Offshore Hydrate Engineering Handbook

a manuscript funded by ARC0 Exploration and Production Technology, Co.

E. Dendy Sloan, Jr. Center for Hydrate Research Colorado School of Mines Golden, Colorado 80401 assisted in production by M.B. Seefeldt

January 1, 1998

Table of Contents
Topic

Table of Contents

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..ii

Disclaimer and Acknowledgements.

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.v

Introduction ..........................................................................................................

1

I. Safety First: A Gallon of Prevention is Worth a Mile of Cure.. _.

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1

II. Prevention by Design: How to Ensure Hydrates Won’t Fog

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5 .6

A. Where Do Hydrates Form in Offshore Systems?. ....................................

B. A One Minute Estimate of Hydrate Formation (Accurate to *SO%). ....... .l 1 C. A Ten Minute Estimate ofFormation/Inhibition (Accurate to &25%).......12 1. Hydrate Formation Conditions by the Gas Gravity Method.. ........ 13 2. Estimating the Hydrate Inhibitor in the Free Water Phase ............ .14 16 3. Amount of Inhibitor Injected Into Pipeline .................................. 16 ............................................... a. Amount of Water Phase.. b. Amount of Inhibitor Lost to the Gas Phase ..................... .17 c. Amount of Inhibitor Lost to the Liquid Phase ................. .17 4. Example Calculation of Amount Methanol Injection .................... .17 .20 5. Computer Program for Second Approximation ........................... D. Most Accurate Calculation of Hydrate Formation/Inhibition. ................. .23 1. Hydrate Formation and Inhibitor Amounts in Water Phase ............ 23 2. Conversion ofMeOH to MEG Concentration in Water Phase........2 5 .25 3. Solubility of MeOH and MEG in the Gas .................................... 4. Solubility of MeOH and MEG in the Condensate ......................... .26 5. Best Calculation Technique for MeOH or MEG Injection ............ .26 E. Case Study: Prevention of Hydrates in Dog Lake Field Pipeline ............. .30 F. Hydrate Limits to Expansion through Valves or Restrictions ................... . 1 1. Rapid Calculation of Hydrate-Free Expansion Limits. .................. .33 2. More Accurate Calculation of Hydrate-Free Gas Expansion..........3 4 3. Methods to Prevent Hydrate Formation on Expansion ................ ..3 6

ii

G. Hydrate Control Through Chemical Inhibition and Heat Management .... 1. Inhibition with Methanol or Mono-ethylene Glycol.. ................... a. Methanol ...................................................................... b. Monoethylene Glycol.. .................................................. c. Comparison of Methanol and Glycol Injection ................. 2. Kinetic Control by Anti-Agglomerants and Kinetic Inhibitors ....... a. Anti-Agglomerants.. ..................................................... b. Kinetic Inhibition ........................................................... 3. Guidelines for Use of Chemical Inhibitors.. ................................ 4. Heat Management.. ................................................................... a Insulation Methods.. ...................................................... b Pipeline Heating Methods.. ............................................ H. Design Guidelines for Offshore Hydrate Prevention ...............................

..4 1 .42 .42 .44 .45 .45 ..4 6 .47 ..5 0 .53 ..5 4 ..5 5 .55

III. Hydrate Plug Remediation.. ...........................................................................

..5 8

A. How Do Hydrate Blockages Occur?. ................................................... ..5 9 1. Concept of Hydrate Particle and Blockage Formation ................. .59 2. Process Points of Hydrate Blockage.. ...................................... ..6 1 B. Techniques to Detect Hydrates.. ........................................................... .62 1. Early Warning Signs for Hydrates ............................................. .63 a. Early Warnings in Subsea Pipelines.. ............................... ..6 3 b. Early Warnings Topside on Platforms .............................. .66 2. Detection of Hydrates Blockage Locations.. .............................. ..6 7 a. Inhibitors or Mechanical/Optical Devices. ......................... .68 b. Pressure Location Techniques ......................................... .69 c Measuring Internal Pressure through External Sensors ....... .72 d. Recommended Procedure to Locate a Hydrate Plug .......... .73 C. Techniques to Remove a Hydrate Blockage.. ........................................ ..7 4 1. Depressurization of Hydrate Plugs.. .......................................... ..7 4 a. Conceptual Picture of Hydrate Depressurization ............... .75 b. Hydrate Depressurization from Both Sides of Plug ............ .77 c. Depressurization of Plugs with Significant Liquid Heads.....8 3 d. Depressurizing One Side of Plug(s) ................................. .85 2. Chemical Methods of Plug Removal. ......................................... ..8 8 3. Thermal Methods of Plug Removal.. ........................................ ..8 9 4. Mechanical Methods of Plug Removal.. ..................................... ..9 0 D. Avoiding Hydrates on Flowline Shut-in or Start-up ............................... .91

