NATURAL GAS CONDITIONING THROUGH ADSORPTION TECHNOLOGY by J. M. Campbell W. P. Cummings Copyright 1964 by W. R. GRACE & CO., DAVISON CHEMICAL DIVISION No part of this manual may be reproduced in any manner whatsoever without written permission from W. R. Grace & Co., Davison Chemical DivisionPREFACE Devison has been menufacturing and selling synthetic silica gels to varied industries and governmental agencies for numerous applications since the 1920's, Some of these applications have been discovered by Davison, others have been developed by customers after consideration of the ‘unique properties of gel as applied to their products and processes. Sales to most of the major users have been supported by detailed Technical Service for the specific need. When the dehydration and hydrocarbon recovery ability of silica gel was found to be applicable to natural gas in the 1950's, technical support to sales was initiated. But, compilation of industrial and academic information on the use of gel in the gas industry could not be obtained by standard methods. Chemical Engincering texts, rules of thumb from operating people, and scientific society publications did not satisfy our requirements for leaming the relationship between the basic adsorption fundementals and applied gas conditioning unit design methods. The implication is not that design engineers used non-universal methods but, a faster (basic) approach was mandatory for quality service on the product. Davison initiated an academic program sponsored at the University of Oklahoma Research Institute to investigate the mechanism of adsorption-desorption in the recovery of Liquid hydrocarbons from natural gas. A study of dehydration of air and gas wos undertaken at the Washington Research Center of W. R. Grace & Co, From these two research efforts has come the information used by Dr. J. M. Campbell and W. P. Cummings in preparing this booklet. ‘The information was not obtained without solving major research equipment problems that deterred previous investigators. The equipment as finally developed is the result of many tedious attempts to prove the reliability of mathematical models for predicted systems behavior. Now pilot scale testing equipment is available which will produce quality data for ges conditioning investigation based on mathematical models which represent @ reasonable, if not rigorous, picture of the adsorption mechanism involved. Notural Gos Condit the detail of equation derivation has been omitted for the sake of brevity, but not so much as to ning Through Adsorption Technology is for engineering people. Much of prohibit follow through by the academically inquisitive. The sections on silica gel (I and Il) are presented to point out the reasons why this chemical is especially suited for gas conditioning. The section on the selection and design of units (III) was included to put the measurable dependent and independent variables into focus. The operations section (IV) points up factors which, both as a result an objective analysis of of field knowledge and applied fundamental technology, must be consideres the efficiency of the working unit. Design Criteria (Sections V & VI) are presented last to emphasize the conclusions which have been drawn from our research. By following the procedure for the design of either @ dehydrator or reliable operation can be anticipated. For the readers’ convenience, appendices a recovery unit, covering vital phases of the design concept are provided.Research on adsorptiondesorption is now a continuing phase of the Davison Chemical Division, W. R. Grace & Co, research effort. It is the Company’s hope that through this presentation, usable contribution has been made to the total knowledge of gas condition 1g through adsorption. A.W, HemphillINTRODUCTION ‘The information contained in this booklet is based on reliable data gathered from both field and pilot plant adsorbers operating chiefly on raw naturel gas. The authors believe that in such an atmosphere silica gel will behave as predicted; however, because of the semi-empirical nature of the basis for the design criteria, the reader is cautioned against applying this information directly to gas streams having different characteristics. For example, in clean, non-hydrocarbon gases, silica gel normally exhibits higher capacity and longer life.Section T Section 11 Section It Section IV Section V Section VI Nomenclature Bibliograpny Appendix A Appendix B ‘Appendix C TABLE OF CONTENTS Introduction to Silica Gel . . A. Chemical Properties B. Physical Properties CL Mechanical Stability Performance Characteristics of Silica Gel... « A. Dehydration « B. Hydrocarbon Recovery : 1, Equilibrium Behavior - . 2. Dynamic Performance « ‘a, Adsorption b. Regeneration . .« . ‘Teble II-I Summary of Common Regeneration Systems «+. Factors Influencing the Selection and Design of Adsorption Units .... +++ ++++ 11 ‘A. Gas Composition... .0sseeeeeeeeeeeseereeee uw B. Flow Rates. .scccccceceeeeeateeas ences MW Cl Pressure. ss sss iesteesseeseeereeeeeae ee en en 12 D. Temperature... eee seater E. Utilities Available and Locel Conditions Fa sea | Function of Unit. sere sere ree esse BB G. Time Factors. 2-0... e ree 8 H. Supervision and Maintenance B Things to Avoid Specifying - : 4 Review of Quotations . . . 1 14 K. Summary... eee : 14 Siete sate ee: Operations, Control and Troubleshooting with Adsorption Units . . A. Operational Records . B. Plant Tests . - CC. Good Operational Techniques D. Controls - E. Troubieshooting . Design Criteria for Natural Gas Dehvdrators ‘A, Sizing the Desiccant Bed . - B. Special Configurations... 1. Multiple Beds « 2. Radial Flow Dehydrators . « 3. Horizontal Beds . . 4. Guard Driers . . - 5. Partial Bypass... ©. Minimum Bed Depth... ++ D. Reactivation Requirements . Design Criteria for Hydrocarbon Recovery Units . « « A. Basie Design Considerations . B. Establishment of Cycle Time . - C. Special Considerations . . D. Regeneration and Cooling . - - E. Calculation of Recovery. + + FL Summary - 7 Table Viel Smoothed and Adjusted K Values « Table Vi22 Smosthed and Adjusted K Values for Mean Boiling Point Factors. 32 Table VI~3 Convenient Conversion Factors for Adsorption Design « - 35 : a 37 Suggested Gas, Oil and Condensate Sampling Procedures . « «+ + Ad Sample Specification Summary Sheet for Adsorption Plants . . .- «+ we BD C2 Development of @ Correlation Procedure... «FIGURES 24 2.2 2.3 24 25 26 27 2.8 2.9 2.10 241 2.12 2.33 2.14 2.35 2.16 248 LIST OF FIGURES Equilibrium Adsorption of Water by Silica Gel Maximum Velocity for Natural Gas Upflow Through Davison Grade 03 Silica Gel Equilibrium Capacity of Pure Geses as a Function of Pressure Effect of Percentage Adsorbate in Methane Binary on Equilibrium Capacity Effect of Other Components on Equilibrium Adsorption Pressure Correction Factor for Use With Figure 2.4 ‘Temperature Correction Factor for Use With Figure 2.4 Variation of Adsorption Zone Front With Time Character of Breakthrough Curve Schematic View of Bed Saturation at Pentane Breakthrough Eifect of Particle Size on Shape of Breskthrough Curve Example of Displacement of Hydrocarbons by Heavier Components Gas Temperature at Various Points in Tower vs. Time Example of How Zone Length is Independent of Tower Length Once the Zone has’ Stabilized Schematic View of a Typical Three Tower Plant Usiag Cooling and Regeneration in That Order Schematic View Showing Heating and Cooling on Regeneration in That Order Schematic View Showing Effluent Gas Cooling Schematic View of Closed Cycle Regeneration Using Effluent Gas CoolingFIGURES 5a 5.2(@) ®) 53 54 5.5 56 87 5.8 6.1 6.1 (a) 62 63 6.4 6.5 6.6 67 6.8 6.9 6.10 611 6.12 6.13 6.14 6.15 (0) &) (©) 6.16 6.17 LIST OF FIGURES Water Content of Natural Gases With Corrections for Salinity and Gravity Water Vapor Content of Natural Gas at Saturation Water Content of Carbon Dioxide Water Content of HS Silica Gel Capacity as @ Function of Natural Gas Water Content Correction Factor to be Used With Figure 5.5 Silica Gel Capacity os a Function of Time in Service in Natural Gas Pressure Drop Through Davison on 8 Mesh Silica Gel Dynamic Equilibrium Saturation of Normal Paraffin Dynamic Equilibrium Capacity of Silica Gel ‘Comparison of Dynamic and Static Equilibrium for Binery Mixtures Saturation of Hexene at Breakthrough Saturation of Pentane ot Breakthrough Residual Saturation of Component on Bed When Heaviest Component has Reached Dynamic Equilibrium Breakthrough Time for Pentane as Function of Inlet Analysis ‘Adsorption Zone Length as a Function of Mass Velocity and Bed Length faction of Tower Occupied by Pentane Adsorption Zone Containing Primarily Butane Stabilized Adsorption Zone Front Velocities ‘Typical Regeneration Behavior of Lean Gas Containing Butane, Pentane and Hexane ‘Typical Regeneration Behavior of Lean Gas Containing Pentane, Hexane and Heptane Percent Pentane in Regeneration Gas as a Function of Temperature Outlet Bed Temperature as @ Function of Time Heat Available From Regeneration Gas as 2 Function of Pressure and Gas Specific Gravity Equilibrium Constants Mean Average Boiling Points of Liquids as Function of Mol. Wt. and Gravity ‘A Means of Estimating Optimum Second Stage Pressure in Three Stage SeparationSECTION 1 INTRODUCTION TO SILICA SEL. The heart of any solid bed dehydrator or recovery aystem is the adcorbent. Yet few design engineers have a thorough knowledge of the matedials commonly used for this purpose. Davison silica gel excellent as both a desiccant and hydrocarbon adsorbent. More efficient utilization of the properties of silica gel can result in more efficient adsorber design and longe- desiccant life. A Chemical Propertios Davison silica gel is en extremely pute form of silicon dioxide (99.7 + %Si02). Tt is manufactured under carefully controlled conditions from sulfuric acid and sodium silicate, The fact that silica gel is the result of controlled reaction between other manufactured chemicals frees it from any deviation which might be introduced by naturally occursing raw materials. Silica (silicon dioxide) is an extremely inert material. Only strong alkalies or hydrofluoric ecid react with it to any appreciable extent, It is insoluble in !i common solvents. ‘The purity of Davison silica gel contributes to long life in hydrocarbon systems. Thi it exhibits minimal catalytic activity, contrary to the behavior of silica-alumina combinations with similarly large surface areas. A typical analysis of Davison silica gel is as follows: Chemical Analysis Typical Anolysis (dry besis) s because Silica as $i02 Iron as Fe20s ‘Aluminum as, A203 ‘Titanium as TiO Calcium as C20 Sodium as Naz0 Zirconium as ZOs Trace Elements Physical Properties 1. Size and Shape ~ In applications where adsorbents ate used under static equilibrium conditions, the size and shepe of particles is unimportant. However, in dynamic operations, the kinetics of mass transfer and considerations of pressure drop exert much more influence. As a rule, the kinetics of a system require small purticie size for supid transfer of adsorbate to the adsorbent, Optimization of this factor ceanot always be tolerated because of the increased pressure drop resulting from small particles. In any system, the pressure drop requirements must be balanced against the edsorption efficiency of a given size Of particles. The shape of the particles also influences mess teansfer because of variations in extemal particle surface per quentity of adsorbent. Taus, the irregular granular shape of Davison Silica gel improves kinetics even when a large average particle size is utilized to minimize pressure drop. Density — The particle density of an adsorbent is largely dependent on the volume of pores Within the structure, As less pore volume is built into an adsorbent, the density will increase. Although it would be desirable to make adsorbents very dense; so as to occupy a minimum space, a reasonable compromise must be made in order to leave enough pore volume to hold a Practical quantity of adsorbate. As pore volume is increased, it becomes easier for adsorbates fodiffuse within particle; but al the seme time, the skeleton of the particle becomes more delicate, co durability may suffer. Over the years, the density of Davison granular gels has been undergoing cubtle change until optimum graces for Gifferent applications have beer developed. Strength — The physical strength of an adsorbent is partially a function of the intemal pore structure, As the structure of Davison silica gel hos bees improved, one criterion hs always teen particle strength. In addition to the strength impacted by the basic structure of the gel, all Davison graded geis are ‘pre-atteited” prior to packaging to knock off aay cracked comers which could produce dust, or fines, in normal use 4, Silica Structure ~ The fact that silice ge! ie an omotphous rather than a crystalline form of Silica is also very importent. Such a form will not contribute to possible physiological effects Certain grades are actually used as anti-ceking material in food and feed products in compliance with FDA end USDA regulations. ‘As can be deduced, the structure and resulting prope: during manufacture. Experience in such process men. jes of silica gel can be manipulated polation has resulted in a silica gel 1c superior for naturel gas service, These properties end performance characteristics are summarized in the table below: Physical Properties Moisture Adsorption Equilibrium Adsorption (77°F } 10% Relative Humidity TAB 20% Relative Humidity 12.25 40% Relative Humidity 24.85, 60% Relative Humidity 34.60 80% Relative Humidity 37.80 Total Volatile at 1750° F. 5.0 to 6.5% Pore Diameter (Average) 22 Angstroms Surface Area 832 Square Meters/Gram Specific Heat 0.22 BTU/Ib./"F. Apparent Density (bulk density) 45 Ibs./cu. ft Density of Individual Particle 75 Ibs. /eu. ft. ‘True Density of Silica (no porosity) 137 Ibs./cu.ft. ‘Thermal Conductivity 1 BTU/sq. ft./he./F-/i Reactivation Temperature Range _250-600°F. (350°F. bed temperature is adequate for most uses) Mechanical Stability In the consideration of adsorber design and adsorbent choice, certain properties which can be classified under the heading of mechanical stability must be considered, 1, Particle Strength ~ One critical factor is the ability of the adsorbent to withstand crushing under its own weight. In addition to the adsorbent weight the gas flowing in « down-flow tower exerts a significant pressure, measured as pressure drop. For example, consider a bed of Grade 03 Silica Gel ten feet high through which gas is flowing at 30 ft./min. under a pressure of 800 psi. The density of the silica gel is 45 Ibs. per cubic foot so the maximum Pressure on the bottom layer of particles contributed by the desiccant weight is: we tee 14 in? The calculated pressure drop is 2.02 psi. So, the maximum pressure on the particles will be S15 psi. It is impossible to measure the crushing strength of individual silica gel particles because of their irregular shape. Experience has shown, that dehy have operated in natural gas service under a variety of conditions particle crushing. The absolute safe limit cannot be stated, but towers higher than this usually have intermediate supports. 2. Thermal Shock ~ All components of a gas dehydrator, including the desiccant, are subject to sudden thermal shocks when the regeneration and cooling gases enter the system. Davison silica gel will withstand such sudden temperature changes repeatedly and show no degradation, Temperatures above GOOF. may injure the gel regardiess of how gradually they are applied. This should, therefore, be the upper limit of regeneration gas temperatures. 3. Gas Velocity ~ Silica gel is not affected by gas velocities normally encountered in dehydrators. There are, however, limitations to good design practice which are based on preventing actual movement of the particles of desiccant. 4. Pressure Change ~ It is not uncommon for an adsorbent bed to be depressured several times: during its service life. The sudden release of pressure from a particle of silica gel containing adsorbed water of hydrocarbons may result in cracking of the particle because of the very high pressure differential between the pores and the external atmosphere. Controle should limit the rate of depressuring so as not to exceed 30-50 psi. per minute. The same caution should be observed in pressuring a desiccant bed, although the rate can be faster ~ 50-70 psi, per minute. Another danger in rapid pressure release is the possibility that the escaping gas bubble will actually lift, or “hump” the bed. This type of bed movement can also occur downstream from reciprocating compressors, although there is usually enough damping ection in the system to avoid damage. 5. Filling a Tower ~ Silica gel can withstand the physical drop to the bottom as a tower is filled. However, silica gel, like all desiccants, contains patticles with a narrow, but definite, size range and a free fall onto the natural cone which will form may result in some size segregation. This can lead to channeling of gas and unequal utilization of desiccant. Therefore, it is suggested that @ sock or chute of some sort be used to distribute the falling desiccant around over the area of the tower, 3.13 peiSECTION I PERFORMANCE CHARACTERISTICS OF SILICA GEL ‘The behavior of silica gel, in adsorbing # componeat or components from a gas stream, is dependent upon specific physical factors. A general knowledge of this relationship will assist ia optimum utilization of the adsorbent. A. Dehydration When silica gel is used primarily for water adsorption gas composition, pressure, temperature, and particle size are influential in its performance, 1. In considering gas composition the water content is ctitical, since it will influence both the amount of water which will be adsorbed by the gel and the rate at which it will be adsorbed. ‘The maximum amount of water which can be adsorbed is defined by a measurable equilibrium relationship, between the water in the gas phase and the water adsorbed in the gel. This felationship at atmospheric pressure is graphically illustrated in Figure (2.1). The directional effect of inlet gas water content on the maximum useful capacity of the gel is shown by the following: ‘Assume two gas streams, each at the same temperature, 80°F., and the same pressure. Stream “A” has a water vapor partial pressure of .20 in Hg, 30 the maximum water content of gel in equilibrium would be 11.5% | from Figure @.1)._) If stream “'B” contains more water, say a partial prossuro of .40 in Hig, the maximum water content of gel in equilibrium would be 21% [from Figure (2.1). ‘This relationship defines the maximum water which will be adsorbed by silica gel in the feed ‘end of @ dehydrator when exposed to gas at @ given temperature and water content. The rate at which the water is adsorbed will influence the time required for contact between the desiccant and the gas fora piven degree of dehydration. The unsteady state conditions present in a desiccant bed under dynamic adsorption operation makes accurate determination Of the water transfer rate beyond the scope of this presentation. However, a qualitative tnderstanding of this effect will assist in dehydrator design. Hougen and Dodge (I.) express the rate at which silica gel will adsorb water vapor from 0 gas in front flow as: Ges ac" dp wher ater content of silica gel G= mass velocity of the gas based on specified area of bed {p= difference between the vapor pressure of water in the gas and in the gel From this expression it can be seen that the rate of adsorption is a direct function of the vapor pressure differential, so higher vapor pressures of water in the gos will increase the initial rate of adsorption, As the mace transfer zone (section of the bed where water is being ttansferted from the gus to the desiccant) develops the effect of inlet water content of the gas is masked by other factors. Fo: practical parposes it cen be assumed that the length of this transfer zone, or the contact time for a gas to teach @ given dryness, will increase with inlet water content. ‘This will not be a straight-line function of water content, however. 