyclic nature of adsorption processes (Pig. 1). Adsorbent internals consist of inlet and outlet distributors and a support for the bed. An inert ballast is installed on top of the bed. Moreover, a layer of support balls on top of the adsorbent bed serves as a fluid buffer and prevents movement of adsorbent on the surface caused by high local velocities. Simple baffle plates are installed for inlet and outlet distributors. They function well over a wide range of fluid velocities and are not subject to plugging or fouling, Baf- fling ensures low pressure drop past the baffle and breaks up the flow into several directions. Because the adsorber beds operate at elevated tem- peratures, they are externally insulated. This includes all systems that are thermally regenerated, because heat losses add to regeneration purge requiréments. The insu- lation covers all hot lines and vessel heads.!2 ‘During normal operation, two of the three beds are on “ing service while the third bed is on regeneration. Bed «generation becomes essential once the bed is saturated with water. The normal cycle time for the adsorption pro- cess (for one bed) is 24 hr, whereas regeneration time is 12 hr. The change of a bed from drying service to regenera- tion and vice versa.is done by.a preset programmer. The programmer operates ona timer that trips microswitches to send an electrical signal to solenoids mounted in the air lines of the air operating valves. The'timer ean be changed. to extend or shorten the regeneration process. ‘During regeneration, the water saturated bed is heated toa temperature of 200°C for a period of 8 hr. The regen- eration gas is a portion of the deethanizer offgas, which is heated in two gas heaters by 41 atm desuperheated ‘steam. The regeneration gas flows ata rate of 40 MMscfa, 2.7 atm back pressure and 220°C temperature. After the heating period, the bed is cooled down to 25°C, by the same gas stream bypassing the two gas heaters. During the cool down of a bed, a minimum flow of the gas is maintained through the heaters.? \ Dryer performance. Actual dryer performance, the amount of water it'ean hold up to the breakthrough and 10K ‘Used commorcialy for general gs eying, ‘ar plant eed purification slmutancous Femoval of HS and CO, an Baul Ihydroearbon and natural gas ewoetening. Fig. 2. Effect of H,S concentration on COS formation. degree of dryness of the product leaving is governed by several operational conditions. These conditions are: 1 Temperature 2. Pressure 3. Water content of the gas 4. Water content of the desiccant 5. Gas velocity 6. Gas composition. ‘Temperature. System temperature has a definite effect on the vapor pressure of the adsorbate in the pores of the desiccant, where the micro liguid-vapor system behaves as if it: were independent of the overall system pressure, However, it has no effect on the adsorbate's vapor pressure in the flowing gas phase, where the system pres- sure and molecular concentration hold partial pressure virtually independent of temperature. So as temperature increases, the partial pressure differential between the pores and the flowing phase decreases, thus reducing the Ariving force for establishing equilibrium. Pressure. System pressure has the opposite effect of temperature. A higher system pressure can produce a higher partial pressure of water in the gas phase, thus the driving force increases and adsorption capacity bene- fits eomewhat.9 The increase in total pressure increases the adsorption capacities ofall species present in the gas. Gas water content. Water molecules, having the strongest affinity toward molecular sieve surface, are adsorbed near the inlet section of the bed by displacing H,S and CO, molecules already adsorbed. The capacity of some molecular sieves is directly related to the water concentration in the gas. However, there is a threshold level above which only a minor effect is apparent. For instance, the capacity of molecular sieves for water changes only slightly above 15% relative saturation of the gas phase, Desiccant water content. Ifregoneration leaves some quantity of water in the desiccant, there is obviously less capacity for the adsorption of additional molecules dur- ing the next adsorption cycle, Also, the rate of adsorption HYDROCARBON PROCESSING /APRIL 1983 69‘Table 3. Composition of dryer feod