E. Recommendations and Future Development Areas ................................. 1. Recommendation Summary for Hydrate Remediation .................. 2. Recommendations for Future Work.. ..........................................

.93 .93
.94

IV. Economics ..................................................................................................

..9 5

A, The Economics of Hydrate Safety.. ...................................................... ..9 5 B. The Economics of Hydrate Prevention.. ................................................ .95 1. Chemical Injection Economics.. ................................................. .95 a. Economics of Methanol and Mono-ethylene Glycol... ........ .96 b. Economics of New Types of Inhibitors.. ............................ 98 2. Heat Management Economics.. ................................................. 100 a. Economics of Insulation.. ............................................... 100 C. The Economics of Hydrate Remediation .............................................. ,101

Appendix A. Gas Hydrate Structures, Properties, and How They Form.. ............... .I03 1. Hydrate Crystal Structures.. ................................................................ 103 2. Properties Derive from Crystal Structures.. ......................................... ,104 a. Mechanical Properties of Hydrates ............................................ ,104 b. Guest: Cavity Size Ratio: a Basis for Property Understanding ...... 105 c. Phase Equilibrium Properties.. .................................................. ,106 d. Heat of Dissociation ................................................................ ,107 3. Formation Kinetics Relate to Hydrate Crystal Structures ...................... ,107 a. Conceptual Picture of Hydrate Growth. .................................... .I07

Appendix B. User’s Guide for HYDOFF and XPAND Programs.. ........................ B.l.HYDOFF.. .................................................................................... B.2. XF’AND.. ......................................................................................

,109 .I09 ,123

Appendix C. Additional Case Studies of Hydrate Blockage and Remediation..

128

Appendix D. Compilation of Rules-of-Thumb

in Handbook .................................

.I45

References ........................................................................................................

149

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Dr. Mr. Carl Argo and Chris Osborne (Sunbury) and particularly Dr.) kindly provided the most detailed North Sea case study. Phil Lynch (ARC0 British Ltd.J. the student worker who aided in production of the figures. While every effort has been made to present current and accurate information. British Petroleum contributed heavily through Drs. Conoco’s Mr. George Shoup and J. Other contributors order by company: who have contributed generously are listed in alphabetical Amoco’s Mssrs. Use of the information in these notes is solely at the risk of the reader. Mr. and he provided access to offshore engineers. This work to Mr. and IIA) were made available to this project.DISCLAIMER The description. methods. Xiao provided hydrate plug transientflow simulation results and they reviewed the preliminary draft. Pat Shuler generously contributed his spreadsheet program HYDCALC to determine inhibition amounts. This manuscript was intended to supplement. ACKNOWLEDGEMENTS The by Mr. but not to replace engineering judgment. John Cayias of Oryx Energy contributed by providing for visits to offshore platforms and by providing travels funds and funds for Mr. Bloys’ continuous contributions. Tony Edwards (Dimlington). has provided an invaluable supplement to the manuscript. the author (and sponsoring and contributing organizations) assume no liability whatsoever for any loss or damage resulting from use of the material in this manuscript. Ben is a paean engineering. Cayias’ questions have been very useful in re-thinking and re-stating the concepts summarized in the handbook. The power of a multi-company consortium. Carl Gerdes reviewed the guidelines for safety. in addition to Mr. Bloys’ foresight regarding the state of knowledge in hydrate coupled with intelligence and a magnanimous perspective. At ARCO. Seefeldt. who related North Sea commercial operating experiences with new inhibitors. idea for the Handbook was conceived Bloys of ARC0 Exploration and Production Technology Co. II. Dr. and operation. Chevron’s Dr. state. Dr. or municipal regulations. Two others have been fundamental to the project. design. demonstrated by Deepstar. Stan Swearingen and Mobil’s Mr. Barry Ho&ran were helpful in reviewing both guidelines and manuscript drafts. Jim Chitwood of Texaco has ensured Deepstar hydrate-related reports (Phases I. V . or for any infringement of patents or violation of any federal. and cases discussed in this manuscript are presented solely for educational purposes and are not intended to constitute design or operating guidelines or specifications.