2. Hydrocarbon compounds in the gos stream siso influence desiccant performance. However, onty butanes and heavier are of practical consideration. Silica gel will preferentially adsorb ‘Water so that theoretically hydrocarbons will not be strongly adsorbed until they pass beyond the zone of water adsorption. This distinction is not 100% efficieat, however, and some hydrocarbons are actually adsorbed within the water adsorption zone. AS more water enters the zone it will displace most of these adsorbed hydrocarbons and they will move down the bed to be edsotbed again. This hydrocarbon displacement slows down the rate of water adsorption snd increases the Tength of the weter adsorption zone. Some hydrocarbons, because St ther molecular size or type. will be more strongly held by the silica gel and will not be completely displaced “The foregoing refers to hydrocarbons which enter the dehydrator in the ges phase. There moy be additional compounds such as lube oil, adsorber oil, glycol, etc. which enter a8 entrained Tiguide. ‘These are rolotively large molecslar weight, high boiling compounds which will adsorb near the inict end of the bed and will not be completely displaced during subsequent Water adsorption. Light materiais which may sffect water capacity on individual cycles are usually completely removed during normal regeneration, along with the water, The heavy oils, on the other hand, tre clable at regeneration temperatures of else decompose and produce tars which are very Stable. Such material eventually “cokes” in the silica gel and teduces capacity for water by blocking or filing pores. Minimizing the effect of such hydrocerbens 1s covered in Section VI.Natural gas contaminauts such as H2$ and CO> have adsorption characteristics similar to the butanes. During water adsorption much of the HaS or CO2 previously adsorbed will be displaced, but Some are concentrated in the adsorbed water or hydrocarbons, In this phase they have @ minimum effect on desiccant capacity, but their presence in the regeneration pas stream should be recognized so possible corrosion can be anticipated. Alcohol, which is sometimes injected for temporary dew point control, behaves very much like water in the silica pel and is easily removed on regeneration, It has no lasting effect, although it very definitely competes with the water vapor for the adsorption capacity. When it is present it should be included along with the water for estimating required capacity. Amines have a serious effect on the capacity and life of silica gel. They are readily adsorbed, and during regeneration are decomposed. The ammonia resulting from the decomposition attacks the intemal structure of the gel particles. As the intemal structure deteriorates, the pores become larger, and the surface area is reduced. This attack, if carried to extremes, will reduce adsorption capacity. Gel that has been severely attacked cannot be reconditioned. Other strongly alkaline materials, such as mist from caustic scrubbers will attack silica get in a similar fashion, Oxygen is enother, less common, component which should be recognized, In sweet gas it hastens the buildup of carbon, of coke, within the gel and thus shortens desiccant life. Ia sour gas it reacts with the hydrogen sulfide and produces free sulfur, which not only piugs the pores of the gel, but also the voids between gel particles. ‘The operating temperature of a silica gel bed, within the range usually encountered in natural gas processing, has little effect on the performance of the unit. In general, lower temperatures result in greater capecity although the increase in equilibrium capacity at aay level of relative saturation is increased only about 5% over the temperature range 120°, to 70°F. Above 120°F., capacity decreases rapidly, and the use of silica gel is usually not recommended without auxiliary cooling. ‘The total pressure of a system has virtually no effect on silica gel capacity for water, providing it is above 100 psi. Below this pressure most gases do not have sufficient heat Capacity to dissipate the heat of adsorption. The heat of adsorption is the sum of the heat of condensation for the water and the heat of wetting of the silica surface (about 325 BTU per 1b, of water). Consequently, if this heat is not removed by the gas, or by other means, the bed ‘temperature may, under certain conditions, rise as much as 200°F., resulting in a definite decrease in capacity. Velocity ~ In the design and operation of gas dehydrators velocity must be considered, during both drying, and regeneration. ‘The length of a mass transfer zone varies with gas velocity, because contact time is a direct function of this factor. However, the length of zone to velocity relationship is modified by i 4 higher ve Thus, the mass transfer zone length is not directly proportional to velocity. This assumes, of course, that the minimum velocity is high enough to be above the laminar range flow, but below a level which might cause bed movement. During regeneration the flow rate is usually much less than during dehydration, so velocity maximums are not a problem. However, the other extreme must be considered, At very low velocity the effects of channelling or wall effects may cause very poor gas distribution and spotty activation of the bed. Care in distributing desiccant around the tower daring filling, use of beffle plates or layers of inert balls to assist distribution, and reasonable height to diameter configurations all minimize this problem, Ledoux (2) has studied the effect of velocity as related to physical movement of desiccant patticles and suggests the following limiting upward velocity: st 0.0167 2a A, Po Dog, where: G! = mass velocity of gas, 1b./(see.)\sq. ft.) Pog = gos density (actual), 1b./cu. /ft Po = desiccant bulk density, 1b./eu. ft. Dy = average desiccant particle diameter, ft. 2 & =acceleration due to gravity, ft./sec. ‘This equation is based on upward flow of gas. For silica gel a velocity approximately twice as great may be used down flow. In down flow operations care must be taken to provide good distribution over the face of the bed to prevent “jetting” in localized areas of high gas velocity. Figure 2.2 is a graphical presentation of this equation 2.1. Further details of the effect of the above variables may be found in Reference 3.Hydrocarbon Recovery Silica gel bus some capacity for most hydrocarbons found in natural gus. Since the predominance of pores have a diameter about 20-25 A, they eun accommodate all hydrocarbons normally available. The selectivity for normal paraffin hydrocarbons is proportional to their molecular weight, hexane displacing pentane, pentane displacing butane, etc. It shows a preference for olefinic and Unsaturated hydrocarbons over the paraffins. Silica gel also shows some affinity for HeS and COz fas mentioned in Section II, A, 3, Because of its chemical properties, structural strength, ease of reactivation and favorable density, Sillea gel is an ideal material for hydrocarbon recovery. Under current operating practices ultimate recovery is limited to the pentanes and heavier hydrocarbons. Use of longer towers and/or shorter cycles would extend the effective use of this latent capacity. As a basic principle it may be stated that silica gel has an equilibrium capacity for all types of molecules normally in hydrocarbon gases. This capacity is a function of pressure, temperature, Composition and relative volatility of the component. 1. Equilibrium Behavior of Silica Gel — Data on the equilibrium behavior of natural gas components with silica gel ace very limited in the range of pressures and temperatures used commercially. (W. R. Grace Is currently sponsoring research in this area). ‘The equilibrium capscity represents the maximum amount of a component that may be adsorbed regardless of the time of exposure. This represents the theoretical upper limit of the dynamic ‘Commercial process. The degree of approach to equilibrium is a function of contact time between gas and desiccant, As contact time increases, a closer approach to equilibrium is achieved. Equilibrium data serve several useful purposes. They may be used to determine if a given adsorption process is feasible, They serve as en upper boundary in the standard form of the mass transfer equation, and are essential if one desires to use mess transfer constants for design of dynamic systems. ‘The equilibrium data presented in this section represent a compilation of all available information. The curves presented are in some cases based on few points but yield a pattem of behavior that is reasonable. ‘The bulk of the equilibrium data shown are based on the work of Mason and Cooke (4) who have performed one of the most exhaustive studies to date, These data apply to Davison silice gel only. The authors have suggested a means of predicting the isotherms of gas mixtures utilizing the BET theary of adsorption (5., 6.) fugacity, and the assumption of two layer adsorption. Based on present data this is the recommended procedure for celculating isotherms at pressures to 1500 psia, Figure 2.3 shows the isotherms of many common pate paraffin hydrocerbons at LO0°F. No date ate shown for pi ‘above the dew point for they apply only to the gas phase. It is, apparent from this figure that silica gel has a substantial capecity for hydrocarbons. The curves also show a substantial reduction of capacity in the low pressure region, Figures 2.4 to 2.7 have been prepared from equilibrium data available for natural gas mixtures. ‘They are not suggested for use as a correlation since they are based on too few data points. They do, however, show the effect of pressure, temperature, and composition on the equilibrium behavior of hydrocarbon systems. Figure 2.4 (4) shows the effect of composition on the equilibrium capacity of silica gel for butane, pentane, and hexane at 100°F. and 1000 psia. These curves are based on binary mixtures of methane end the hydrocarbon in question. As one would expect the curves tend to tion increases. flatten out as concent Figure 2.5 shows how the presence of other components in the butanes plus range affects each adgorbate. This figure is to be used with 2.4 to estimate how @ multi-component mixture would behave in comparison to the corresponding binary system containing only the component ia question. Once again the result is es expected when other adsorbed materials occupy some Adsorption sites. ‘The figure uses only the butanes plus as a parameter even though substantiel Quantities of lighter ends can be adsorbed. At 100°F. and 1000 psia., for example, silica gel May adsorb about 4.8 Ibs. methane per 100 Ibs. gel. At 2000 psia. this increases to about 6.2 Ibs. per 100 tbs. gel Figure 2.6 is a pressure correction factor for Figure 2.4. The exact shape of the curve is a fanetion of composition but in the range of hydrocarbon gases normally processed those curves shown are typical. The shape of these curves is somewhat analogous to those obtained from flash vaporization calculations, Optimum separation is obtained from 400-800 psia. At pressures, above 1000-1200 psia. more very light ends condense, At 2000 psia. a substantial portion of the adsorption sites ere occupied by methane and ethane just as a liquid at this pressure will have an abnormally high amount of these components. Figure 2.7 is also @ correction chart for use with Figure 2.4. It shows the relative effect of temperature on equilibrium capacity. An increase in temperature from 100-120°F. reduces capacity about 1% per °F. This is tangible evidence of the advisability of effective coolingAlthough equilibrium data cannot be used to predict the dynamic performance of units, they ‘are useful for estimating the relative effect of the above variables. Once dynamic data are available at a given condition, equilibrium data are useful for extrapolating and/or interpolating it to new conditions. If an approximate anewer suffices, Figures 24 to 2.7 may be used for this purpose. The equation would b C=CixCex Cex Ca where: C= equilibrium capacity at given pressure and temperature Cx = capacity for given mol. % of component in gas assuming that methane was the only other component as found from Figure 2.4 ‘orrection factor found from Figure 2.5 to correct for presence of butenes plus components in actual gas -orrection factor for changing pressuse from 1000 psie. to actual pressure (Figure 206) rection factor for changing temperature from 100°F. to actual system temperature (Figure 2-7) Where more precise estimations are needed the method of Mason and Caoke (4) is suggested. Dynamic Performance of Silica Gel ~ The performance of a silica gel adsorption plant is dependent on bed depth, flow rate, particle size, pressure, temperature, method Of regeneration, cooling medium, condensation efficiency and basic mechanical design. Variations in eny one of these will effect performance. Ih some ways an adsozbent plant for hydrocarbon recovery is analogous to adsorption and refrigeration type plants. Each uses the PVT behavior of hydrocarbons to achieve recovery. Adsorption utilizes basic equilibrium relationship and concentration differences to achieve mass transfer from the gas to liquid phase. Refrigeration takes advantage of equilibrium constants decreasing with temperature Adsorption recovery is really a two step process. In the first step, the desired components are Concentrated on the solid surface. In the second these components are moved from the silica gel to @ condenser. Unless the concentration of recoverable components in the regeneration gas is substantially more than that ia the initial gas, the adsorption step is wasted. It is for this reason that regeneration is sometimes spoken of as the key to an effective plant. Since there is a practical limit to how far equilibrium can be shifted by concentration or temperature changes, it is not too surprising that each type of process has ite inherent range of optimum operation. Based on present economics and operating practices most applications for silica gel adsorption are in streams with entering pentanes plus composition between 0.1.0.5 gal. per 1000 std. cu. ft. Since silice gel is also a superior desiccant, there are many factors that could make hydrocarbon adsorption d - me If dehydration is the primary goal, hydrocarbon recovery is virtually free of extra cost. Extremely lean gases can thus he processed economically. In many cases the recovery of saleable hydrocarbons will more than compensate for the greater cost of adsorption units Compared to glycol dehydrators. Rich streams also can be effectively processed by adsorption. The economics are particularly favorable, compared with refrigeration, when flow rates aie ow. Because of this flexibility over 350 units ste located on individual wells, Held gathering and transmission systems. kis convenient for purposes of this discussion to divide the adsorption process into two parts ~ adsorption and regeneration, ®. Adsorption ~ The general mechanism of adsorption is analogous to jon exchange and miscible displacement of fluids, in terms of the variation of effluent concentration with time, Several mechanisms are occurring simultaneously ~ diffusion and dispersion through the gas phase, condensation on the surface and imbibition (intemal diffusion) of the liguid from the outer surfaces of the particle into the interstices, The fect that these occur simultaneously makes it difficult to pinpoint the exact role of any one mechanism or to quantitatively describe the process in academic detail, It appears that gaseous ditfusion and dispersion within the particle play # minor role and may be ignored. ‘The effects of surface liquid "film" and internal diffusion on the rate of adsorption is of interest. The predominance of either can influence optimum flow rates, bed geometry and Particle size for a dynamic system. At the present time, however, not enough is known about their teletive influences to make much difference. Commonly used techaiques which assume @ “film” resistance to calculate mass transfer tates do so more out of convenience then as a matter of fact. : In spite of the exact mechanism, a given adsorbate will continue to collect on an active surface as long as free surface is available and there is a positive concentration driving force from gas to liquid. Adsorption can continue to occur after all available surface ‘sites”” are covered. A concentration driving force exists even though the surlace forces have been satisfied, c cs c‘The bed concentration of a given adsorbate follows the sequential pattem shown ia figure 2.8. The lending edge of an adsorption zone moves into a portion of the bed that contains none of that particular adsorbate (except what may have heen left from the previous regeneration or cooling cycle). The degsee of saturation atthe inlet increases Inti! the frst layer of gel is saturated. Once this has oveucred a so-called adsosption ot tmass transfer zone has been formed. This zone grows in length but rapidly stabllizes tnd moves through the tower with no further effective change in length. AS the leading edge of this front reaches the exit of the bed, “break-through” of the particular ‘adsorbate occurs and the concentration in the exit gas rapidly approaches that of the inlet, This breakcthrough curve hes the characteristic "shape shown in Figure 2.9. ‘The ordinate in this figure is the concentration of the particular adsorbate divided by its concentration in the entering gas. When C/Co reaches 1.0 no farther net adsorption is occutring. Ae'e motter of practicability, the brealthrough time (Op) has been taken at C/Co = 0.08. Likewise the equilibrium time (Og) has been taken at €/Co = 0.95. In the vicinity of C/Go equal one and zero, the precision of the data together with rapid curve Inflection gives poor reprodacibiity Figures 2.8 and 2.9 are comparable since time and distance are related variables. A typical breakthrough curve can be obtained even though the zone has not completely formed and stabilized, Ifthe bed is too short, it is apparent from 2.8 thet breakthrough wll occur before the zone forns and even then desiccant atthe inlet will not be Enturated. A loss in capacity results Curve 3 (Figure 2.8) illustrates the transitional phase when the inlet to the bed is Saturated but the zone has not as yet stabilized in length. In Curve 5 the length has Stabilized for all practical purposes and the zone is moving down the tower at tubctantially constant velocity v, If the rate of adsorption were instantaneous, Curve 1 in Figure 2.9 would represent the breakout curve on the effluent ges, For # given gas analysis the shape of the actual curve depends on particle size and flow rate, Curve 3 represents different conditions than Carve 2. If the adsorbent surfaces is already paitially saturated with « component ‘which is being displaced, zone length increases, ‘This means, for example, that hexane in'a methane-hexane system would have @ sharper zone front that it would exhibit in @ taulticcomponent mixture. Figute 2.10 is a schematic view of the bed saturation at pentane bresithrough. Tt illustrates the successive displacement of one component by another. At the tine corresponding to