aff@iregeneration gases® ‘Component jer feed, eration. por Diver fee Regeneration a0, Hs. 873 1030 cb, 368, 3282 oy 1563 2140 @ 3498 ea7e o 26.34 204 1Gync, 199/487 = IGyncy, o7a0.a8 - 0.28 = ‘Molecular weight 5 22 ofthat additional amount will be slower than if the same * amount were adsorbed by completely vacant pores. This produces a longer mass transfer zone in a dynamic cal- umn.? Thus, the overall effect of incomplete regeneration is to reduce system capacity by decreasing the desiccant’s available pore capacity and increasing the length of the ‘mass transfer zone (MTZ). Gas velocity through the bed also influences MTZ length. Since it takes a finite time to transfer all the adsorbate from the gas phase to the pores of the desic- cant, it follows that the zone through which an inere- ment of gas passes during the transfer will be longer at higher velocity. The MTZ length has a significant effect on overall capacity of any bed of desiccant. In general, a longer bed is preferred (provided pressure drop can be tolerated) since MTZ length is a portion of the overall bed height.® Gas composition. In a mixed system, such as natu- ral gas, several MTZs form, in a chromatographic fash- ‘on, down the column, The most preferentially held water will form a zone near the feed end. This will be followed by zone of the second preferentially held molecules, and so on. So, for a given set of conditions, the MTZ length for any molecule ean be greatly influenced by other molecules in the feed system? ‘To achieve continuous operation for the dehydrator beds, the system must be such that a freshly reactivated ‘bed can be switched on-line asa loaded bed nears its break point, As the second eclumn picks up the adsorption oper- ation, the first column goes into the regeneration cycle. Regeneration procedure. Regeneration considerations are often the key to successful and economical application ‘of molecular sieves for natural gas drying” In a typi- cal NGL plant, usually two beds are in adsorption and the third bed is in regeneration for a 12-hr cycle time. A por- tion of the deethanizer offgas is first passed through two heaters and has its temperature raised to an appropriate temperature of the system (220°C), Then itis allowed to flow concurrently through the loaded bed. This provides the media for heat transfer by raising the temperature of the desiccant and the adsorbed water, and it increases the capacity of the gas to hold water. ‘As hot dry gas moves through the bed, the driving force is now switched so that the adsorbate moves from the des- icant to the regeneration gas in a sort of reverse MTZ. After an Shr heating period, the same gas used for strip- ping is allowed to bypass the heaters and act as a cooling, media for the hot bed. Sometimes it is much simpler to pass cooling gas through the bed in the same direction taken during regeneration. Ifa high degree of drying is required, gas flow direction shaula be reversed, from tipflow 70 HYDROGARNON PROCESSING? APRIL. 1685 * during heating to downflow during cooling in order to have any water deposited by the cooling gas at the top of the bed, This wil minimize the amount of water picked up by the product gas during the adsorption period. As soon as the bed is cooled it ean go back to adsorption service.1? ‘The cycle time of the regeneration period consists of: ‘Time (min) Regenerated bed out 5 New bed in for regeneration 5 Depressurizing 30 Heating 480 Cooling 45 Repressurizing to 27atm 40 Stop repressurizing/switeh 5 ‘heater to minimum flow Ropressurize to feed gas wo pressure (30 atm) Total 720 (12 hr) COS formation in commercial dehydrators. Carbonyl sulfide (COS) can occur naturally in natural gas contain- ing high acid gas concentrations (HS + CO,). COS, formed in a variety of thermal and catalytic conversio\ processes in the petroleum and natural gas industries." However, published literature on COS formation provides only limited assistance to study the gas-phase, solid eat- alyzed, reversible reaction: H,S + CO; * COS + H,0 a Elevated tomperature favors both the rate and equi- brium for COS formation.