L. Dr.-H. and he provided information on inhibitor economics.At Phillips Dr. T. This handbook is limited by a personal perspective. and in arranging interview with Texaco offshore engineers. Lund (SINTEF) provided two fin1 days of interviews regarding hydrate prevention and remediation in the Norwegian sector of the North Sea. Chitwood’s tie-in with Deepstar. vi . Austvik (leader). Dr. the Hydrate Team composed of Drs. Urdahl and A. Bill Parrish provided a hydrate perspective gamed over a quarter century of research and plant optimization. Their efforts have been an invaluable supplement in moving the handbook toward industrial utility. 0. At Texaco. and reviewed the draft of the manuscript. The readers’ constructive critiques are solicited with the goal of improving subsequent revisions. in addition to Mr. feedback on guidelines. At Statoil’s Research Center in Trondheim. Gjertsen. The efforts of the above personnel have contributed in an essential way to this handbook. intended to assimilate and synthesize the above contributions and those in the literature. Mr Jack Todd at Texaco was extremely helpful in providing the Texaco Reliability Engineering Manual for operating personnel. Parris’s collaboration provided an essential bridge between the theoretical and industrial perspectives. Phil Notz has been a hydrate colleague for over a decade.

The low temperatures and high pressures of the deepwater environment cause hydrate formation. depressurization sometimes prevents normal production for weeks. Appendix A gives hydrate crystal details at the molecular level. in a ratio of 85 mole % water to 15% hydrocarbons. A Russian hydrate perspective is presented in Makogon’s (1981. hydrate masses usually form at the hydrocarbon-water interface. as a function of gas and water composition. This handbook was written to provide the offshore facilities/design engineer with practical answers to the following four questions: • • • • What are the safety problems associated with hydrates? (Section I) What are the best methods to prevent hydrates? (Section II) How are hydrate plugs best removed? (Section III) What are the economics for prevention and remediation? (Section IV) Field case studies. a dislodged hydrate plug can be a projectile with high velocities. diagrams. In a pipeline. Depressurization of pipelines is the principal offshore tool for hydrate plug removal. Safety First: A Gallon of Prevention is Worth a Mile of Cure There are many examples of line rupture. sometimes accompanied by loss of life. I. are considered as background material in Appendix A. attributed to the formation of hydrate plugs. Less pressing questions regarding hydrate structures. Hydrate densities are like that of ice. but rapidly grow and agglomerate to sizes which can block flow lines. In the 1997 DeepStar Wyoming field tests. etc. or valves and meter discharges. plug formation mechanism. pictures. A computer program disk and User’s Guide (Appendix B) are provided to enable prediction of hydrate conditions. along with similarities and differences from ice. Hydrates can form anywhere and anytime that hydrocarbons and water are present at the right temperature and pressure. The hydrocarbons are encaged in ice-like solids which do not flow. however. and accumulate as flow pushes them downstream.Introduction Natural gas hydrates are crystals formed by water with natural gases and associated liquids. Both gas and liquid can frequently be transmitted through the plug. 1997) books. such as in wells. and example calculations are the basis for this handbook. The resulting porous hydrate plugs have the unusual ability to transmit some degree of gas pressure. Appendix C is a compilation of Case Studies not in the handbook body. flow lines. Hydrate safety problems are caused by three characteristics: 1. while they act as a flow hindrance. plugs ranged from 1 . lower viscosity and surface tension favors the flow of gas. An in-depth. theoretical hydrate treatment is given by Sloan (1998).