the condition shown, substantially all of the pentenes plus entering the tower have been adsorbed on the gel.If the cycle is stopped at this polat, final stock tank recovery is dependent solely upon tegeneration and condensation efficiency. Figure 2.11 illustrates the effect of particle size on the shape of the breakthrough carve at commercial flow retes, Steeper curves coincide with chorter zone lengths, at break through. Finer gel is clearly superior in its performance, if all other factors remain the Figure 2.12 shows the type of breakthrough curves obtained for multi-component nnixtures, The atea above the curve between C/Co = 0 and C/Co= 1.0( {1-C/Co) d @ ) fepresents the amoust of component adsorbed when multiplied by the rate of mass Input ‘The area under the curve above C/Co = 1.0 represents the felalive amount of material displaced by another. The difference betvieen these two aceas, times the input rate, represents the net amount adsorbed at any tine 0. For exanple, at pentane breakthrongh tine, all of the pentanes plus have been adsorbed. At that time none of the intanes have fs yet been displaced. Therefore the area above the butane curve at the Op for petene times the butone input rate equals the amount of butane on the bed. Knowitg the bed ‘weight, concentiations of each component are found. Adsorption is not an isothermal process. Temperature rises of the order of 20°F. have teen observed long the adsorption zone front. Figure 2.13 shows a plot of gas temperature at various points in a tower versus the squere soot of time A rise of almost 18°F. is shown even though the inlet temperature wes dropping slightly. However, the concentration of pentane 18 unusually high. At more common concentrations arise of not tore than @10°F" is normal. ‘There ate several implications that no one isotherm can fepreseat equilibrium adsorption behavior, and the assumption of isothermal adsorption Isat least technically in error Itis likely that non-isothermal behavior causes a discontinuity in the breakthrough Carve, i.e, there are actually two fronts, a major one followed by a lesser one, as the Bed coois behind the main front and regains some capacity Figure 2.14 shows that bed length has no effect on zone length once said zone has Stabilized. Thevefore © bed length, as a parameter, ie valid only when the Tength is not adequate for zone stabilization. Regeneration — The purpose of regeneration is to remove and recover the adsorbate, and prepare the adsorbeat for another cycle. Available data show that desorption sndadsorption equilibrie sre affected in exactly the same way, no observable hysteresis occurring. This means that the maximum emount of desorption is also represented by Figures 2.4 to 2.7. These figures show that maximum equilibrium removal would involve both low pressure and high temperature. The rote of removal would be governed by these factors plus the concentration driving force from solid to gas. Large concentration differences increase the rate. The presence in the gas of a material immiscible with hydrocarbons, such as water vapor, also accelerates. the rate, A substantial nunber of new commercial plants for hydrocarbon adsorption use the system shown in Figure 2.15. It consists of three down flow towers, one on stream, one heating and one cooling. It is known as an open cycle plant since portion of the process stream is used for heating and cooling and then retumed to the main stream. ‘The bed being regenerated is heated at substantially plont pressure before being cooled. ‘There ate many variations of this system, two of which are shown in Figures 2.16 and 247, Figure 2.18 is a schematic view of a closed cycle unit. Although not shown, the liquid from the condenser is staged into a stock tank or fractionated. Table 2.1 summarizes the relative advantages of these basic systems. The number of small variations possible is almost endless. Tail gas cooling as shown in Figure 2.18 is sometimes used to overcome the possible disadvantages of preloading the adsorbent during cooling. ‘The regeneration flow pattem for a given plant depends on economics. The basic pattem shown in Figure 2.15 is the simplest and for cost reasons alone has been an almost automatic choice for smaller plants. Where the volume of liquid being recovered is fairly lenge and small increases in efficiency involve a relatively large cash return, 0 more sophisticated plant can be justified. The real problem is fo obtain high stripping efficiency in the shortest possible time with a gas that will promote condensation of the desired components. This presents an enigma for the former would require the leanest gs possible in large quantity and the latter just the opposite. Compromise is the only Solution if full pressure regeneration is adhered to. Preloading of s gel tower during cooling is a critical consideration. It is obviously @ function of regeneration gas flow rato and composition. Tests show that at least 80% of the pentanes plus in the cooling gas may be adsorbed during the cooling cycle when using the system shown in Figure 2.15. This does not represent a loss of these components but it does require a bed large enough to contain the material from the cooling gas, plus that coming in during the adsorption cycle. Since many plants use about 30% of the main flow rate for regeneration and cooling this premature deposition of adsorbate means that a markedly leaner gas is entering the adsorbing tower than indicated by the inlet analysis. This partial protoading of the adsorbent and change in gas composition has @ marked effect on adsorption performance A coteful evaluation of the factors influencing regeneration of the adsorbent indicate that full pressure regeneration and cooling hes some inherent limitations. Deta show that the most effective regeneration cen be carried out at low pressure, using a reduced amount of cartier ges, followed by compression to about S00 psig. for condensation. Such ‘process should save enough on heating costs to at least partially compensate for compression costs. Whether or not such a process is practical has not been tested. It would however, take more complete advantage of the characteristics of silica gel hydrocarbon processing,TABLE I -1 Summary of Common Regeneration Systems Open Cycle ~ Flow from Cooling to Heating (See Figure 2.15) ‘Advantoges Disedvantages 1. Requires least amount of equipment 1, Leaner gas yields poorer condensation efficiency. 2. Less heat Ioad, recovers a patt of the heat left in cooling tower. 3. Offers least pressure drop. Open Cycle — Flow from Heating to Cooling Gee Figure 2.16) Advantages Disodvantages 1. Inlet gas yields better condensation efficiency. 1. Greater preloading of bed during cooling. 2, Requires one more heat exchanger. Open Cycle ~ Effluent Gas Cooling (See Figure 2.17) Advantages Ditodvontages 1. Uses lean gas for cooling, minimizes 1. Extra equipment costs. preloading of bed. Greater hest load and theretore 2. Uses inlet gas for heating, better more fuel cost. condensation efficiency. 3. Potential loss of recoverable product in effluent gas from the unit. Closed Cycle (See Figure 2.18) Advantages Disedvantoges 1. More efficient on condensation if closed 1, Added expense of purchasing and cycle gas analysis properly controlled maintaining a blower. Preloading of bed when closed cycle gas used for cooling.ADSORPTION OF SILICA GEL EQUILIBRIUM RY WATER 9 WON’ L 1 [eqputh— [poi | © + nN un oN ow LHOIEM O31vA g 2 w 1L0V JO % ‘LN: vow io j3LNOD ualvm 100 120 140 160 180 200 40 60 80 SILICA GEL TEMP, °F Fig. 2.127 MAXIMUM VELOCITY FOR NATURAL GAS UPFLOW THROUGH DAVISON 6 ceeeaaeeag fee Neer eceeree GRADE 03 SILICA GEL BASED ON GAS TEMP - 80°F 25}- -—-\j—- mn ee pi 24 — 23 sete z = i | S fee > hal 3 ° S $20 BEE a z Oo z 19} « ti a 2 a8 4 j | | 7} + j { | | 16} —_{—____}- —_—____|- ~ | I 15 400 500 600 700 800 300 1000 N00 ABSOLUTE PRESSURE (PS!) Fig. 2.21600 40 50 60 70 80 PRESSURE - psio 30 $ | arte | | ' | oe i | | | g °9 Sp ee Zoofu | i T 1 >b¢ | | | | i ;&So | / | | | | 8 geo | | | | | % IeSreeeee-ia rf eeeccag Pence ara ae De | | | Sak | Sie ete = 8 syu eg o- ao it 2 2u5 | j y 3 «uw | e S a aeR & ‘ol S68 wo = & -—— oe e©€O 2ua | ee | Bo a | | = o-———_ ao Oo oO} v O So & } Tv a 149 VOITIS "81 OO! 43d G3aNOsay ‘a1 Pree100 LB. SILICA GEL LB. ADSORBED PER ErFECT AT 4, OF PERCENTAGE ADSORBATE IN METHANE BINARY ON EQUILIBRIUM CAPACITY 000 psia_ AND 100 °F (AFTER MASON & COOKE, REF. 4) 16 x 3 2 4 Fig. a . 6 . MOL % in GAS PHASE 4 8 1.0CORRECTION FACTOR FOR COMPOSITION EFFECT OF OTHER COMPONENTS ON EQUILIBRIUM ADSORPTION AT 1,000 psia AND 100° F 2 4 6 8 MOL FR, COMP,/MOL FR. C4+ Fig. 2.5FACTOR FOR 2 PRESSURE CORRECTION 4 USE WITH Fig 100° F AT YyOLOVS NOLO3ZYYNOD 3YuNSS3ud 400 600 800 1000 1200 1400 1600 {800 PRESSURE - psia 200 2.6 Fig.TEMPERATURE CORRECTION FOR USE 1,000 psio AT WITH Fig. 2.4, 60 80 i00 120 140 6c TEMPERATURE 40 2.9) ai ai = 7 YOLOVA NOILOZYYOO BYuNLVYadWIL 0.9) $6 oF Fig. 2.7ADSORBATE é sar, g a 5 2 t a 2 0 wW 8 > v3 ° BED LENGTH hr VARIATION OF ADSORPTION ZONE FRONT WITH TIME Fig. 2.8 TIME CHARACTER OF THE BREAKTHROUGH CURVE Fig. 2.9ADSORBATE BED SATURATION oO > a | x 2 ° ° o + oO © Ca ° BED LENGTH SCHEMATIC VIEW OF BED SATURATIONS AT PENTANE BREAKTHROUGH Fig. 2.10 1.0 123 4 1- 14-20 MESH c 2- 8-10 MESH Co 3- 5-6 MESH 4- 3-8 MESH ° TIME EFFECT OF PARTICLE SIZE ON SHAPE OF BREAKTHROUGH CURVE Fig. 2.11ere “B13 SLN3NOdWOD UY3IAVSH AG SNOSYVIONGAH 3O LN3W39VIdSId 40 31dWVX3 S3LANIW - BWILere ‘by AWIL "SA Y3MOL NI SLNIOd SNMOINWA LY auNiwY¥adWaL svO 2,(NIAW) — Vy f O'b g's ove sz oz SI ou s‘0 Q, HS3W 8-9 ‘139 VOITIS ¢O 3avUD VISd O28-3uNSS3Yd L3INI Tee 4611 - NOILISOSNOD S¥9 L3ANI LS1NI MO1ag ‘NI 98—~—\— LZINI MOT3E "NI £97 jeeereee 4L37NI M0738 ‘NI a-——\ 43NI MO139 ‘NI 1z aS LZ 1N!I MO13¢ ‘NI O ~~ ——— | + SINODOWY3SHL JO NOILVOOT ZOl 901 Olt do - JUNLVYFdWAL SOEXAMPLE OF HOW ZONE LENGTH IS INDEPENDENT OF TOWER LENGTH ONCE THE ZONE HAS STABILIZED O° le ° 0.2: (SHIFTED BY 32.3 MIN. anf | | 40 50 6 70 TIME - MINUTES Fig. 2.14f L FRC 1 porta boo-4 1 1 I ' y y 1 t y I g oO 1 i} 2 E ula {| @ « er 1 fea 7 w ° ! 1 in Z 3 I ! ° o oe 1 i 78 2 1 ! 7 i 1 OUTLET | ' et HEAT ! | ox i eee HEATER 1 1 t m ! ° i E 1 Oo = a 2) CONDENSER SCHEMATIC VIEW OF A TYPICAL THREE TOWER PLANT USING COOLING AND REGENERATION IN THAT ORDER FIG. 2.15f el 1 ' 1 t i ' ‘ 1 ' ' 1 1 i 1 1 1 1 ' 1 1 ' 1 L HEATER ' Seeder HAH aCe ae came 4O1Lvuyd3S| i x 1 3 Meee | ONIT009 =O ' \ ; ; 1 ; CONDENSER \ ° z a a ° a ° < ol GAS SCHEMATIC VIEW SHOWING HEATING INLET o < ° IN LIQUID 16 AND COOLING ON REGENERATION FIG. THAT ORDERFRC p>] ONIguOsav O77" " 2) ONL LYY3N3934]} HEATER th SCHEMATIC VIEW SHOWING EFFLUENT GAS COOLING 217 FigINLET GAS ONIGYOSsay € CONDENSER = LIQUID 8OLvevd3as)}->- COMPRESSOR SCHEMATIC VIEW OF CLOSED CYCLE REGENERATION USING EFFLUENT GAS COOLING AB FigSECTION Ill FACTORS INFLUENCING THE SELECTION AND DESIGN OF ADSORPTION UNITS A review of the performance of adsorption plants, particularly those encountering some operational difficulty, has shown that many are processing gas streams of dilierent composition or under different Condition’ than were used as a basis for the original design. The greatest problem seems to arise from inadequate specification, although over-specification also occurs. The discussion thet follows outlines those factors that shouldbe specified in asorpton plants to obtain optinum perfortence. Obviously many of these factors are specific for hydrocatbon recovery units, while others apply to straight dehydrators as well. ioe _ As a matter of oracticability, one must design an adsorber to operate under the most common conditions expected, with allowance for the normal variations, One can seldom justily designing for those conditions that occur infrequently. A practical assessment of the limits to be placed on the designer con be made after a careful review of the purpose of e given unit in the total production and processing operation. In ‘2 hydrocarbon recovery unit, for example, & higher rate of retum may be generated by making no provision for processing high flow rates and/or unusually rich gases that occur infrequently. A. Got Composition ‘The designer needs « complete gas analysis that includes at least the percentages of methane through the heptanes plus fraction, as well as the molecular weight and specific gravity of that hheavy fraction. Also needed is the composition of the ges “contaminants”? such as hydrogen sulfide, carbon dioxide, nitzogen, and other non-bydrocarbon components. If the feed gas 1s a high pressure gas condensate it is also desirable to outline the PVT properties of the gas, particularly the dew point. ‘Any analysis, to be usable, must be representative of the ges composition under which the unit will operate. ‘This implies proper sampling. Much current sampling is inadequate. This probably stems from ¢ lack of understanding about the critical effect of sampling procedures on the Subsequent analysis. Appendix A outlines a suggested sampling procedure. A sample should always be taken by one experienced in this area. If experienced personnel are not available an independent testing laboratory should be utilized. If the inlet gas comes more of less directly from a well it is essential that the sample represent Stabilized well performance. This usually means that the well(s) should have been producing at constant rate for at least three days before sampling. Samples from unstabilized wells are absolutely unreliable and should not be taken. The unceliability becomes more acute es the reservoir rock becomes less permeable, Once a good sample is obtained, an estimate of the to plan ahead and thus reduce the ultimate cost of processing. A reservoir engineer can normally supply the data needed on both this and well stabilization Random variations in composition occurring within @ reasonably short time period must be considered. Such variations are likely to be moze dramatic for a unit serving only a few wells but they are always a matter of concem. ‘The expected normal range of composition as well as the frequency of such variation should be estimated if possible ‘The probable water dew point of the gas as it enters the unit should be specified. Do not automatically assume that the gas is saturated. This, of course, will lead to the highest bed Toading, but relative seturation affects the dynamic perfornance of a unit. Gases will normelly Teave @ reservoir saturated with water but variations in pressure end temperature can substantially alter this. In some reservoirs the gas will not be saturated, particularly those where gas production comes from a producing horizon substantially removed from an aquifer. A cleat understanding needs to exist between the customer and the designer about the correlation to be used to convert water dew point to equivalent water content. Water content is not independent of gas composition. Aromatic hydrocarhons, carbon dioxide and hydrogen sulfide have the predominant effect with the latter two being the most critical. Dats on these systems are extremely Sparse and may vary somewhat with source, so it is important that agreement on a basis for correlation be established 8. Flow Rate Flow rate specification chould include the frequency of variations expected. Admittedly, this would be an educated guess but is infinitely better than a mere average. An adsorption plant can accommodate relatively large velocity changes so long as the frequency is not too pronounced. Situations are Sometimes encountered, particularly with longer cycle dehydration units, wherein the flow rate falls to a point that efficient regeneration and cooling hecomes a problem As with composition, it is desirable to specify the rominal flow rate, with estimates of the normal variations and their frequency. In doing this it will usually be necessary to review pipeline or field practices and guess (professionally) what they are likely to be in the future,©. Pressure Pressure may usually be specified with accuracy for initial operations. Where the residue gas is being sold under contract, that contract governs the minimum pressure. Where operating pressure is fixed by reservoir pressure some consideration for future pressure decline must be made unless water drive or pressure maintenance of the reservoir is involved. In most cases a hydrocarbon recovery unit operates most effectively in the pressure range 500-800 psig. Where other conditions permit this is a good design range to specily. If widely varying pressures for short periods of time are expected a back pressure control should be specified. Normally, accurate specification of design pressure is a straight-forward problem requiring only a ‘minimal amount of good judgment. Temperature The proper specification of temperature requires a careful appraisal of the operating conditions if the gas being processed comes more or less directly from producing wells. Both adsorbent capacity and water content are fairly sensitive to increases in temperature above 100°F, Gas should never enter @ unit above the temperature to which it could be reduced by means of available cooling media. For water cooling this would be about 15°F. above the design wet bulb temperature. For air cooling this would be 20~30°F. above the design ambient ait temperature, depending on the economics. Cooling is the cheapest way to dehydrate where gas temperatures are above these ranges. Positive cooling ahead of the tower also allows positive control of inlet temperatures. Inasmuch as effective cooling is an integral part of most regeneration systems, inlet gas cooling, where useful, can usually be accommodated as Separate pass within the same cooling unit. Design of the regeneration gas cooling system requires proper temperature specification. The design wet bulb and dry bulb for the given location should be specified along with the available utilities. Wherever possible, natural convection air coolers should be avoided. They are cheaper but are less efficient and at the mercy of the vagaries of nature. Where recovery of liquid is ctitical to the economics or where extreme temperature fluctuations ate encountered their use is particularly not recommended. For most efficient recovery in watm climates (design ambient above 90°F.) water cooling is preferred if a sufficient quality and quantity of water is available. Refrigeration may also be considered. Sufficient latitude should be given the designer to teke maximum advantage of local conditions. For example, in some localities it is convenient to pump water from a river, bayou of lake over the coils and then let it flow from a simple catch basin back into the source. This is relatively crade but effective. Even saltwater may be used although an occasional hosing of the “‘coils"” with fresh water is required. Utilities Availability and Local Conditions ‘The utilities availabe and their celiabilty are significant parameters in optimum design. The 1. Availability of electricity with specification of voltage, amperage, phase, KWH and reliability 2. Availability of water with specification of quality and quantity. 3. Character of soil and allowable loading. 4 5. Design wet and dry bulb of air. Amount of supervision and maintenance normally available and/or preferred. 6. Normal climatic conditions ~ temperature range, rainfall, snowfall, prevailing wind, etc. 7. Altitude. 8, Availability of “sweet” natural gas suitable for use as fuel and instrument gas. Function of Unit This includes: Allowable outlet water dew point. Allowable outlet hydrocarbon dew point. Saleable hydrocarbon product desired, if any. Equipment that precedes and follows subject unit along with the conditions that are expected to prevail, 5. Allowable pressure drop actoss adsorption unit. ‘One must recognize that in a cyclic type operation such as adsorption a plot of outlet hydrocarbon dew points versus tine will also have a cyclic characteristic. 