* Most desiceants, however, increase COS formation by removing H,0 and by hetero- sgeneous catalysis. COS has been found to be highly detri- ‘mental in the sweetening process since it forms, with MEA, astable nonregenerable complex, thus increasing operat ing cost.? Moreover, COS is a source of corrosion. Figs. 2 and 3 show the effect of some conditions on COS formation. Various techniques are used to control COS formation, which include molecular sieve, produet and process mod- ifications as well as introduction of auxiliary process sys- tems. Some parameters that can alter and control formation in natural gas drying are: Feed gas Operating Molecular composition conditions _ sieve H,S concentration Temperature Crystal type CO, concentration Pressure Composition H,O concentration Flowrate Binder Hydrocarbon levels Vessel size Manufacture Other contaminants Service exposure Raw materials ‘The physical properties of COS are such that essentially all the COS recovered from sour gas is concentrated in the propane stream. In the presence of trace quantities of water, COS can hydrolyze to form H,S by reversing Eq. 1. COS can also poison ammonia synthesis catalysts being fed with natural gas-derived hydrogen. ‘Sample calculation. Let’s do a sample calculation of COS formation in a typical NGL plant that uses molecu- lar sieves for drying, The natural COS content in the feed ‘gas is 40 ppmv. An experimental study (10 mol% HS, 10 mol% CO,, T = 50°C) states that COS formation is aboutte 605 ppm at the experimental conditions.? ‘The feed gas plant to the NGL dryer contains 110 Ib of water/MMef and gas flows at a nominal rate 0 90 to 180 MMsefd, 27 atm and 50°C to 57°C. The moisture content is reduced to les than or equal to 5 ppm. Dryer feed gas com- psition and regeneration gas is presented in able 3, Trans- lating this to NGL plant conditions and assuming a similar approach to equilibrium and effective HO con- (HO) = ((H,8),(CO,),)(COS), = ((H,S},(CO2)e¢ (COS), @ (COS), = (COS) ((HsS)y(H_8)))(COz)9(CO2))) (3) (cos), (605)((5.73V(10.0)0(8.68)10.0)) =301 ppmy “ Eq. 4 is the GPA standard for total sulfur and will require COS removal during fractionation, which is both, Sfficult and expensive. Trouble can be avoided if the is treated for acid removal before dehydration, ACKNOWLEDGMENT ‘The author acknowledges the support of the Research Institute, King Fahd University of Petroleum and Minerals, Dhahran, and ‘Saudi Arameo, Abgaig, Saudi Arabi, fr conducting this worle Caring WF and Chi CW, "at Gas Prtn Wiha Sever ‘endings ofthe 2th Canon Chom Brag CofC Aber Ta few keystrokes, a Maynard” quarterinch tape drive can store the entire contents of your computer — unattended — on a cartridge that ts inthe palm of your hand, Instead of feeding your PC a pile of diskette, store every. thing — operating system, applications and fles—-on a single 3M brand data cartridge. Whether you need 60 MB up to 1.35 GB capacities, you'll have access to >. our Gata hati $6 mab: ‘Total systems sating rom $198! Maynard’ ‘An ARCHIVE'Company The author ‘Abdullah Bt, Altanl is a chemical engineer in the petroleum and gas technology division ofthe Research Institute of King Fahd University of Petroleum and Minerals. He is a member ofthe Catalyst group, which is engaged in catalyst preparation, evaluation and testing. Mr. Altani " hhas also worked on methanol conversion to ligt ‘ 21 olefins on zeolite catalysts, laboratory reduction (of steam reforming and methanation catalysts, and characterization ‘and evaluation of FCC and reforming catalyets. Previously, he worked for Saudi Aramco at the Abgaia plant operations gngineering unit ‘Me. Aitani holds a BS degree in chemical engineering front King Fahd University of Petroleum and Mineral, and be fs a member of the Catalysis Society, ASTM and AICHE. ‘Rand Seige Husa Sieve Passing inthe Natal Ons {Bh fwd ei Porno Ian ent, oa Parry Hs * Gh dW and Comming WP, “Ader Soper ‘hema eng HOt, a Now den Wy ee rn a aera Cy pr Dan Ce n Seen ere marin Pain sand Geapn Mek. Ba New York, Marcle « Gees HR Hat M dies © Mat Soto oer © Kegehy Band Sand, hy Miler Sven Dabyrat igh id Ga at Pine rt and esearch Nap Be ee lpi of hein Prec Proven reliability andthe affordable cost of Maynard’ MaynStrear Archive and Irwin branded systems and 3M brand data cartridges are why more and more businesses are buying them. But you've got an even beter reason, Your data CallJ-800-888-1880 ext. 36 for you fee QuartorInch Solution Guide” and “Disaster Avoidance Planning Guide’ Circle 94 HYDROCARBON PROCESSING APRIL 900 73