When a plug is depressurized using a high differential pressure. An air ambulance was deployed. At 2:00 a. the overhead line came apart. 1991 Gulf Incident On January 10. When hydrate plugs are dissociated by heating. 2. hydrate impact can fracture pipe. Such velocities and masses provide enough momentum to cause two types of failure at a pipeline restriction (orifice). rose rapidly due to warming winds around midnight. First. even when the discharge end of plugs are depressurized. The line had been depressured to the flare system. No pre-existing pipe defects were found. They had bled down the pressure in the distant end from the wellhead. downstream of the plug. probably from the impact of a moving hydrate mass. hydrate plug heating is not an offshore option due to the difficulty of locating the plug and economics of heating a submerged pipeline. However. any confinement causes rapid gas pressure increases. as the below three case studies (from Mobil’s Kent and Coolen. 1991 Chevron Incident. Such small. Field engineers discuss the “hail-on-a-tin-roof” sounds when small hydrate particles hit a pipe wall. approximately $6 million damage was suffered by the plant. _____________________________________________________________________ _____________________________________________________________________ Case Study 2. obstruction (flange or valve). 1992) indicate. Hydrates can form either single or multiple plugs. however the foreman was declared dead on arrival at the hospital. High differential pressures can be trapped between plugs. with no method to predict which will occur. _____________________________________________________________________ Case Study 1. mobile particles can accumulate to large masses occupying a considerable volume. They were standing near the line when the line failed. 2 . The ambient temperature which had been -30oC. elbow. Attempts to “blow the plug out of the line” by increasing upstream pressure (see Rule-of-Thumb 18) will result in additional hydrate formation and perhaps pipeline rupture. A large piece of pipe struck the foreman and the operator summoned help. with velocities between 60-270 ft/s. Hydrates contain as much as 180 volumes (STP) of gas per volume of hydrate. killing the chief operator. In addition.25-200 ft. A hydrate or ice plug formed in the overhead line from the amine contactor. and second. the dislodged plug can be a dangerous projectile which can cause pipeline damage. extreme compression of gas can cause pipe rupture downstream of the hydrate path. A foreman and an operator were attempting to clear a hydrate plug in a sour gas flowline. or sharp change in direction (bend.m. 3. 1991 the Rimbey gas plant was in the start-up mode. often filling the pipeline to tens or hundreds of feet in length. or tee) as shown in Figure 1.

1992) 1a) A hydrate plug moves down aflowline at very high velocites. Where the pipe bends. 1b) A hydrate plug moves down a flowline at very high velocites. the hydrate plug can rupture the flowline through projectile impact. Closed Valve If the velocity is high enough. the momentum of the plug can cause pressures large enough to rupture theflowline.Figure 1 .Safety Hazards of Moving Hydrate Plugs (From Chevron Canada Resources. Closed Valve .

4. Had high differential pressures across plugs for short periods. with intermediate plugs or pressure as shown in Figure 2a. The systems: 1. by an employee of a well-control/firefighting company.100 psig. At 12:15 p. The downstream side of the plug had been completely depressured. and • restrictions/bends exist downstream of the plug. was completely depressured to a truck within a 5 minute period. _____________________________________________________________________ Case Study 4. _____________________________________________________________________ In the above three case studies several common equipment circumstances existed. but they did reduce the piping strength under the transient (impact) conditions when the plug broke free. Were out-of-service immediately prior to the incident. because both ends of the hydrate plug were depressured. 3. 1980’s Statoil Incident In the mid-1980’s a hydrate plug occurred topside on a platform in a Statoil oil Field in the Norwegian sector of the North Sea.m. Did not have hydrate or freeze protection.m. which had been plugged about three days. 3 inch. screwed pipe nipple. Were pressurized while out-of-service. The upstream portion of the line. The failure was caused by the eruption of a hydrate plug at a Schedule 40. originally at 1. After some time of heating. 1991 two operators attempted to remove a blockage in a sour gas flowline. _____________________________________________________________________ _____________________________________________________________________ Case Study 3. 5.Contributing to this failure were pre-existing cracks in the pipeline. the work crew went • • 3 . Note that. 1991 Mobil Incident At 11:30 a. there may have been two end plugs. on January 2. the flowline failed and gas began flowing from somewhere around the casing. Were being restarted. low downstream pressures provide less cushion between a plug and restriction. The line section was valved-off and heat was applied to remove the plug. The leak was isolated at 3:18 p. 2. The Chevron Canada Resources Hydrate Handling Guidelines (1992) suggest that the danger of line failure due to hydrate plug(s) is more prevalent when: long lengths of pressurized gas are trapped upstream.m. These cracks did not impair the piping’s pressure-containing ability under steady-state conditions.