12HYDROCARBON TIME ‘The “humps” occur at the end of one cycle and possibly overlap into the beginning of the next one. The water dew point normally presents no problem since the highest dew point is still well below normal pipeline specifications. It is uneconomical and impractical to specify that the hydrocarbon dew point not exceed the maximum represented by A in the above figure. It might cost as much as 25% more to achieve this. A more realistic specification would demand that the time average hydrocarbon dew point (B) not exceed that specified. The time average is found by determining the atea under the curve shown above and dividing it by the time involved. For most plants this time average would be very close to the minimum shown. In an adsorber using an open cycle regeneration system it is seldom that the overell pressure drop ‘can be reduced below 20 psi. for optimum operation. About @ 2-3 psi. drop is attributable to the adsorbent and the remainder is necessary to achieve the desired regeneration gas flow rate. If pressure drop is critical the solution is nat to reduce bed length or velocity below that necessary for optimum performance. These factors have an almost insignificant effect on total pressure drop. A better solution involves use of oversize valves and piping, cecompression or some type of closed cycle regeneration. Although pressure drop can be @ problem, there are many producing situations where it is not. In such instances the designer allowed more freedom regarding pressure drop, can reduce plant cost and permit more flexibility in plent design. Some information is needed about the facilities that precede and follow the adsorption unit, with ‘emphasis on the former. Of particular importance are situations that might lead to fouling the System. Chief among these are compressor oil, adsorber oil, amines, ammonia, glycol, and some corrosion inhibitors. If the entrance of any of these, or liquid water, is a reasonable likelihood, design provisions need to be made. By the same token, if there is equipment downstream that ‘might suffer from even a small amount of desiccant ‘fines” that might occur, corresponding provi ould be made, In essence then, the role of the unit in the total system is an integral part of the knowledge necessary for optimum design. Time Foctors Maximum economic edvantage is only obtained if it is recognized that many of the design parameters will vary with time. It is exceedingly important that at least a professiohal guess be made about fature flow rates and compositions. This allows the designer to so lay out the unit that any fature modificetion may be performed at minimum cost and “down time" ‘The cash flow concepts used by most companies to assess economic worth of a sroject are very sensitive to initial investment. They also emphasize the revenue from the first 4-5 years with Succeeding years having a rapidly lessening impact. Therefore, in an area where field development is taking place, it is unwise to install a unit whose full capacity cannot be utilized within a two yeer period. A wiser approach is a unit predesigned for orderly expansion, Proper initial lay-out an allow for the addition of towers, more heat exchange and the like. It is probable that regeneration gas heater and separator, as well as controls would be installed for the ultimate anticipated capacity. In those cases where an increase in flow followed by a decrease is anticipated, such as in depletion type oil reserves, similar flexibility mast be anticipated. An oversized plant has 8 poor fue! efficiency as well as excessive depreciation charges. Furthermore, high desiccant efficiency is maintained for a longer time if it is completely loaded prior to regeneration. ‘The difficulty of forecasting future events is obvious but (0 do so is infinitely better than ignoring them. Supervision ond Maintenance ‘The proper design of controls and other accessories requires at least minimal knowledge of the type and degree of supervision aad maintenance that will likely be available. The designer needs to: 1. Provide controls that can be readily maintained by the available personnel, B2. Provide necessary safety and shutdown controls for unattended periods. 3. Provide monitoring equipment (at least connections for same) that will be needed under the customer's operating practices. A common operating problem involves controls and valves which existing personnel cannot maintain, This results in unnecessary “‘down time” and corresponding loss of revenue. Things to Avoid Specifying If the vendor is responsible for plant performance it is not reasonable to specify the desiccant capacity to use in design. This has been common practice in dehydrators and has not been @ serious problem as long as the specified value was within the capacity normally experienced in using silica gel. This is a completely unrealistic specification, though, tor hydrocarbon recovery units. Effective capacity is a function of many variables. To arbitrarily fix it reduces necessary design flexibility. As long as total allowable pressure drop is specified, there is no need to specify desiccant size or the allowable gas velocity. The specification of tower length is also unwise. Each of these affects performance, and optimum design requires # ‘balancing of these with the other parameters. To arbitrarily fix them, therefore, will likely inhibit optimum design. ‘The vendor should be free to use any regeneration technique that is suitable, providing it is compatible with the customer's requirements. ‘One should be careful that specifications are general enough to encourage more than one bidder. Each vendor of equipment has some unique differences in design, and if specifications are too detailed, it often amounts to picking the vendor. Review of Quotations ‘The system of using competitive bidding only works to the customer’s advantage if the quotations received are carefully scrutinized. The difference in initia! cost between a plant which simply “*works”” and one which offers the best economics can be’significant. Initial cost is only one of many criteria. The following should be considered in comparing quotations: 1. Initial cost, 2. Does the unit proposed meet all pertinent specifications? Relative fuel and utility costs for the different designs presented. Suitability of the unit for its intended use. Operational flexibility. Quality of controls, valves and accessories. Probable case and reliability of operation with the personnel «: Reliability and service record of the vendor. fias provision been made to protect the adsorbent from the probabie contaminants such that reasonable life can be expected? 10, Is the number and type of controls, valves and accessories suitable for the service and compatible with warehousing of parts? Under (2) the word pertinent has been emphasized, for instances often occur where a specification is not really important or an alternate offers advantage to the customer. All specifications are arbitrary to at least a minor degree regardless of the writers competence. Vendors can often suggest revisions or altemates that may save money or improve performance, with no sacrifice in quality of an installation, Following detailed appraisal of the quotes it is advisable to discuss them with the vendors. The purpose fs not to play them against each other (this is unethical) but simply to assure complete understanding. The flow of information at this point normally leads to a better plant. lable. ‘Summary A clea: understanding of the factors influencing design and the preparation of concrete specifica tions plays @ critical role in the ultimate economics of adsorption plants. Both over-specifying and under-specilying result in a tangible loss of efficiency. By the same token the practice of having vendors quote on a number of alternatives is @ poor practice. Quotations are expensive and the vendor must recover the cost through Sale of equipment. Itis to the consumes's practical advantage to clearly specify his needs. He pays the cost anyway, and knows the most about the problem. Appendix B summarizes the type of information requited for plant design and quotation. “4SECTION IV OPERATIONS, CONTROL AND TROUBLESHOOTING WITH ADSORPTION UNITS Although the adsorption plant is basically simple and easy to operate, there ate certain details that must be appreciated if both satisfactory performance and adsorbent life ate to be assured. Inherent in good operation are facilities with which one can test the unit to diagnose its behavicr. This invoives measurement of temperature and flow, as well as sampling connections, at key points. Ideally, the location and type of such facilities should be indicated. The vendor will not normally fumish complete testing facilities unless they are specified. ‘The discussion in this section will be based on a three tower system with open cycle regeneration in which the gas flows through the cooling and heating towers in sequence. This is not meant to imply superiority for this type system. It was chosen simply as @ matter of convenience to illustrate various points. For purposes of brevity it is written for hydrocarbon units. Those parts that apply to dehydrators fare apparent. A. Operation Records Adequate record maintenance and periodic tests are keys to good operation. Such records should include a diary of plant probleme as well as the usual information. The professional troubleshooter without good records has no basis with which to compare operating irregularities. Routine records should show daily gas volume processed, inlet pressure and temperature, pressure drop across unit, daily liquid recovery, regeneration temperatures and regeneration gas flow rate, Recording of such data on a routine basis is advisable. B. Plant Tests The usual purpose of a plant test is to provide data for compositional material and heat balances around the unit. A simple overall balance is made quite easily since the unit may be pictured schematically as follows: (8) Vv OUTLET r | aa © GAS 1} \ Ni Z ©) L HIGH PRESSURE RECYCLE SEPARATOR LIQUIC For purposes of en overall balance any recycle causes no difficulty, providing the inlet gas sample is taken upstream from the point at which the regeneration gas re-enters the system. There are two Quantities available for measurement in each of the three streams shown, (flow rate and composition) 8 total of six, At least five of these must be measured to complete the balance. Inasmuch as the ‘outlet gas is usually very lean and is difficult to analyze precisely, the following is recommendet INLET ay cas Flow rates for streams A, B, and C. Analysis of streams A and C. ‘The materia! balance will then yield the analysis of stream B. Where plant recovery is the primary interest this type of balance yields the necessary data. The above balance may be expressed in equation form as (for each component): Fyg = Vyy + Lx, 4d where: F = mols of inlet gas per unit of time V = Mols of residue gas per unit of time L = mols of liquid per unit of time mol. fraction of each component in feed mol. fraction of each component in residue ges ‘mol. fraction of each component in high pressure liquid Yes We v7 LO 1sNote: The number of mols of ges per unit time may be estimated from the flow rate in million std. cu. ft. of gas per unit time, by multiplying the latter by 2638, regardless of the gas analysis. The stock tank recovery may be calculated from the high pressure separator liquid by using a standard flash calculation. The basis for a stream analysis can be @ composite sample taken during an entire adsorption cycle. This is easily done using the water displacement technique shown in Appendix A. The displace ment rate is adjusted so that sample time coincides with cycle time. If one is interested in the performence of the adsorption bed proper a different technique is required, utilizing @ modified sampling program. INLET GAS A REGENERATION GAS yy ©) RESIDUE GAS A composite sample is obtained at point A, and 5-8 samples, per cycle are taken at point B. The Jatter can be accomplished by setting up @ multiple sample cylinder manifold or by means of a high- ‘speed chromatograph. The precision of sampling at point B is inherently poor but results are usable if the samples are carefully taken and analyzed. The flow rate at point A is the total of the regeneration gas rate plus the main inlet gas. The gas analysis at A could change drastically since it includes recycle gas but if all other factors ere constant, the recycle composition and rate should remain relatively constant. Deta from such a test are useful for analysis of the dynamic performance of the bed. A plot of comparative results over a period of time serves as a guide for the degree of degradation. Any abnormality in the curves points up an operating problem. If the breakthrough time of the pentanes plus is shorter than normal it is @ good indication that either the inlet portion of the bed is fouled or that channelling has occurred. The latter will usually be a result of a leak in the liner or internal insulation. One case has been encountered where a uni repeatedly been slugged with saltwater and the bed was simply a “cake"’ of salt, All flow was channelling through cracks. It is possible to distinguish between bed fouling and channelling from the regeneration portion of the cycle. If channelling is the problem, the outlet bed temperature will rise faster than normal because the hot gas will be bypassing a portion of the bed. Channelling may also cause @ lower than normal pressure drop. A larger than normal pressure drop is usually indicative of fines in the bed, screen plugging, or the like. Routine operating date cen provide the necessary information about the regeneration portion of the system without need for special tests. A continuous temperature recorder whould be a standard item on the gas outlet. By means of the inlet and outlet temperatures and the flow rate a heat belance around this portion of the cycle can be written, Several purposes may be achieved by analysis of this portion of the cycle. One is to minimize the ‘amount of regeneration gas. This will improve condensation efficiency, reduce fuel gas requirements and reduce the amount of adsorbable components reentering the inlet gas stream. The latter factor effectively reduces the unit capacity at excessive regeneration gas flow rates. A second purpose is fulfilled by making it possible to check on the effectiveness of the condensing system. Where e plant test indicates the possibility of faulty desiccant, samples of that material a necessary. Ideally, three samples ate desirable — at the top, in the middle somewhere below any contaminated zone and at the bottom. A sample from the very top will show contamination from entering deleterious materials. The middle sample represents some kind of an average material. The bottom sample usually represents a section where regeneration might not have been as effective because the adsorbent has received minimum heating. A pint sample is normally adequate. The middle sample can be taken with a sample probe. Visual examination of the samples plus activity tests in the laboratory lead to meaningful conclusions. Caution should be taken in using stock tank recovery tests as a means of comparing relative performance of competitive brands of equipment or adsorbents. One very strong conclusion reached as a result of a detailed reseerch program has been that a quantitative appraisal of all pertinent factors requires equipment and controls of a degree of sophistication seldom encountered on a field 16unit, Smo! changes of operating conditions or in operating practice can have significant effects on Stock tank recovery. Inasmuch as the gases being produced are very lean, very very smal] absolute changes in analysis are magnified in terms of relative stock tank recovery. Good Operational Techniques In addition to keeping good records there are several operating practices that lead to optimum plent performance. 1. Protect the towers from the entrance of all liquids. This implies a good scrubber with @ good mist extractor element. 2. If there is any possibility of liquid carryover, a layer of Grade 59 buffer gel should be placed on top of the regular desiccant grade silica gel. Grade 59 can adsorb en amount of Fiquid water equal to its own weight, and has almost this much capacity in equilibrium with saturated gas. So, using it as a buffer zone not only protects the regular silica gel but also provides high capacity where the eas is saturated. The amount of buffer desiccant may vary with conditions, but a depth of 812 inches is usually adequate. Keep ammonia or caustic mist from the desiccant. The very nature of the silica gel chemical end physical structure which contributes to its efficiency as an adsorbent also makes it subject to chemical attack by compounds of an alkaline nature. Water washes, traps and various dry scrubbers can be used to prevent loss of desiccent capacity due to chemical attack. c. Keep lube oil, glycol and other heavy hydrocarbons in the gas to an absolute minimum. Carbon compounds such as these are not removed during normal regeneration procedures. All such material that reaches a desiccant hed may eventually coke, and reduce efficiency. Reasonable regulation of lubrication uses at compressor stations coupled with efficient coalescing type separators can minimize this problem. d. Alcohol, which may be used in the system, has no harmful effect on the gel. However, it will be co-adsorbed with water, and should be included along with water in calculating the load on the desiccant. Normal regeneration removes it. Use the minimum regeneration and cooling gas necessary to perform their functions in the time allotted. 3. Never allow a rapid pressure release or increase on the towers. Severe breakage can result, particularly in the former case. 4, Inspect scteens and gratings when a tower is empty. They should be tight so that none of the bed can pass through them. 5. Inspect liners and internal insulation. A vibrating, loose liner can cause adsorbent breakage. 6. Maintain valves so that leakage is at least undetectable. Hot regeneration gas leaking into an adsorbing gas stream seriously affects performance. Leakage can usually be detected by feeling the piping on the ‘‘cold” side of the switching valve. 7. Service recorders and controtlers on @ routine basis so that reliable date are available. Make an effort to maintain as constant an inlet gas flow as possible. Minimizing repid variations in inlet analysis is also desirable if feasible. 9. Use low volatility corrosion inhibitors, if these are necessary preceding the unit. 10. Periodically perform plant tests so that performance can be assessed in detail. This is particularly important where operating conditions are changing. 