1992) 2a) Low Pressure High Pressure Low Pressure Hydrate Plug WELLHEAD Hydrate Plug SATELLITE 2b) Heat Addition Gas Hydrate Plug Pipeline Rupture Gas Hydrate Plug .Safety Hazards of High Pressures Trapped by Hydrates (From Chevron Canada Resources.Figure 2 .

such expenses are easily overshadowed when plugs form and production is stopped. from both safety and economic considerations. Upon their return the crew found that the section of line had exploded during their absence. preventing offshore production for a matter of weeks or months. the force was so great that the platform was said to rise 20 cm in the ocean. _____________________________________________________________________ The Canadian Association of Petroleum Producers Hydrate Guidelines (1994) suggest three safety concerns in dealing with hydrate blockages: • • • Always assume multiple hydrate plugs. • • The above case studies warn that hydrates can be hazardous to health and to equipment.to lunch. Yet hydrate plugs can be safely dissociated through the procedure indicated in the Remediation Section (III) of this handbook. any heating should always be done from the end of a plug. Heat had apparently been applied to the mid-point of hydrate plug and the plug-end portions served to contain very high pressures until the line ruptured. The last recommendation could be expanded in consideration of a subsea line: Heating a subsea plug is not recommended due to the inability to determine the end of the plug as well as provide for gas expansion on plug heating. Attempting to move ice (hydrate) plugs can rupture pipes and vessels. intending to complete the task on their return. In Section II it is shown that pressure increases exponentially with temperature increases when hydrates are dissociated. it is not uncommon for several hundred yards of hydrate plugs to form. 1970’s Elf Incident In the 1970’s a plug occurred on a floating platform riser in the North Sea. When the plug was expelled into the ocean. Blocking valves were closed and the pipeline was disconnected downstream of the plug. Figure 2b is a schematic of such a situation. with the intent of using high upstream pressure to extrude the plug from the line. and Depressuring a plug gradually from both ends is recommended. during remediation. While heating a plug is not normally an option for a subsea hydrate. _____________________________________________________________________ _____________________________________________________________________ Case Study 5. through design and operating practices. The discharge end of the pipeline was aimed overboard. 4 . While the usage of many gallons of inhibitors may be costly on a continuous basis. there may be pressure between the plugs. The preferred procedure. is to prevent the formation of hydrate plugs. rather than heating the plug middle. As the case studies in this handbook show.

This leads to the concept of designing system pressure drops at high temperature points (e. c) High pressures commonly cause hydrate formation. Prevention by Design: How to Ensure Hydrates Won’t Form The purpose of the prevention section is (1) to indicate common offshore sites of hydrate formation. 3. High reservoir fluid temperature may be retained through insulation and pipe bundling. Maintaining high temperatures keeps the system in the hydrate-free region (see Section II. and water dissolved in the gas is removed by drying with tri-ethylene glycol to obtain water contents less than 7 lbm/MMscf. at high pressure. (2) to indicate design methods to provide hydrate protection. and H2S.g. At 38oF. or additional heat may be input via hot fluids or electrical heating.G. although this is not economical in many cases. b) Low temperatures are normally witnessed in hydrate formation. the system temperature need not be below 32oF for hydrates to occur. The system may be decreased below hydrate formation pressure. Free water is removed through separation. which decreases the hydrate formation temperature below the operating temperature. common gases form hydrates at 66oF. Usually the pipeline residence time is insufficient for hydrates to form either from water vaporized into the gas. 4. while hydrates are 85 mole % water. Below about 3000 feet of water depth.II. Water removal provides the best protection. Hydrates can easily form at 38-40oF as well as the higher temperatures of shallower water. at 1500 psig. The above three hydrate requirements lead to four classical thermodynamic prevention methods: 1. Three conditions are required for hydrate formation in offshore processes: a) Free water and natural gas are needed. However. common natural gases form hydrates at pressures as low as 100 psig. Since pipelines typically operate at higher pressures. yet. The water in hydrates can come from free water produced from the reservoir. bottom-hole chokes). Most frequently hydrate prevention means injecting an inhibitor such as methanol (MeOH) or mono-ethylene glycol (MEG). hydrate prevention should be a primary consideration. 2. N2. or from water condensed by cooling the gas phase. including CO2.4). the resulting lower density will decrease pipeline efficiency. or from gas dissolved in the liquid water. 5 . and (3) to provide designs to make remediation easier if a hydrate plug occurs. Water removal processing is difficult and costly between the wellhead and the platform so other prevention schemes must be used. the ocean bottom (mudline) temperature is remarkably uniform at 38-40oF and pipelined gas readily cools to this temperature within a few miles of the wellhead. Gas molecules ranging in size from methane to butane are typical hydrate components.