11. Always design and operate for maximum cycle length, consistent with the purpose of the unit. Naturally, straight dehydrators will have much longer cycles than hydrocerbon recovery units, but if a meximum cycte length is used in any case, benefits will come from two factors. There will be fewer cycles in treating a given volume of gas, which counters the established fact that desiccant life is some function of the number of regenerations. In addition, there will be 2 maximum amount of water on the gel at the beginning of each regeneration to assist in purging, or displacing hard to remove hydrocarbons which otherwise collect on the gel. ‘The above are primary factors which contribute to adsorption efficiency. Silica gel has a high affinity for water and hydrocarbons and is “tough” but careful attention to detail is necessary to get the ultimate benefit of its outstanding characteristics. Likewise, the adsorption plant is simple end easy to operate, but small, easily corrected, mechanical problems can impair performance. Controls ‘The controls and the control system should be the simplest available of those compatible with need and maintenance capability. Unfortunately it seems as if the sophistication and sensitivity of ‘2 control is proportional to how fragile it is. Since most of the controls are exposed to the weather this must also be a matter of concern, ‘The switching valves may be controlled on a time basis, outlet regeneration gas temperature or outlet gas analysis, The latter is best (and most expensive) but requires a time or temperature Override to insure that a properly regenerated and cooled tower is ready when switching occurs. WwRegardless of the system; accurate temperature measurement and recording plays a key role. Many people overlook how difficult it is to accurately measure temperature et 400-500°F, Because of radiation, and allied effects, errors of 50°F. and more are possible. The thermowell in which the Probe is located should be “‘shielded”” so that radiation losses are reduced. Long leads from the Sensing bulb to the instrument should be avoided. If necessary such leads should be well insulated. Some instruments provide compensation for the effect of lead temperature on recorded temperature, Periodically, recorded temperatures should be checked with carefully calibrated thermometers Likewise, temperature recorders should be periodically calibrated. Exposed portions of the thermoweil should be insulated and the opening sealed. The flow controller on the regeneration gas line should be calibrated periodically. As previously mentioned, fairly close control of regeneration rates is of practical importance. Troubleshooting No one plant is like any other and it is difficult to set up a norm as a standard of comparison. Analysis of plant data is much like electrocardiograph data on @ human heatt, There is no “normal heart” to compare it with. The key is the change with time. Some plants, of course, ate in such bad shape that it is possible to pinpoint the problem(s) by ‘simply comparing their performance against the principles outlined herein. This represents the straightforward end not too common (unfortunately) troubleshooting approach. More problems seem to arise from subtle and/or gradual changes where it is not obvious that some basie physical Principles are being violated. In such cases it is the change in performance that usually furnishes. the key clues. One of the best places to start is a careful examination of the operating data to ascertain what changes, however small, have taken place, The cause of these changes, once found, will usually pinpoint the trouble. It is for this reason thet an attempt has been made to outline those factors that play a role in the adsorption process. Attention to these details cen make silica gel adsorption equipment easy and profitable to operate. 18SECTION V DESIGN CRITERIA FOR NATURAL GAS DEHYDRATORS, AND DEHYDRATORS FOR SIMILAR HYDROCARBON STREAMS Date associated with the design of a dehydrator falls into three categories: 1. Fixed operating conditions 2. Gas flow rate (or rates, if variable). b. Ges temperature. c. Inlet water concentration. d. Inlet pressure. 2. Fixed factors to be estoblithed a. Desiccant type. b. Desigs useful capacity of the desiccant. 3. Flexible factors which con be monipulated for optimum performence fabrication and performance stondpoint a. Size of desiccant beds. 1b. Number of beds. ind or economy, both from a ©. Configuration of beds. Cycle time. Gas flow directions ~ drying, heating, cooling. Gas volume — drying, heating, cooling. g Regeneration temperature. h. Regeneration pressure. i, Regeneration purge gas source. je Pressure drop. Although certain of the items in the Hirst category may be manipulated by the engineer designing a complete processing plant they are usually fixed at the point of entrance to a dehydrator, and will be so ‘The desiccant type is Davison silica gel. This particular product has been proven in hundreds of installations to have the all-around qualities to make it a superior desiccant in natural gas service. The design useful capacity will be dependent on service conditions which are ngt known quantitatively when the design is initiated. ‘There is a certain freedom to the establishment of other elements in the design which allows for optimization of the adsorption process to fill a particular need. The following is a step-by-step method ‘suggested for arriving at such optimization. A. Sizing the Desiccant Bed Step 1. Establish the water load to the desiccant on an hourly basis. Assume all the water in the incoming gas will be adsorbed. The water content of the gas may be obtained by actual measurement, or if it is a saturated natural gas which has received no prior processing it may be taken from one of the correlation charts commonly used, Figures (5.1), (6.2), with suitable correction for H2S or CO2 constant. Water content of high pressure natural gas is particularly sensitive to the concentration of HeS ‘and COs, Data for quantitatively determining the effect is extremely limited, however, Figures 5.3 and 5.4 provide the best available means for making such a correction. The procedure for using these curves is as follows: a. Calculate the specific gravity of the hydrocarbon portion of the gas on a COz and HaS free basis. Determine the water content of the hydrocarbon portion from either of Figures 5.1 or 5.2 Determine the water content of CO2 from Figure 5.3. Determine the water content of H2$ from Figure 5.4. Find the total water content of the gas by multiplying each of the three water contents above (Steps b, c, and d) by the respective mol. fractions of each of the three parts. Is. Hat MMSCF gas Hourly Loading ee 5a MMSCF ges ER 19Step 2. Set the minimum cycle time. This time may be specified by the operating agency, or left to the discretion of the design engineer, Certain factors associated with the plent may dictate a desirable cycle tine. If not, # reasonable petiod for dehydration is 8 hours. Step 3. Determine the design useful capacity for silica gel under the service conditions. 4. From Figure 5.5 determine the base capacity, which is dependent on the relative saturation of the inlet gas. This curve is based on accumulated plant data, If the gas is not saturated the % relative saturation is 100 times the actual water content divided by the theoretical saturated water content from Figures 5.1 or 5.2. 100 | Ib. Hz0 (Actual) MMSCF = HRS MMSCF Ib, HzO (at saturation) b, Multiply the base capacity by the temperature factor token from Figure (6.6). ‘Adjust the useful capacity thus obtained for any excessive contaminants which may be in the gas stream, and for expected useful life. This adjustment is impossible to predict exactly, rather it must depend on the judgment of the engineer. Various contaminants and the way in which they effect silica gel have been discussed previously Usually the maximum adjustment which should be mate is a reduction in the capacity determined in ‘*b"", above, by 15%. This would apply if heavy oil carryover is expected from an adsorption plant ot if the inlet stream contains a large amount of glycol. The design useful capacity is that found in “'b” with the proper adjustment for contamination. This design useful capacity or “U.C."” will be in Ibs. H2O per 100 Ibs. silica gel. “Useful capacity” is an “equilibrium value”. That is, it is a value which the silica gel will oxhibit after the initia! loss in capacity normally exhibited by all desiccants. Figure 5.7 illustrates the effect of age on silica gel capacity in natural gas dehydrators. Months in service are arbitrarily used as the units of service time, although number of regeneration ‘cycles or cubic feet of gas processed per pound of desiccant could also have been chosen. Because of the many variables contributing to such aging an exact prediction on any basis is impossible. Thus a rather broad band is used to show the typical range, based on many Jplteduol datapoints from nuncrous commercial istllations. I is obvious fem the plot that any dehydrator will exhibit an initial useful capacity in excess of design. To take advantage of this fact, and to prolong desiccant life, cycle length shoule be regulated by exit dew point monitors rather than arbitrary time periods. As the desiccant ages, and change in useful capacity stabelizes the unit can be switched on a time cycle corresponding to that used for the original design. Step 4. Calculate the minimum amount of desiccant needed for each adsorption cycle. Ibs. H20 | HRS. | 100 ths. gel _ = Ibs. gel Step 5. Determine vessel size and shape. A minimum volume for the desiccant bed has been established, based on the amount of desiccant required per cycle. The configuration of the vessel may be adjusted to accommodate available sheli plate, heads or other structural members, within limits established by ceasonable L/D (length of bed to diameter of bed) ratio, gas velocity and pressure drop. As a rule of thumb an L/D ratio of at least 2.5 hes become a suggested minimum in the industry. Lower values can be used if the problem of gas distribution is recognized, and suitable precautions are observed. For up-flow conditions the maximum superficial velocity can be taken from Figure (2.2) For down-flow the ebsolute maximum velocity is twice the value for up-flow, although 1.5 times the up-flow value is preferred as an operating limit. It is unlikely thet an arbitrary velocity figure will result in « calculated diameter exactly compatible with standard shell or head sizes. Thus, the exact determination becomes one of trial and adjustment, as follows. a. Choose a superficial velocity within the limits of Figure (2.2). b. Calculate the diemeter required for this velocity 1. Correct the flow cate of gas, a& given, (usually in standard cubic feet per minute) to actual flow rate under operating conditions. ve 5.2 where: V = volume of flow per unit of time at operating conditions. compressibility factor for the gas. P = absolute pressure of gas (psi). sbsolute temperature of gas (460 + °F.) NV = Ib, mols of gas per unit of time = MMSCF X 2638, R = @ constant (10.71). 202. Calculate a preliminary face area of the desiccant bed. reo = actual flow from “1 53 supetficial velocity 3. Calculate a preliminary diameter. D-V127 x area 54 c. Calculate @ preliminary bed depth. h, _ 1b: of silica gel from Step 4- Pe 45 x area from (b.) ‘The preliminary dimensions thus calculated must ke examined for compatibility with standard steel components, for L/D, and for pressure drop. ‘Assume h,, the actual bed depth, it epproximately the same as L, the head seam to head seam dimension of the vessel. d. Assuming that L/D is > 2.5, calculate the velocity after adjusting D to standard dimension ‘close to the preliminary D calculated above. ye __Betual flow rate 56 Area based on adjusted D Compare this value with Figure (2.2). If it exceeds the recommended maximum, recalculate using @ larger standard diameter. When D has been finalized, the height of the bed is found by dividing the volume of the desiccant by the cross-sectional area produced by this diameter. 3m Step 4, jt e D*¢inal) fe. Calculate expected pressure drop for final bed depth and velocity. Pressure drop predictions for adsorbent columns are subject to slight errors due to packing itregularities end variations in gas composition and conditions. However reasonably accurate ‘estimates for systems operating below 1000 psi. may be made as follows 1. Using the final superficial velocity, determine the pressure drop from Figure 5.8 2. Correct for difference between the actual gas stream and air (on which the curves are ESECGS Ka convert units to psi over the entire bed. Ap - ressute drop igure 5.8)» (not tof ead)? 2.307 (2 For systems above 1000 psi. or for gases of high molecular weight (above 35~40) Sonaction for wiscosity should be made. i either the preliminary or the final forms of and D give an L/D less than 2.5, oF the Fein ee eesseanip is excessive, sone GUsign changes may be in onder. For L/D ratios between 2.5 and 1 a conveational vertical cylintical bed can be ased if rae L/D ratios Metter co gas dicuibuton. In down-flow systens special gue eae atten Hitted sothednfet piping, In addition, # layer of inert bells, such a3 str bata aes i desiccant will improve diotibution. In such an arrangement it is Malton ot ee inet material from the desicesot with a suitable wire screen © ae epi ts dossity differences: In upllow towets similer headers and layers of ree ee used, but separating screens are unnecessary. Fer tow L/D values, expecially those below 1, economics usually dictate a different type Fee eval a reciy for larger volume, high pressure gas sean. Several alternatives tre porsibie in such sitution, Special Configrations 1 Maltiple Beds ~ Dividing the total bed area between two oF more vessels can result in wale eae inp vecaute smatter heads and lighter shell plate may be used, even though ining will be somewhat more expensive. In addition, it is sometimes possible to reduce total desiccant and regeneration requirements, Fae tee tinge, When the low L/D results fom relatively small amounts of ds a eae tein cyete mes of § to 12 hours frequently result in very shallow cate ae toe iret eier multiple beds of a depth several tines the minimum calculated allow aed Oa ae ee ooiai umes ee Iong.at a normel cycle. Thus, instead of two large cach vessel to pers Sion and one on regeneration, several small dryers share the toad Fee tearm de ofthe grove Te removed periodically for regeneration. Consider the fotlowing example: 5.8 aCalculation shows that 10,000 Ibs of Grade 03 Silica Gel will be required for an 8 hour cycle. Velocity consideration indicates the area of the bed must be 75 sq. ft. and the depth 3 ft, To get 75 sq. ft. in a single tower D would be 9.1 ft. Splitting the flow among 4 vessels would result in diameters of about 5 ft. The depth of the beds could be increased to 5 ft. This will provide a workable, if marginal, L/D. With the added depth, each bed will be able to remain on stream over 13 hours. It should be possible to reactivate a bed of this size in slightly over 3 hours, so that only one additional vessel will be required to maintain continuous operation, The total beds would be 5, with one on regeneration at all times. The total gel required would be about the same as if two vessels, each holding 10,000 Ibs, were used. The regeneration system can be smaller since only 4,000 Ibs. of desiccant will be regenerated at a time. Under some circumstances the total desiccant requirements for a system of multiple beds is ess than for the more conventional double towers. Obviously, it would require a rather detailed investigation to find the actual cost of such alternates, but this effort can be well worthwhile, 2. Radial Flow Dehydrators ~ Occasionally dehydrators are designed for radial gos flow. The gas enters a distribution tube which runs full length through the central axis of a vertical cylindrical shell. It exits through an annular space between the desiccant and the shell itself. This configuration provides a large facial area in a shell of reasonable cost. There is an added expense of support screens to provide the annular space outside the desiccant. The system also provides very short contact time, 50 dew points as low as those obtained with more conventional designs are not usually possible. 3. Horizontal Beds — Supporting a bed with large area and relatively shallow depth in a cylindrical vessel resting on its side is another altemative. In such an arrangement the desiccant depth can be about 60% of the diameter of the vessel. Thus a ten foot diameter shell would hold a six foot deep bed supported parallel with its axis and about two feet above its lower side. This two foot space, and the equal space above the desiccent, act as plenums for gas distribution. Various mechanical headers and baffles may also be incorporated to improve gas distribution. Guard Dryets ~ Previously the possibility of multiple beds was considered whereL/D ratio was a problem. There are other variations on this theme which should be considered. They are presented merely as examples of how engineering ingenuity may be applied to peculiar problems. In certain phases of industry processing hydrocarbon gases extremely low dew points are required, and it has been a practice to place a ‘guard dryer” after a conventional dehydrator to catch any water that may have gotten through. Sometimes this guard dryer does not operate on any regular cycle, and is reactivated only after a plant upset is known to have allowed some water into it. More recent practice has been to place this dryer in series with the regular dryers and reactivate it on a segular cycle. A typical arrangement is to have three towers where normally oaly two would be used. While one is being reactivated the gas being dried goes through the other two in series, At the end of the cycle the tower that has been receiving wet gas goes to reactivation, the second in series switches to receive the wet gas, and the freshly activated desiccant assumes the “guard” position. Partial Bypass ~ Another system may be used where the requirements are exactly opposite — only nominal drying is cequired. Because solid desiccants, by their very nature, tend to produce very dry gas a portion of a wet Stream may sometimes be bypassed and blended downstream of the dryer. This saves on vessel size and reactivation costs. Also in a very large system where ‘multiple beds must be used in parallel it may be possible to save @ complete unit, and bypass that amount of gas. Minimum Bed Depth Pressure drop in any gas handling system is always important. However, over-zealous attempts to minimize pressure diop by making desiccant beds very shallow may result in inefficient desiccant utilizetion and inability to obtain low dew points. Unfortunately the complexity of the adsorption mechanism, coupled with some co-adsorption of hydrocarbons, and further confused by the ageing effect, makes it impossible to calculate exact minimum bed depths for specific operations. In general, dew point below ~50°F. at the operating pressure of natural gas systems require beds at least 6 feet deep, while a minimum depth for dehydration to dew points of 0 to 10°F. is about 3 feet. As in the case of any generalization there can be exceptions to these limits, but they may be used as guides. ‘An oversimplification of the complexity of ali the factors involved may also guide the design engineer in this area. This involves the contact time concept, wherein the actual time the gas and desiccant are in contact are related to a minimum time required for the mass transfer of water from the gas to the desiccent. Ideally this time, for silica gel is less than half a second, but one second is a more realistic value. The contact time, or residence time of any increment of gas in the adsorbent may be calculated from the superficial velocity and the bed depth. Since the volume between gel particles is about 40% of the total bed volume the contact time, in seconds, is: 40x by x 60 59 22It must be remembered that hy decreases as the inlet end of the bed becomes saturated, and to maintain the desired exit condition the miniium tt, af the end of the cyele, must still be long enough for the desired mass transfer, of the required contact time. This concept is far too general for design purposes, but does illustrate the danger of designing short beds for the Sake of minimum pressure drop Reactivation Requirements Various investigators have covered the subject of desiccant reactivation. A particularly straight forward epproach was published by Wunder (7). This method is adaptable to various conditions and may be used as a guide or for comparison with the methods of other design engineers. A critical factor in any such calculation is the temperature to which the desiccant must be heated. In most natural gas service the presence of heavy hydrocarbons dictates that temperature must be higher than would be the case if only water were being desorbed. For Davison silica gel this temperature is usually in the range of 450~500°P. If extreme contamination is present it may be increased to $50-600°F. Bed temperatures of over 600°F. will result in permanent damage to the desiccant, so this should be the maximum for gas inlet temperatures. Some driers processing “‘clean”” gas operate satisfactorily with regeneration temperatures as low as 350°F., but the 450-500°F. range is recommended. ‘A method of calculation similar to that proposed by Wunder is as follows: 1. Heating Requirement ~ The procedure used to calculate reactivation gas rate is shown step-by- step. First, the total heat requirement for desiccant reactivation is determined. Then, by @ trial-and-error process, the constant outlet temperature and heat available per pound of reactivation gas are evaluated. At the correct constant outlet temperature the heat available equals the heat required. ‘The trial-and-error process ie shortened by plotting several values of heat available per pound of ges and heat required for reactivation pet pound of gas versus assumed values of constent butlet temperature, The intersection of the two curves gives the constant outlet temperature find the heat available per pound of reactivation ges at this temperature. “The total heat required to reactivate the desiccant includes the amount needed for the vessel, desiceant, and inerts, desorption of water and hydrocarbons, and radiation and convection losses. Step 1. Heat to desiccant ~ (wt. of desiccant) x (bed temp. required ~ bed temp. at end of drying cycle) x (specific heat of desiccant). ‘The bed temperature at the ond of the drying cycle may be taken as that of the gas stream being dried. The specific heat of Davison silica gel is 0.22 BTU/Ib. °F. Step 2. Heat to vessel = (wt. of steel in vessel) x (AT as for gel) x (specific heat of steel). If internal insulation is used @ suitable adjustment should be made in this calculation. 0.12 RTU/Ib. °F. carbon Step 3. Heat to any inert material being used as bed support or for gas distribution ~ (wt. of inert material) x (AT aa for gel) x (specific heat of material). Step 4. Heat to desorb water. (Assume 250°F. for constant temperature desorption period and check later). fa. Sensible heat = (wt, of water to be desorbed) x (1.0 BTU/Ib. °F.) x Q60'F. — bed temp. at end of drying cycle). b. Heat of desorption = (wt. of water) x (1850 BTU/Ib.) Step 5. Heat to desorb hydrocarbons. (wt. of hydrocarbons) x (150 BTU/Ib.) x (1.33). Use 150 BTU/Ib. for the latent heat. An approximate value of the total heat required for desorption is 1.33 times this. In the original presentation Wunder assumed a hydrocarbon load of 10% of the desiccant weight, however, for most long cycle (8 hours ot mote) dehydrotors this appears high, and @ vaiue of 5% is more realistic. Obviously the ges analyses aad other factors can be used as # guide in modifying this calculation. Step 6. Make a sub total of the heat requirements calculated thus far. Step 7. For radiation and convection loss, assume 5% of total heat, therefore, total heat required = (ub total from Step 6 * 0.95), Step 8. Sensible heat available per pound of reactivation gas: Calculate sensible-heat loss by reactivation gas from inlet of S00°F. to three assumed constant temperatures S00” to 150. ontulpy chege = 219 BTU 500" te 200°. enthalpy chinge = 190 BTU 500" ta 250 enthay chong = 163 BTU Total Heat fom St 7, pryp, Hs0 23Step 10, Water pickup per pound of reactivation gas at thee assumed constant temperatures: @. Constant bed-outlet temperature, °F, 150 200 250 b. Total system pressure, psia, cc. Water partial prossure at inlet, psia (mol. fraction H20 x system pressure), Water vapor pressure at outlet, psia. 3.716 11.525 29.82 Lb, HsO/1b, reactivation gas at inlet for each period __(€)_ mol wt HzO () — (©) mol wt gas £. H20/Ib, reactivation gas at outlet for each period @)_y molwt Ho, ©) —@ mol wt gas & Lb, H20 picked up/Ib. reactivation gas [(-(e]] ce h. BTU required/Ib. HzO picked up (Step 9). ‘ i, BTU required/Ib, reactivation gas [{e) x (h):] A 7 Step 11. Constant outlet temperature and heat available: Plot heat available (Step 8) and heat requited (Step 10) per pound of reactivation gas versus exit bed temperature, ‘The intersection of the hest-available and heat-requited curves indicates a constand bed-outlet temperature, and a reactivation-gas heating value, Step 12. Required reactivation gas rate: For heating period = Total Requirement, Step7 Ibs. /hr. of (Heating Period, Hrs) x (Heating Value, Step 11)” Reactivation Gas Correction for nonsteady-state heating ~ The procedure for calculating required reectivation- gas rate during the bulk-water-removal period was developed for long heating-ap petiods and assumes a steady-state heat transfer process. In addition, the effect of temperature approach between inlet gas and final bed temperature is not recognized. Since the desiccant bed must be heated to reactivation temperature in a short time, the reactivation-gas rate calculated by the above procedure should be increased by some factor which will correct for nonsteady-state heatup and temperature approach. A divisor of 0.6 Is used to attive at a design reactivation-gas rate, This factor assumes a SOF. temperature approach between inlet gas and final bed temperature and appears reasonable in light of plant experience, ‘Step 13. Apply the 0.6 factor to the problem, the required reactivation-ge (Gas Rate, Step 12)+0.6 =... Ib./be, Superficial Velocity ~ The superficial velocity of the reactivating gas through the desiccant bed during the constant-temperature period is usually below § to 10 fpm. This is considered ‘adequate to sweep desorbed water from the bed and fo prevent channelling. Pressure drop should also be checked at the most severe reactivation-gas temperature. Cooling Requitement — Cooling of the hot reactivated bed is normally carried out at the same as rate as heating, with the heater bypassed. The adequacy of this rate to col the bed within the desired time is checked by the following method: of desiccant) x (Effective specific heat), 1,, Te~Te Gas rate x av. specific heat of gas TeTs where: Effective Ib. of desiccant = weight of vessel and contents, Effective specific heat « weighted av. specific heat of vessel and contents Gas rate = 1b. hr. = initial bed temperature, °F. initial exit gos temperature, °F. 24POUNDS OF WATER PER MILLION CUBIC FEET OF GAS AT 60°F & 14,7 PSIA WATER CONTENTS OF NATURAL GASES WITH CORRECTIONS FOR SALINITY AND GRAVITY 89000} 60000] 40001 20% 10000) 8000} 6000} 4000} BRINE 201 FR 10001 13299 261354 00 LG_TOTAL SOLIDS IN BRINE.% s 200) 100} 20) DEW POINT OF NATURAL GAS [|] dd. McKETTA AND A.H. WEHE THE UNIVERSTY OF TEXAS 1958 0-40-20. 0 20 40 60 &0 100 120140160160 200 240280 TEMPERATURE, °F Fin. 5.1WATER CONTENT LBS, PER MM CUBIC FEET AT 14.7 PSIA AND 60°F 1000 900 t ‘ 800 t 700 pes WATER VAPOR CONTENT ae OF NATURAL GAS AT_ SATURATION 400}—— MCCARTHY BOYD AND REID PRESENTED AT A.LM.E. PETROLEUM BRANCH 300 f--—)"| SAN ANTONIO MEETING OCT 5, 1949 200 NOTE: THE CHARTS SHOWN ON THIS| 70| PAGE ANO THE NEXT PAGE ARE ONE CHART, DUE TO THE SHAPE FOR RE- PRODUCTION THE ORIGINAL WAS SPLI 50] at BOF. FOR READINGS ABOVE THAT SEE 3 2 ov wg “60 -50 -40 -30 "20 10 0 10 2 30 40 50 60 TEMPERATURE °F Fig. 5.20PER MM CUBIC FEET AT 14.7 PSIA AND 60°F. WATER CONTENT LBS 8 8 Bw orow o WATER VAPOR CONTENT | OF NATURAL GAS | AT SATURATION { MCCARTHY BOYD AND REID { PRESENTED AT 2 + zl pol] A.LM.E, PETROLEUM BRANCH SAN ANTONIO MEETING OCT 5,1949 | Ty | i \ | EE EEA | 30 90 100 110 120 130 140 150 160 170 180 190 200 210 220 TEMPERATURE °F Fig. 5.2bWATER CONTENT OF CARBON DIOXIDE R, CHEM. REV 29, (I941) 475 FROM WEIBE, 3000 5000 6000 7000 8000 PSIA 4000 2000 1000 600; 550) 500} o 8 00} z < " a 301xX01d NOsUYvd OSWW 43d YBLVM PRESSURE , Fig. 5.3WATER CONTENT OF HeS BASED ON DATA FROM SELLECK, CARMICHAEL AND SAGE, + 44, (1952) 2219 E.c 67891000 15 PRESSURE - PSIA 5 LS 5.4 Fig. 100 g geek ee se 4 a ae S (4.09 8 WiSd Zp!) S?H 4OWW 43d S87 -INBINOD Yaivm e 7DESIGNS USEFUL CAPACITY (%) 12; SILICA GEL CAPACITY AS A FUNCTION OF NATURAL GAS t WATER CONTENT (% RELATIVE SATURATION) ly 10 20 30° 40 50 60 708090100 % GAS RELATIVE SATURATION Fig. 5.5USEFUL CAPACITY FACTOR 2 # 04 03 CORRECTION FACTOR TO BE USED WITH Fi 8 8\— 1. 0 80 90 100 110 120 130 GAS TEMPERATURE, (°F) Fig. 5.6 1402° Old BOIANaS NI SHLINOW pe 2b Ob BF OC HE 2E CE B2 92 be 22 02 BI 9! vi ZO! 8 9 F 2 0 T 7 ier fe bet ed eel oe fee (ee rt eet le etic | { —_— SV9 WWYNLVN) NI } __ 2 BOIAMTS NI-3WIL JO NOILONNA i v Sv ALIoVdVI 139 VOITIS PH eee EEE HEHE ; | i : a9 vos 4o “9 'NDAVISON SILICA GEL PRESSURE DROP THROUGH (BASED ON AIR) 8 MESH ON = “| g 3 ia 3 3 oo Sooo o fo Oo SOS oo oa OG 3 8 on 5S 8 Boe a 2 26 gesess 8 oe eheF oR F RS SBLONIW U3d ‘La ‘ALIOOT3A IN. SILICA GEL PRESSURE DROP, IN. WATER PER 5 Fig.SECTION VI DESIGN CRITERIA FOR HYDROCARBON RECOVERY UNITS ‘The design of a hydrocarbon adsorber must necessarily be divided into two parts if optimum operation is to be achieved. The first is an estimation of the concentration of the various components on the bed at the time the adsorbing tower is to be switched. The second is the development of a regeneration process that will strip and cool the bed in the time available. This latter step includes estimation of the recovery of liquid in the high pressure separator, from which stondard flash calculations will yield stock tank recovery. To date the common methods of estimating performance involve some combination of the above into one step. This requires expressing stock tank recovery, ot percentage removal from the inlet ges, as some function of the mass of the bed and the input rate of pentanes plus. This is a reasonable and simple approach as long as it is applied to units which are exactly the same in all their physical details. However, it is self-defeating for optimum design considerations may require the physical configuration of the unit to vary with the conditions under which it operates. New design critetia are proposed which involve the following calculations: 1. Estimating the time at which the front of the pentane adsorption zone reaches the exit of the bed. 2. Estimating the length and shape of that pentane adsorption zone. 3. Estimating the concentrations of each of the butane plus components at the time of pentane breakthrough. 4. Checking to sae thot the shove concentrations are within the available saturation cepacity ofthe adsorbent. Writing @ heat balance for the regeneration and cooling cycle that is based on the time in (1) above. Establishing a rate of desorption for the necessary regeneration gas flow rate fixed in (5). Establishing the composite analyses of the high pressure separator liquid. Flashing the liguid in (7) above to the stock tank. Correcting, if necessary, the inlet analysis for the gas being recycled to the tower inlet from the high pressure separator. ‘The above method is based on data taken in a research program that utilized 2, 3 and 4 in. towers, 5-15 ft. long. The superficial flow velocity (based on empty tower cross-section and assuming ideal gases) varied from 945 ft. per minute, Most of the data used herein were taken at an inlet temperature of 90°F, and a pressure of 800 psig. Included, however, are runs at pressures from 400-1200 psig. No formal investigation of temperature effects has as yet been made. Data involving temperature effects have been engendered from outside the research program proper. A standard 3-8 mesh, Davison silica gel was utilized for the bulk of the data reported. ‘The program investigated both binary and multi-component mixtures. The lean gas was commercial gas for town supply and was the effluent from 2 high propane recovery gasoline plant. Periodic analyses of this gas showed that it contained a negligible amount of butanes plus and very little propane. The desired amounts of condensibles in this gas were obtained by a carefully calibrated injection pump capable of injecting three liquids simultaneously. All data represent substentially new gel. Regeneration and cooling was with the very lean pipeline gas land bed preloading was negligible. In every case the bed was regenerated at a superficial velocity of about 10'ft. per min. to a final temperature of 490-S00°F. Although the research program has furnished a clear insight for the first time into dynamic hydrocarbon ‘adsorption behavior, there are many aspects that need further clarifiction. This program is, therefore, being continued, The design criteria outlined are necessarily based oa data now available and may be revised and improved as more data become available. It is, however, a significant improvement over existing methods. ‘The method outlined is based on the following: 1. The adsorbing tower will be switched at the time the pentane adsorption zone front reaches the bottom of the tower, (0) 2, Essentially ell of the pentanes plus have been adsorbed up to the time @,. 3. A three tower unit with regeneration and cooling as shown in Figure 2.15 is to be used Although the specific calculation procedure has been set up for a three tower arrangement, it could be easily modified for other systems. A. Basic Design Considerations ‘The design depends upon predicting what the concentration of each component is on the bed at any particular time. From this, a material balance will yield the fraction recovery. The procedure therefore involves the relations of time and distance parameters. Such a relationship must satisfy 28material balance considerations as well as desctibe the rate of mass transfer, In the past this hes been done in many ways, some of which bear little resemblance to the physical process. Unfortunately, most investigators have had too little data to develop a general correlation that could be used with the proper degree of confidence. This is pointed out here solely for the purpose of emphasizing that some of the Published calculation methods are not as useful or reliable as it might appear. One of the significant Secondary edvantages of this research program has been the ability to assess the validity of various models (8). The differences among these models is academic and of little concem to the designer. In order to develop a workable approach that was useful and yet simple, it was found that a combination of the differential material balance, overall material balance and the mass transfer equation (in its simplest form) yielded an arrangement of the measurable variables that was amenable to simple empitical correletion. The method involves showing the concentration change as the ges passes through the bed in terms of both the differential material balance and the mass transfer equation. One solution in terms of senso ft he il {ce 1] see 0 fads 61 where: C+ mol fraction of adsorbate in the entering gas C= mol fraction of adsorbate in the effluent gas k = macs transfer coefficient © = time, min. X,, = equilibrium concentration of adsorbate on adsorbentsIb. per Ib, h, = adsorbent bed length, ft. Yq + superticial gas velocity, ft. per min. ‘The overall material balance is then used, along with breakthrough data to evaluate the key terms in the expression. The mass transfer constant "k"” may be evolved from breakthrough time, vg end h,. ‘A more detailed development of the method is shown in Appendix C. Figure 6.1 is a compilation of data showing X+ as a function of inlet adsorbate concentration. At superficial velocities ranging from 9-45 ft. per min, X is substantially independent of velocity. The Curves shown represent the dynamic saturation of a given component obtained from plots of C/Ce vs. time, for both binary and multi-component mixtures. Even though a few points were substantially off the curve the correlstion was generally excellent. Based on present data Figure 6.1 is considered to be very reliable for design purposes. Figure 6.1(a) is a replot of 6.1 that expresses saturation in volumetric rather than mass units. It is interesting to note that the curves for heptane and hexane would appear to become coincident et larger concentrations. This tends to confirm one of our hypotheses that all peraffin hydrocarbons heavier than hexane have about the same volumetric concentration on silica gel af saturation, In order to compare the static and dynamic equilibrium capacity the data from Figures 2.4 to 2.7 and 6.1 vwere compared and shown in Figure 6.2. As one would suspect, the dynamic cepacity is less. It was surprising however, that the deviation was the same for both hexane and pentane. Apparently the dynamic factors are of the same order of magnitude. This figure should be useful to convert static data to dynam conditions. Figures 6,3 and 6.4 are included even though they do not represent a correlation in the strict sense of the word. The scatter of points is quite pronounced. It should be noted that all points falling near @ ‘curve do not necessarily go with that curve, The dashed lines simply indicate that region in which most of the points correspond to the velocity shown. The curves are presented to show both the gross and relative effect of velocity on breakthrough capacity. At 11 ft. per min. the curves approach dynamic equilibrium but are lower by 2 measurable amount. In effect, the difference represents that part of the bed occupied by the adsorption zone in which full eaturation does not exist. In most calculation methods it is at least implied thet full quantitative displacement of light components by heavy ones occurs. Figure 6.5 shows that this chromatographic effect is not quantitative in the time and under the dynamic conditions used in the tests. Qualitatively this figure shows that there will be more butane left in the bed than most models show. Since this butane necessarily occupies some of the active surface, the amount of heavier components has to be affected. B. Estoblishment of Cycle Time Step 1. Determine a cycle time for a given gas analysis, flow rate and bed length. Figure 6.6 is designed for this purpose and is based on ©, for pentane being the key factor, ‘The superficial velocity may be found from the following equation; @syQMCRD)CTD 69 2 Pr D’ where: Tp = inlet temperature —°R Pr = inlet pressure — psie. D_ = adsorbent bed diameter ~ ft. superficial velocity ~ ft. per min. 6‘The design is essentially trial and error. In ordinary circumstances vg would be fixed by pressure drop considerations and hr by fabrication economics. If these two are tentatively fixed, Figure 6.6 gives the corresponding cycle time. ‘This figure, although empirical, bears a relationship to Equations 3 and 4 in Appendix C. By the nature of its determination it reflects in a real way the variation of the mass transfer constants with adsorption conditions. Although not shown here, for the method is not as yet operational, we have demonstrated to our own satisfaction that the prediction of mass transfer constants ig feasible and that an equation at least similar to 6.1 can ultimately be