Section II..000 ft. (b) the pipeline. Prior to the well. Water is then removed at a platform or onshore.B. and this section provides a brief description of each in Examples 1. The above methods are used individually or jointly for prevention. These inhibitors work by bonding to the hydrate surface and preventing crystal nucleation and growth for a period longer than the free water residence time in a pipeline. When the suspended water droplets convert to hydrates. the flow characteristics are maintained without blockage. respectively. Such depths and distances provide 6 . Where Do Hydrates Form in Offshore Systems? Figure 3 shows a simplified offshore process between the well inlet and the platform export discharge where virtually all hydrate problems occur. Design practices are provided in Section II. C. a flowline. two unusual aspects of the system should be noted: (1) the water depth is shown as 6. The emulsion is broken and water is removed onshore or at a platform. and after the platform export lines have dry gas and oil/condensate with insufficient water to form hydrates.F for hydrate prevention with rapid cooling across a restriction like a valve. Offshore design for hydrate thermodynamic inhibition with slow cooling of a pipeline is the topic of Sections II. D.000 ft. Hydrates form in offshore systems in two fundamental ways: (a) slow cooling of a fluid as in a pipeline (see Example 2 below) or (b) rapid cooling caused by depressurization across valves as on a platform (see Example 3). The prevention section of this handbook provides a method to use the six above methods to prevent hydrates in the design of an offshore system.A. II. provides general design guidelines for hydrate prevention in an offshore system.H. In Figure 3. Kinetic inhibitors are low molecular weight polymers and small molecules dissolved in a carrier solvent and injected into the water phase in pipelines. 6.. and E. but it may range to 10. and a platform. Alternatively the surfactant may transport micro-crystals of hydrate into the condensed phase.Two kinetic means of hydrate inhibition have been added to the thermodynamic inhibitor list and are being brought into common practice: 5.A. Section II. and (2) the distance between the well and the platform may range to 60 miles. Anti-agglomerants are surfactants which cause the water phase to be suspended as small droplets in the oil or condensate. and 3. or (c) the platform. 2. Section II. provides typical offshore system examples of hydrate formation in a well. high reservoir temperatures prevent hydrate formation.G gives procedures for prevention of hydrates through inhibition and heat management. In the figure hydrate blockages are shown in susceptible portions of the system: (a) the well.

and Platform COMP. Ocean Riser . Transport Pipeline.Depth 6000 ft Well with X-Mas Tree Transport Pipeline (2-60 miles in length) Platform Export Flowline Blockage in Riser Blockage in Tree. DRY SEP. Manifold.Offshore Well.Figure 3 . Well Mudline Blockage in Flowline Downhole Safety Valve Bulge from Expansion or Topography .