substituted for Figure 6.5 Step 2. Estimate the zone length and the fraction of that zone saturated with pentane. Figure 6.7 is useful for estimating zone length hz. It has been found that the zone keeps growing in length until it has travelled about twice the distance of its final stabilized length. ‘This relative effect of hr/hz is shown clearly in the figure. Where the proposed h+/hz > 2.0 the pentane zone length for hr = 14.75 ft. should be used in design. This represents the hz at the ©, previously found. ‘The table in the top portion of Figure 6.7 shows a series of conection factors for particle size, Smaller gel particles shorten the zone and therefore increase pentane saturation at breakthrough. The 3-8 mesh gel used for the bulk of the investigation hod a weight average size of 5 mesh (Tyler Screen Scale). Figure 6.8 shows the fraction of the zone (F) in Figure 6.7 that is saturated with butane. The points used to establish the lines in this figure are fairly scattered and the precision is not as close as desired. However, a series of sample calculations using this figure showed that lack of precision in this value had little effect on predicted recovery. Step 3. Predict the quantity of the components on the bed at ©, for pentane. ‘The amount of pentanes, hexanes and heptanes plus may be found as follows: Q-4%, where: q = lb./min. of component entering the bed = (1.83) x(MMCFD) (Mol wt) Cos mol. fr. of component in entering ens. Mol. Wt, = molecular weight of component. The amount of butane may be found from the equation: Q=hz Af eo X+F where: Q = amount of component adsorbed to time @, (butane) hz = pentane zone length, ft. A « cross-sectional area of bed, 1 sa. ft. Bo = bulk density of silica gel « 45 1b. per cu. ft. X+ = Saturation value for component (butane), 1b. per tb. F = fraction of bed length covered by adsorption zone ‘The appropriate Xr for butane is obtained from Figure 6.1, hz (for pentane) from Figure 6.7 and F (for pentane) from Figure 6.8. For purposes of this calculation the isomers of butane and pentane can be lumped together in the inlet analysis. Use a silica gel bulk density ( 4s) of 45 Ib. per ou. ft, Step 5. Cross-check bed weight. ‘The bed weight corresponding to the essumed vg end hy is: Woe .785D? Zehr One can also estimate the bed weight needed to adsotb the total amount of components in tine 1\e w a2 100 2x where: Q; = amount of any one component adsorbed to time Oy. Xrj+ saturation value for each component found from Figure 6.6 ‘The sum represented by the above equation is the total weight of bed required (Figure 6.1). Step 6. Adjust vessel diameter and/ot length until W's = We within limits imposed by fabrication economics. In doing this the relationship between D and vg expressed in Step 1., for @ given flow rate, is used. ‘The above procedure will design a bed to adsorb substantially all of the pentanes plus in the gas. It assumes no water loading, To the length hr, found as above, must be added sufficient Tength to accommodate the mass of gel needed for water vapor adsorption in time ©. This letter amount of gel may be found using the methods described in Section V, Steps 1-4. For 7all practical purposes this method of adding hydrocarbon plus water lengths is very satisfactory. The water adsorption zone is very short and water displaces hydrocarbons almost quantitatively, C. Special Considerations Circumstances can arise wherein the cycle length may be different from the pentane breakthrough time. Figure 6.9 is designed to predict different frontal positions Tor such cases. The zone front velocity (vz) showa is based on a number of different analyses. No data points are shown but an excellent correlation was obtained. This corelation is particularly useful for analyzing existing plants, where the cycle length end , for pentane do not coincide. The value (04) fora given length of bed may be found (at @ siven velocity). If the eycle time is different than ©, for pentane the zone positions may be usted using Figute 6.9. Using the normally good assumption that zone length, as found fom Figure 6.7, still applies, the saturation of each component may be determined. Many towers row in existence are too short for optimum recovery, which means that in these plants at least a portion of the pentane zone has left the tower before the end of the cycle. D. Regenerat 7 ‘The design of the regeneration and cooling portion of the cycle involves using the least amount of ges necessary to heat the gel and desorb water and hydrocarbons. To furnish the necessary design data over 40 runs were made st varying flow rates. Each bed was heated to a terminal temperature of 480—S00°F. A continuous temperature profile was obtained at 8-10 points throughout the tower. Only the outlet temperature is used in the calculation method presented since that is all that is normally availeble. The regeneration gas entered the unit at about 600°F. in all cases. Figures 6.10 and 6.11 are typical of the results obtained. The latter is probably more typical of ommercsi units since i contains heplare: itis iaveresting to ole thal rene obd pentane decor fairly rapidly even though the temperature in their part of the bed is relatively low, The absolute analyses are, of course, fairly high because of the relatively low gas flow rate. In order to further clarify the mechanism, the time-temperature axes were cross-plotted and typical results are shown in Figure 6.12. There may be quite a difference in the vertical displacement of the curves due to variations in bed saturation and regeneration gas flow rate. However, the character of the curves is surprisingly uniform for a given component, The balk of the adsorbed components, through heptane, ace gone by the time the temperature reaches 360°F. The rest of the heat is needed to remove the “heel” from the bed. From previous data itis knovin that the bulk of the water comes off between 240-275 tis probable, although not tested in the research program, that the addition of water vepor to the Fegeneration gas, once the bed outlet temperature reaches 300°F., would accelerate desorption, reduce regeneration time temperature requirements and improve condensation efficiency. ‘As a means of developing @ calculation, a composite curve was made of all runs, with outlet euperoiure being piotied versus relative Ume. The curve showa in Figure 6.13 ie the result. It has surprisingly litle change with regeneration gas flow rate and bed saturation. An examination of all data shows that the bulk of all desorption occurs during the first 50% of the cycle when the gas temperature is varying from about 100°F. to 360°F, This represents the period of highest heat Toad. yn and Cool ‘The heats of desorption of the various components are as follows: Component Allads, - BTU./Ib. Propane 186 i-Butane 178 n-Butane 195 i-Pentane 173 n-Pentane 192 n-Hexane 190 ‘A value of 200 BTU. per Ib. of adsorbate is suitable for design purposes since it introduces 9 Slight safety factor. This is about 33% higher than the average latent heat of 150 BTU. per Ib. The heat of desorption of water from silica gel may be estimated as 1350 BTU. per Ib. The sensibie heat of silica gel is 0.22 BTU./Ib. °F. Step 1. The total heat load for the critical 50% of the cycle is, therefore, equal to: Gb, of each component adsorbed x heat of desorption) 4 (weight of desiccant bed x 0.22) x (360 ~ initial bed temperature) + (0.10 x sum of above to account for line and insulation losses). This calculation assumes effective internal insulation of the vessel. Step 2. Regeneration gas flow rate. ‘The regeneration gas flow rate mst be such that in time (0.5) it will give up an amount of heat equal to that calculated above. Figure 6.13 shows that fhe gas gives up its heat at a 28Lime average temperature of 180°R, for the first half of the cycle. The necessary flow rate is found from the following equation: (0b. gas per min.)(0.5 0,) ( H between inlet temp. and 180°F.) = Heat Load calculated above. Figure 6.14 has been prepared to facilitate this computation where the gas enters at 600°F. Using Figure 6.14 to determine the BTU./100 Ib. gas the necessary regeneration gas flow rate, can be found from the following: MMCFD=_________HeatLoad 6.14 (0.268) (Sp. Gr. gas) (0,) (BTU./100 Ib. gas) Ifthe cycle time is different than the breakthrough time for pentane, the actual cycle time may be substituted in all of the above equations for ©... Step 3. Cooling load. The cooling load may be found from the equation: Cooling load = 1.10 (Wt, of bed) (0.22) (Initial temp. — tinal temp) If the same gos is used for both heating and cooling, some compromise is needed in flow rate since the cooling load is smaller. To prevent over-cooling and thus minimize preloeding, the tower being cooled should be bypassed if its temperature reaches 130-150, before the heating tower reaches its desired temperature. Colculation of Recovery Inasmuch as the components are desorbed at different rotes, the analysis of the gas going to the high pressure separator will vary with time. The liquid in the stock tank will be @ composite of that formed during @ eycle. A flash calculation may be simplified by recombining the leas regeneration ges with the total Liquids adsorbed to find a pseudo-overall analysis. A preferable approach is to divide the cycle into several parts and calculate a recovery for each part. The sum of the parts is the composite quantity per cycle. From the data available it is estimated that the following represents the va during each third of the cycle: tion of desorption Wt. Fr. of Adsorbed Component Desorbed Butane Pentane Hexane Heptanes Plus First thitd of cycle 9 50a 0 Middle Third 5 0 56 89 Last Thied 0 0 2 uw ‘The above percentages, although approximate, appesr to be reasonable representation of desorption behavior and very suitable for the intended purpase. For the flash colculation utilize the stendatd equation: Kismat Vea ae 1.0 62 where: Xj = mol. fraction of any component in the feed stream. K = vaporization equilibrium ratio (constant), V = mols vapor off sep: L = mols tiquid off separator in same time as V mols of vapor leave. X_» mol. fr, of any component ia the liquid leaving, The standard procedure is Step 1. Establish the value of Xj for each component from the regeneration gas analysis, its flow rate and the rate of desorption shown above: Step 2. Assume V/L. Step 3. Look up K values at separator P and T Step 4. Calculate X for esch component and cumulate. If sum of X's = 1.0, the correct V/L has been assumed, If not, assume new V/L and tepeat Steps 2-4 until it does. Figures 6.15 (a) to (¢) are convenient K charts designed specifically for separator calculations ‘on hydrocarbon liquids. They are composite charts based on all actual data published in the literature. In the range for which they were designed (to 1200 psig.) no convergence pressure correction is needed since they are based on actual data from the types of systems encountered ‘These charts are conveniently arranged by temperature to facilitate their use. Table 6.1 shows selected values from the charts to further enhance the convenience. tor. 29Table 6.2 shows K values for the heaviest fraction as a function of mean average boiling, point (MEP). The values shown were extrapolated using plots of In K vs. T prepared from the K data, Figure 6.16 furnishes @ means of predicting MBP from the molecular weight and specific gravity of the heavy fraction. If stage separation is used in flashing the high pressure separator liquids to the stock tank, the middle stage pressure has a noticeable effect on stock tank recovery. The best way to ‘optimize this pressure is by means of a compater program. Figure 6.17 is a suitable substitute. In general, the second stage pressure should be between 60-75 psig. Table 6.3 summarizes convenient factors for use in adsorption calculations. Summary ‘The above data and design recommendations are based on the most intensive research effort ever carried out in the field of hydrocarbon adsorption. This work is continuing. It is believed that the information presented represents « significant improvement in knowledge of this process. Thus it contributes to more quantitative design. The purpose has been to furnish a firm but flexible basis ‘so that equipment designers can best utilize the information for their convenience and/or needs. ‘As mote data are obtained, the above procedures will be modified and improved. 30‘syeyo enpea-paoows ayy wor Apoanyp was 9c0: siso: soo oneo"saeu: aan: oem eyo”: co cot Teco grey eee tee aE overeH seo Bao" to” Sat0" camo Toso Se bg oreo" 6520" 0sL0" Oszo" = OLz0" 0640" ‘180° 9E60" orl Sbte Sse" ozt omnyn Qe; sso" HsD: aso: eso”. ovao: nates. 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Yad LN3NOdWOd “87 ° a ow “erg “Big 3006 8B viSd OO8 tv 139 voITIS Jo ALIOVdVD WhissITiNoOs OIWWNAG SVO NI LN3NOdWOd % TOW 2 on s o v Yad LN3NOdWOD V9 739 9871 001COMPARISON OF DYNAMIC AND STATIC EQUILIBRIUM FOR BINARY MIXTURES OF COMPOUND AND LEAN PIPELINE GAS, AT 800 PSIA AND 90°F a | somes i ES n ny cee n ° @ i a | | B | STATIC EQUILIBRIUM - LBS PER 100 LBS SILICA GEL L °O 2 4 6 8 OF i2 tea Gr eH eOr ee: DYNAMIC EQUILIBRIUM-LBS PER 100 LBS SILICA GEL Fig. 6.2eo “br SVO NI 3NVX3H % 70W 31 vl 21 on z T ] | | | i “i F206 8 visa TT] 008 av ‘Hsaw 9-¢7485 od? 30vH9_ ST | HONOYHAVaNE Affi 4v 3NYX3H JO NOlLWUnivs Sf it FEE fate - yy i / | yi | if ti - . tt ! H ioe / NIW/L4 Ob / + ALIDOTBA | TWIDISNBENS / fan NIW/L4 te I cee a + ra} vt 43d 3NVX3H 87 HONOYHINVING Lv 139 VOITIS S87 OO!9 613 SVO NI 3NVLN3d % OW 8 1 vl 21 ol 8 9 v 2" 2, i 1 Gh | | ZI | | AOL7 “LG | gE Ee TE eee el {Isis enter a 2 | So oe ee | fp A07 SL | NIN /L4 Ob Sea aeeeeereee eee ee Peeeeeeeea De “ALIOONBA Aidisyasdns — eed ZL [oes anion pe nr + i : Eee eee 4 Seta aT ie i NIW/L3 SE™ 0 OU 4 \ | t a Zz | be ae re 7 a t 9 | cal Z i tee rere) 2 ' erred | I = { { 7 EQUILIBRIUM CONSTANTS 1,001] —— ~~ 100° F au T | 1 i | | Leen be ah ot tet 2.00015 : was TTT | 10 100) PRESSURE, PSIA Fig. 6.15 (b)199000,-—— 1000). - %, CONSTANT, EQUILIBRIUM Lol 0.00015; 10 100 PRESSURE, PSIA Fig. 6.15 (b)10000) 1000) 100} 2 2 0.01 EQUILIBRIUM CONSTANT "Kk" 1,001 0.0001 ol EQUILIBRIUM CONSTANTS 120° F 0 100 1000 PRESSURE, PSIA Fig. 6.15 (c) 10000WEIGHT MOLECULAR MBP OF LIQUIDS AS FUNCTION OF MOLECULAR WEIGHT AND a GRAVITY , 160}; _ 140 120 100} 14115 80} M20 = 1.0) © 935754, °APr— | 200 250 300 MEAN AVERAGE BOILING POINT Fig. 6.16 350 (MBP) - °F 400DIMENSIONLESS CONSTANT (A), 0 OS 10 153.5 353.0 SPECIFIC GRAVITY OF FEED, DIMENSIONLESS FOR LIQUIDS HEAVIER THAN WATER P2 = A(P1)°-8854 C WHERE c = A+0-057__ 0.0233 FOR LIQUIDS LIGHTER THAN WATER A+ 0.028 P2e=A(Pi)0-765 4 C' WHERE C! = 0.012 Pi = PRESSURE OF FIRST STAGE SEPARATOR P2= OPTIMUM PRESSURE OF SECOND STAGE SEPARATOR {THIRD STAGE IS STOCK TANK AT 14.7 PSIA) A MEANS OF ESTIMATING OPTIMUM SECOND STAGE PRESSURE IN THREE STAGE SEPARATION OF HYDRO- CARBON LIQUIDS. Fig. 6.17NOMENCLATURE rN = cross-sectional area of desiccant bed Co = mol fraction of any component in entering gas. D = desiccant bed diameter, ft. Dp = average desiccant particle diameter, ft F = mols of inlet gas per unit of time (in flash calculation only) F = fraction of adsorption zone not saturated with component comprising zone 6 = mass velocity of gas, Ib. per hr. sq. ft. Ge = mass velocity of gas, 1b. per sec. sq. ft. & = acceleration due to gravity, ft. per sec.* b = distance from top of bed he = desiccant column length, ft. hy = effective bed length by = adsorption zone length, ft. vaporization equilibrium ration (constant) K k = mass transfer constent L = mols of liquid per unit of time (in flash calculation only) = tower length (normally head! seam to head seam) MMCFD = million standard cubic feet pet day (at standard pressure and temperature) M.W. = molecular weight of component N 1b, mols of gas per unit of time Pe = pressure, psia Pr inlet pressure, pie bp difference in the partiel pressure of water in the gos and on the silice gel q mass rate of any component entering, 1b. per min GQ = mass of sny component on the bed at any time, Ib. R = gas constant (10.71) T = absolute temperature, °R. CF. +460) % inlet temperature, °R v mols of residue gas per unit of time v volume rate of flow per unit of time at operating conditions v mols vapor off separator, in flash calculation vg = superficial gas velocity, ft. per min % ——_-Feffective gas velocity W water content of silico gol (normally 1b. water/Ib. silica ge!) Wo = bed weight, Ib x nmol fraction of any component in Liquid leaving (flash calculation) x mass of component on bed per unit mass on bed 35xy = mol fraction of any component in feed stream x = mol fraction of each component in high pressure liquid = equilibrium capacity of adsorbent, Ib. per Ib. adsorbent Xr XT ve = mol fraction of each component in feed Ww = mol fraction of each component in residue gos Zz = gas compressibility factor Greek Symbols “A = constant porosity (packed bed density/absolute density of silica ge!) ¢ Tr = pi @.1416) P 3 — = desiccant bulk density, Ib. per cu. ft. Pq = ess density (ectual), Ib. per eu. ft Oo =tine Q-p = breskthrough time, min. QE = time for bed to become saturated with adsorbate 36BIBLIOGRAPHY Hougen, 0. A. end B. F. Dodge. Ledoux, Edward, Chemical Engineering, March, 1948. Simpson, E. A. and W. P. Cummings, Chem. Eng, Prog., 60, 4, 1964, 87. Meson, J. P, and C. E. Cooke, Jr., to be presented at AICHE meeting in Boston, Massachusetts, December 6-10, 1964, Brunauer, S., P. H. Emmett and E, Teller, Jour. Am. Chem. Sec., 60, 1938, 309. Hill, T. L., Jour. Chem. Phys., 14, 1946, 268. Wander, J. W. J., Oil Gas J., August 6, 1962, 137. Needham, R., J. M. Campbell and H. O. McLeod, Presented at AIChE meeting, February, 1 Tennessee. 37APPENDIX AAPPENDIX A SUGGESTED GAS, OIL AND CONDENSATE SAMPLING PROCEDURES* ‘The purpose of this discussion is to present specifications for sampling equipment and procedures which, if followed, will minimize the chances for error from this source. These specifications are based on extensive experience in obtaining samples and analyzing them in the laboratory. ‘The procedures are based on the usual separation facility available. If a metering separator is available, measurement of the gas — oil ratio is direct. Even though chromatographic analysis and other newer techniques require smaller samples than fractional analysis, it is recommended that the larger samples be taken in the field so that small amounts of contaminants or small errors in sampling will have less effect on the final sample accuracy. Also, standardization of cylinder sizes has practical warehousing advantage. Water displacement is recommended as a preferred procedure even though evacuation can be satisfactory in the hands of a skilled sampler. It is relatively fool-proof and requires no vacuum pumps. Further- more, it facilitates taking composite samples over a finite period of time. Since many wells produce tendom quantities of liquid and gas, some kind of a time average composition is often desired. The Tiquid displacement rate can be adjusted so that a sample is obtained over @ period of hours. In such « case it is necessary to obtain a corresponding composite gas ~ oil ratio. Special stainless steel and other alloy sample bombs which are suitable for corrosive gases are available commercially. They are suitable replacements for those shown but should be printed and tagged as specified, If sample size is critical, @ 10 ~ 30 cc. sample is sufficient for most chromatographic woi Sample Bombs ‘Sampie bombs should be classified in two separate and distinct categories, GAS and LIQUID, and should not be interchanged except in case of emergency. Gas Sample Bombs (Recommendations) Vessel Size. Sample bombs should be extra-heavy seamless pipe whose ends are closed either by by (@) extra-heavy swages reducing to 4” pipe diameter, threaded {4"" NPT, or (b) by extra-heavy pipe caps which have been drilled in the center to accommodate '4"" x 3" extra-heavy pipe nipples welded to the caps. Length of the pipe section of the gas sample bombs should be 2" ~ 0"; i.e., the head-seam to head- seam length. Gas sample bombs should be made in two (2) diameters, 2-3/8" 0.D. (1.939” LD.) and 3-1/2” 0.D. 2.900" L.D.). ‘The 2-inch bombs may be used for taking gas samples at pressures between 225 and 3000 psig. Velves. Each of the nozzles of each bomb should be fitted with a %é"" Metric (or equivalent) Forged Steel Needle Valve, straight pattern, using an ofl or gasoline insoluble thread dope. Paint, Gas sample bombs should be painted ALUMINUM between the round-about weld seams, and the caps or swags should be painted RED. Stencils. Each gas sample bomb should have stencilled in RED the following information on the ALUMINUM-painted shell portion of the bomb: Gas Max. W.P, = mxxx psig. Crates. Sample bombs should be stored and shipped in wood crates, built to contain either two (2) ‘inch bombs or two (2) 3-inch bombs, and should be fitted with either two or three cradle-clamps; the uppet clamp being attached to the hinged and hasped lid. The lid should be fitted with a suitable carrying handle; also a sheet metal plate with the following designation stencilled thereon: CAUTION! NATURAL GAS SAMPLE, KEEP FIRES AWAY! © Based on material originally prepared by Laurance S. Reid a2Liquid Somple Bombs Vessel Size. Liquid sample bombs should be made precisely as specified for gas sample bombs, except that they need be made in 2-inch diameter only for fractional analyse: Volves. Valves for liquid sample bombs should be as specified for gas sample bombs. Point. Liquid sample bombs should be painted red only, so as to be easily distinguished from the 88 sample bombs, both in the field and in the laboratory. Stencils. Each liquid sample bomb should have stenclled in ALUMINUM, on the RED shell, the following information: Liguip Max. W.P. = xxx psig. Crates. Crates for liquid sample bombs should be identical in all respects to those built for 2-inch gas sample bombs. This will permit equilibrium samples of gas and liquid to be shipped in the same crate. General Note. A 2-inch liquid sample bomb may be used at any pressure up to the safe working pressure of the tomb, stencilled on its side. A very small liquid sample, not exceeding 50 cc., is all that is required for fractional analysis, but the additional volume provided by the 2-inch bomb is essential and will be discussed below. Low Pressure Gos Samples Gas somples collected at pressures less than 90 psig. should be taken by water displacement at atmospheric pressure in a S-gallon drinking water bottle. Such # sample bottle need not be painted in any manner, but it must be crated for shipment in a wood erate built for that specific purpose. Such a crate should have a hinged lid fitted with a standard door hasp. SAMPLE BOMB PREPARATION follows: to taking samples, all sample bombs, both gas and liquid, should be prepared 1, Plece in vertical position and open bottom valve to relieve all pressure and drain all free liquid. Open top valve after pressure is dissipated. 2. All bombs from which colored oil or liquid has been drained must be sun half-full of kerosene, ‘agitated thoroughly and drained. Replace with clean kerosene and repeat until the kerosene is no longer showing any color. 3. All hombs treated with keros: in Q)a id be ght, ‘or water-white condensate, agitated thoroughly to dissolve the kerosene, and carefully drained. Repeat this step if the drained liquid seems unusually oily. 4. Place bombs in a vertical position and, by any suitable means, flow fresh, clean tap water upward through the lower valve SLOWLY. DO NOT JET! Watch the overflow until the fluorescent oil film disappears, then (1) close the boitom valve ‘and (2) close the top valve, leaving each bomb full of water which will be displaced later when the sample is taken. 5. Replace the long hex 44"? plugs in the valves of each bomb and STORE IN A COOL PLACE. CAUTION! WATER EXPANDS WHEN HEATED AND, WITH NO GAS CUSHION, THESE BOMBS COULD BE OVER-PRESSURED IF ALLOWED TO GET TOO WARM. 6. PREPARE YOUR OWN BOMBS FOR SAMPLING! DO NOT ASSUME THAT THEY HAVE BEEN PREPARED FOR YOU, FOR CHANCES ARE THAT THEY HAVE NOT! WHERE TO SAMPLE Poor choice of sampling points is @ frequent source of error in determining the composition of a gas stream and, to a lesser extent, the composition of a hydrocarbon liquid. Certain generalizations can be made which will be helpful in making these selections. Bear in mind the fact that there is some combination of pressure and temperature at which condensation will occur in @ ges stream, and that virtually all production from ges, or gas-distillate wells contains liquid along with the gas. It has been found that a substantial portion of this liquid moves along the walls of the pipe while the gaseous phase travels the center portion. In other words, when considering, the cross-section of the pipe, the liquid concentration near the pipe walls is much greater than at the center. If a sample is taken in the line between the well head and the separator, the liquid clinging to the pipe wall will tend to eater the sample line out of proportion to its quantity in the ges stream. This reduces the reliability of sample probes as well as samples from the shell of @ separator.‘The true composition of the stream can be obtained by taking @ gas sample immediately downstream from @ separator, a liquid sample from the bottom of the separator, and @ measured ratio of the amount of liquid accumulated in the separator per MFC of separated gas, These two samples are then analyzed fand their compositions are recombined in proportion to the measured gas-liquid ratio to determine the true composition of the gas-liquid stream entering the separator. ‘The separator samples cited above are known as “equilibrium samples". In this connection several important points should be noted: ‘Wake sure that pressure and temperature are constant when samples are obtained and ratios measured, 2. Equilibrium samples are of little value unless the gas-liquid ratio is accurately measured! 3. The gas sample must be taken from a point close to the separator but downs extractor: De not take the gas semple at any opening in the sepé 4, All wells make some free water. The rate of water accumulation must be measured separately and subtracted from the total liquid accumulation rate. In general, the best sample point for the gas phase will probably be found at the orifice meter manifold. Take the meter out of service by opening both valves on the manifold bypass and connect the sample bomb to the manifold bleeder valve. ‘The liquid sample is obtained from the liquid-level gage glass on the seperstor AFTER THE WATER IS BLED OFF THROUGH THE BOTTOM DRAIN. Free water is withdrawn into @ bucket and measured for a chosen time interval. ‘Total liquid accumulation is measured by noting the time required for the liquid level to rise two or three inches in the separator gage glass WITH THE OIL VALVE DISCONNECTED AND SHUT TIGHT! Calculation of the gallons accumulated per unit of time depends on the calibration of the liquid volume of the separator section at the point where the rise is measured. In a vertical separator, this can be calculated from accurate measurement of the outside circumference of the seperator shell, the shell thickness as taken from the nameplate on the vessel, and by operating during the accumulation period with the Liquid level float raised out of the liquid. It'is also important to note that the liquid rise should be measured low in the glass so as to make sure the section is uniform; i.e., below the float pad opening. A calculated calibration of a horizontal separator is more difficult, but it is possible if the liquid ‘accumulation is measured in the risers connecting the upper and lower barrels. Knowledge of the riser diameters and the umber of risers in the separator is required. If it is impossible to calculate the separator volume for any ' of the data specified above, the only alternative is to shut in, depressure and drain the separator, partially fill it with water and measure the water out while marking the calibration on gummed paper strip stuck to the gnge glass. Ifa liquid sample is desired, make sure that you ate obtaining the hydrocatbon liquid end NOT WATER! Bypass the meter manifold and connect a suitable length of tubing to the bleeder valve located on the manifold. Connect the other end to a tubing connection made up in the top valve of the sample bombs, Which is suspended in @ vertical position, but leave the tubing nut hand-tight for the moment. Then follow this procedure: 1. Open the bleeder valve slightly, allowing enough gas fo flow through the tubing to purge the air it contains. 2. Tighten the tubing nut with a wrench and allow the pressure in the tubing to build up to line pressure. 3. Open the bieeder vaive and the top valve on the bomb completely and tighten the packing nuts if gas leaks are observed. 4. Crack the bottom vaive on the sample bomb and allow the water to bleed off SLOWLY. Take at least five minutes to discharge the water. 5. After the water is discharged, let gas continue to flow through the bottom valve at the same rate for at least 15 or 20 minutes more, 6. DO NOT LET GAS EXPAND INTO THE BOMB THROUGH THE TOP VALVE. ALL EXPANSION MUST BE TO ATMOSPHERE VIA THE BOTTOM BOMB. 7. Close bottom valve, close top valve and close bleeder valve in the precise order named. Disconnect tubing, dope pipe plugs with soap and make up tight in both bomb valves. Tighten valve packing ts! AA8. Head for the nearest water tonk, slush pit, or puddle, immerse the whole bomb and check CAREFULLY for leaks. Take your time with this check and look carefully for minute bubbles. If the gas pressure is low and a 5-gallon water bottle is to be used to take an atmospheric pressure sample, the following procedure applies. Equipment needed includes a rubber stopper, ot a ws impregnated cork to fit the bottle, a fairiy long pierce of rubber or copper tubing, @ 10-quart pal wash tub and a supply of clear, fresh water. Proceed as follows: 1. Fill the bucket or tub full of water and set it adjacent to the sample point. Fill the bottle with ‘water, place palm of hand over opening and invert the bottle immersing neck below water level in bucket or tub. IF AIR BUBBLES APPEAR, TRY IT AGAIN SO THAT THERE IS NO AIR TRAPPED IN THE BOTTLE. 2. Connect tubing to sample valve, crack valve to purge air {rom the tubing, thea pass the free end of the tubing under the water level and up inside the bottle. Gas will then displace the water which will overflow the bucket or tub. 3. Note the time required to displace the water from the bottle and allow gas to pass into the bottle for a peried four times as long. This is necessary to eliminate the effects of adsorption of carbon dioxide by the water. 4. Remove tubing and insert stopper in the bottle while the neck is still immersed. Make sure stopper is tight, then remove bottle from tub. 5. Wire stopper securely to bottle neck and, if possible, dry stopper and glass neck surfaces and coat with wax. Place in crate for shipment. IMPORTANT SOUR GAS NOTE! If stainless stee! cylinders are not available, always take sour gas samples in a glass bottle, regardless of system pressure. H,S reacts with steel making analysis impossible. Obviously, these samples will be at atmospherié pressure. Liquid samples shel! be taken from the liquid level gage glass according to the following procedure: 1, Close gage glass cocks, bleed off pressure, replace drain cock with suitable nipple or swage and @ 14°" bar stock valve. Close drain valve, open both cocks, and bleed liquid from the glass slowly via the drain valve to purge. 2. Connect copper tubing to drain valve and make up other end of tubing hand-tight into top valve of sample bomb. Crack drain valve and allow liquid to purge ait from tubing, 3. Gradually draw up tubing nut until tight. Tum drain valve and top valve on bomb wide open, 4. CLOSE THE TOP GAGE Cock. 5. Crack bottom bomb valve and withdraw the equivalent of a full pint of water. DO THIS SLOWLY, MAKING SURE A LIQUID LEVEL IS ALWAYS IN SIGHT IN THE GAGE GLASS. 6. Close the bottom bomb valve. CLOSE THE BOTTOM GAGE COCK. OPEN THE TOP GAGE COCK. 7. Crack bottom bomb valve and SLOWLY withdraw the remainder of the water. 8. Close the bottom, top valves of the bomb and the drain valve on the gage glass in the order named. Disconnect tubing. Dope pipe plug threads with soap and pull up tight in valves. TIGHTEN VALVE. PACKING NUTS. 9. Test carefully for leaks, under water, as discussed before, 10. Return gage glass on separator to normal service. ‘The above procedure is preferred above all others since it provides sufficient sample at system pressure and temperature for accurate analysis, vastly simplifies laboratory procedure, and insures safety in shipment by providing a substantial gas cap. Be sure to draw water before taking the sample and follow this procedure carefully. With special reference to Steps 6 and 7 in the above procedure, make sure that the liquid level disappears when the bottom gage cock is closed and the top cock opened. Failure to dissipate the liguid level means the bottom cock leaks and the bomb will be filled completely with liquid. This is wholly undesirable, so shut the bottom cock TIGHT! SAMPLE LABELS Wire a shipping tag to one valve of each bomb showing the following information: AS(Well, field, plant, etc.) Sample Point: Pressure: Temperatui Date and Time of Day: Nature of Sample: (Gas or Liquid) Sampled by: If these are equilibrium samples, include with the gas sample data the orifice meter static and differential pressure, the meter temperature, the orifice plate diameter and the diameter of the pipe in which the meter flange is installed. With the liquid sample data, include all data which will permit the rate of liquid accumulation to be calculated. Also include the rate of free water accumulation. CRATING AND SHIPPING Place bombs in special cradled wood crates and wire hasp closed. All samples should be shipped via Railway Express or the equivalent unless special instructions are issued to the contrary. Be sure to advise the agent that you are tendering a ‘Red Lebel”” shipment consisting of oil and/or gas samples under pressure. AsAPPENDIX B BIAPPENDIX 8. SAMPLE SPECIFICATION SUMMARY SHEET FOR ADSORPTION PLANTS Company: Location of Proposed Facility: ——— Purpose of Facility: Dehydration Hydrocarbon Recovery Design Basis (also basis for acceptance tests) Design Flow Rate (MMCFD.): Maximum Minimum Nominal Inlet Temperature CF.): Maximum, Minimum, Nominal —_______. Inlet Pressure (psi¢.): Maximum, Minimam, Nominal —_____. Maximum Allowable Pressure Drop Across Quoted Unit pig. Inlet Gas Anelysis: Component Mol % Nitrogen Hee Oxygen Hydrogen Sultide : Carbon Dioxide Mercapten Methane Ethane Propane Iso-Butane N-Butane Iso-Pentane N-Pentane eae B2Hexanes Heptanes Plus Aromatics 100.00 Molecular Wt. C, +_____, Sp. Gr. Cr + Inlet Water Dew Point CF.): Maximam——_______, Minimum Nominal — Base Inlet Water Content on: (Correlation to be used) Maximum Outlet Water Dew Point: —______ °F. ‘Time-average Outlet Hydrocarbon Dew Point: —____ °F. Specification of liquid hydrocarbon recovery at nominal conditions: Average Reinfall: inches Average Snowfall: ________ inches Wet Bulb Temperature CF.): Maximum, Minimum, Nominal Dry Bulb Temperature (°F.): Maximum_—________, Minimam, Nominal Elevation of Plant; feet. _ Prevailing Wind: Electrical Power Available: Source: KWH of _____ volt _____ phase KWH of —_____ volt — phase Water: ______ gal. per day. Suitable for cooling towers —____, radiators ___ with ____., without ______ treatment. Source of water: BBAll unfired pressure vessels to be constructed, according to: Latest revisions of applicable ASME code no code but static tested to ____ times working pressure no code but “‘hammer tested”? to____. times working pressure NOTES: 1. Where maximum, minimum and nominal values are shown, the nominal value is the one to be used in design as the normal operating condition. 2. In the normal circumstance it is recognized that conditions during any acceptance tests will not agree with those designated above. This in tum will affect any guaranteed recovery. Unless superceded by an agreement made at the time of purchase, it is agreed that the recovery to Satisfy acceptance will be that calculated in exactly the same manner as was the recovery on the above specifications. 3. Attached hereto are pertinent data including: a. A schematic drawing showing the Iocation of the proposed unit in the ‘system and that equipment which preceeds and follows it. b. The best estimate available about future flow rates and analyses, frequency of expected fluctuations in operating conditions, and like items for aid in optimum design. A general description of expected supervision and operating policies and procedures. Signed: Date: Date Quotation Requested:APPENDIX C caAPPENDIX C DEVELOPMENT OF A CORRELATION PROCEDURE A material balance around @ differential slice of an adsorbent bed may be expressed a: 9% do yg do @ 70° 87, where: X = mass of adsorbate on bed per unit volume of bed © = time elapsed from beginning of adsorption C= concentration of adsorbate in ges stream at any point in bed vg = velocity of ges stream (superficial) h = distance from inlet of bed 2x ‘The rate of adsorption,/ ©, may also be expressed by the following equation if one assumes that rate is proportional to the number of “open” sites on the silica gel: 2X = KegX,-¥) 2 Je where: °X, = saturation capacity of the silica gel K = mass transfer rate constant n 2 is substituted into I is: KX,h, in€2 -1 = KCo@+ In TT 3 c One of the possible solutions when Equ: where: h, = adsorbent bed length c. inlet concentration of adsorbate in the gas If the breakthrough time, ®,, is defined as the time when C = 0.05, then, o,+0,- 22% Coy, + oe where: @- 1 in |_fe a Keo | 0.05 Technically Vp should be the actual velocity of the gas in the Tree spaces of the bed which would be a function of the bulk porosity and tortuosity of the flow path. Based on available data the actual velocity ( vg) could be approximated by the equation: vg AD 5 Likewise, because ofthe tortuosity, 4 the 6 here: KM ellective hed length vp = effective velocity = porosity (packed hed density/absolute density) For practical purposes, the above equations may be used with the superficial velocity, vg, the c2difference showing up in the value of “K”". Many other variations in the above approach have been attempted. An overall material balance must also be written at the time when a particular adsorbate’s adsorption zone front reaches the exit of the bed. y= Cod = by AAgKy = Oy -O,)aF 7 °, 0, -trA AX, —@e - 0) F a where: Qe ~ total amount of adsorbate adsorbed on bed 4 = fate of input of adsorbate to adsorption tower A = cross-sectional area of bed Pa = packed density of bed x = time for bed to become saturated with adsorbate (end of zone leaves bed) F = fraction of bed length covered by adsorption zone, h,,'that is not saturated with the adsorbate ‘The term @ (Og — Og) = hy AAX~- In essence, therefore, the second term on the right hand side of Equation 7 simply prorates the concentration in the bed volume occupied by the adsorption zone. This is not the way in which it physically occurs even though the equation expresses a valid equivalency. ca