Hydrate Formation in a Well. etc. (caused by the water density inversion) except in a few cases with cold subsea currents.) into the well to reach any hydrate blockage. A pressure indication just beyond the choke is essential to determination of hydrate formation in the connecting flowline. However.3) provide two experiences with hydrate formation in a well. arising during drilling of the well or shut-in/start-up of the well.C. Hydrates form only in unusual circumstances. Case Studies 11 (Section III.000 ft. as shown in Section II. About 300-500 ft. occurs in almost all of the earth’s oceans. the bottom water temperature is very uniform at about 40oF. _____________________________________________________________________ Example 1. used as the initial emergency barrier between the reservoir and the production system. such as pressurizing the well with water or with an aqueous acid solution. This remarkably uniform water temperature at depths greater than 3. no further than a few miles of the wellhead. as determined by the methods of Sections II.2. which provide an entry way for lubricating hydrate dissociation tools (inhibitor injection. of depth. including two case studies 7 . The plot shows a high temperature of 70oF (or more) occurs for the first 250 ft.000 ft. no matter how high the temperature is at the air-water surface. The rate of cooling with length is a function of the initial reservoir temperature. the ocean bottom temperature of 40oF is low enough to cause hydrates to form at any typical pipeline pressure. heaters. below the mudline is the Downhole Safety Valve. any flowline fluid cools to within a few degrees of 40oF. Figure 5 shows a typical subsea well in which fluids are produced through the wing valve and choke to the pipeline. either through a normal cooling process (Example 2 and Figures 6 and 7) or through a Joule-Thomson process (Section II. The ocean acts as a heat sink for any gas or oil produced so that. the pipeline diameter. when the depth exceeds 3. A typical plot of the water temperature in the Gulf of Mexico is shown in Figure 4 as a function of water depth. coiled tubing. Addressing these blockages should be done using the techniques in the Remediation Section (III). the flow rate.a) and 16 (Section III.B through II.D. Davalath and Barker (1993) provide a comprehensive set of conditions for dealing with hydrates in deepwater production and testing. and other fluid flow and heat transfer factors. However. At the top of the well are Swab Valves.B.B.cooling for the pipeline fluids to low temperatures which are well within the hydrate stability region. The system temperature and pressure at the point of hydrate formation must be within the hydrate stability region. without insulation or other heat control methods.F). Hydrate formation in wells is an abnormal occurrence. The system temperature and pressure enters into the hydrate formation region. Normal well-testing procedures will not promote hydrate formation.

Figure 4 . Depth (Gulf of Mexico) 10 100 Ocean Depth (feet) 1000 10000 20 30 40 50 60 70 80 Temperature (oF) .Water Temperature vs.

Typical Subsea Well Swab Valve Christmas Tree Wing Valve Crossover Valve Master Valve Wellhead Mudline 30 inch Downhole Completion Downhole Safety Valve 20 inch 13 3/8 inch 9 5/8 inch .Figure 5 .

the reader is referred to Sloan (1998.1.3.of problems (summarized in Appendix C Case Studies C.24) and four case studies of successful hydrate management.000 and 7.500 feet. • One should not design a well to operate outside the hydrate region only if flow conditions are maintained. • Several hours may be required for hydrate formation and blockage to occur. This represents a potentially dangerous situation for well control.a on methanol injection. • When hydrates form solids. • As of October 1988 Exxon used salt at the saturation limit range of 150 to 170 g/l to prevent hydrate formation. In offshore well drilling. Section 8. leaving a solid barite plug. While a brief overview is given here. In each well Shell experienced an 8 .G. etc. they remove water from the mud. frequently a water-based drilling fluid is used that can form hydrates and plug blow-out preventors. • Drilling hydrate problems frequently occur. but have only been recognized in recent years. The injection location and amount of methanol injection are specified using the procedure indicated in Section II.23 and C.) <1000 ≤1500 ≤2000 ≥3000 Risk of Hydrate Formation Problems A hydrate problem will probably not occur Without inhibition a hydrate problem may occur Without inhibition a hydrate problem will occur Insufficient experience. kill lines. Hydrate formation on drilling is an area of active research with several joint industrial projects underway. using muds with 20 wt% sodium chloride (NaCl) and partially hydrolyzed polyacrylamide (PHPA). flow will stop at some period and the well operation will be jeopardized. and (2) downhole several thousand feet below the seafloor. the summary given below by Barker may be used: Guidelines for Deepwater Hydrate Formation in Drilling Muds in Water-Based Muds Water Depth (ft. Barker indicated the following rules-of-thumb used by Exxon in considering hydrate formation with drilling fluids.2) for a detailed discussion. If the well will be in the hydrate formation region at static conditions. • As general guidelines concerning hydrate formation at various water depths. when a gas bubble (or “kick”) comes into the drilling apparatus. salt alone will not suffice By 1988 Shell had drilled 16 wells in the Gulf of Mexico at water depths between 2. Typically methanol injection capability is provided in the well at two places: (1) at the subsea tree.

average of more than one gas kick per well. when Shell experienced difficulty disconnecting the drill stack. To the right of the diagram hydrates will not form and the system will exist in the fluid (hydrocarbon and water) region. 7 miles) the flowing stream retains a high temperature from the hot reservoir gas at the pipeline entrance. Recently the number of hydrate problems have increased dramatically as drilling has moved to deeper water. Instead methanol is injected into the pipeline at the subsea well-head.. of water involved the possibility of hydrate formation. (1994) provided a hydrate pipeline case in Figure 6 for a Gulf of Mexico gas. so that hydrates would undoubtedly form.g. Methanol injection facilities are not available at the needed point along the pipeline. and hydrate prevention measures should be taken. and at about 9 miles a unit mass of flowing gas and associated water enters the hydrate region (shaded region to the left of the line marked 0% MeOH). usually at accumulations with some change in geometry (e.21 and C.) the well was abandoned. Such a distance may represent several days of residence time for the water phase. As vaporized methanol flows along the pipeline in Figure 6. a bend or 9 . Texaco’s Notz. Barker and Gomez (1989) documented two occurrences (see Case Studies C. etc. The ocean cools the system. Much remains to be done in this area. In the case of the pipeline shown in Figure 6 methanol is injected at the wellhead so that in excess of 23 wt% methanol will be present in the free water phase over the entire pipeline length. Pipeline pressure and temperature conditions were predicted using a pipe prediction program such as OLGA® or PIPEPHASE® and those conditions are shown superimposed on the hydrate conditions in Figure 6. stack connectors. where losses in drill times were 70 days and 50 days. respectively. Hydrate inhibition occurs in the free water. which signaled the possibility of hydrate formation. Only one instance in 2900 ft. remaining in the uninhibited hydrate area until mile 45.22 of Appendix C) of hydrate formation in relatively shallow waters off California and the Gulf of Mexico. Example 2 represents flow conditions in the pipeline. were not inhibition steps taken. so that approximately 23 wt% methanol is required in the free water phase to prevent hydrate formation and subsequent pipeline blockage. _____________________________________________________________________ Downstream of the well and choke. However. the fluid flows through a pipeline of considerable length before reaching the platform. hydrates will form in the shaded region to the left of the diagram. At low pipeline distances (e. In Figure 6. it dissolves into any produced brine or water condensed from the gas. In several cases where safety was an issue (plugged blow out preventers. by mile 25 the temperature of the pipeline system is within a few degrees of the ocean floor temperature. _____________________________________________________________________ Example 2: Hydrate formation in a Flowline.g.

Figure 6 . 1994) 2500 30% MeOH 20% MeOH 10% MeOH Hydrate Formation Curve 2000 Pressure(psia) 1500 Hydrate Forming Region 30 25 15 20 10 7 Miles 1000 35 500 40 45 Hydrate Free Region 50 0 30 40 50 Temperature(oF) 60 70 80 .Offshore Pipeline Plotted on Hydrate Formation Curves (From Notz.

From mile 45 to mile 50 however. to separate the gas. providing a straight. Pipeline pressure drops are functions of several variables. rather than in the vapor or condensate. The process is shown in Figure 8 with process conditions given in Table 1 and selected stream compositions provided in Table 2. weld slag. resulting in an almost constant pressure cooling. Hydrate inhibition occurs in the aqueous liquid. sand. 344-355) detail a typical offshore platform process for a sweet crude oil with dissolved gas delivered to the platform at 1000 psig and 120oF. typical gas pipeline pressure drops are small relative to the overall pressure. While most of the methanol dissolves in the water phase.g. 10 . with 49 MMscf/d gas produced at 1000 psig and an overall gas to oil ratio (GOR) of 491 scf/Bsto. The process was sized for a product of 100. and oil. horizontal line between the pipeline end points on a plot like Figure 7. to compress the gas for transport to land. In Todd’s simulations. and 3.000 barrels per day (bpd) of oil to the pipeline at the LACT (lease automatic custody transfer) unit. aqueous.. due to the expense of regeneration. and individual systems should be simulated for best results. and condensate phases is usually not recovered. a significant amount of methanol either remains with the vapor or dissolves into any liquid hydrocarbon phase present as calculated using the methods shown later in this section. There are three objectives of the platform process: 1. The heavy ends of the crude are divided into five boiling-point cuts while mole fractions of individual gas components are given. Methanol exiting the pipeline in the vapor. 2. Manning and Thompson (1991. _____________________________________________________________________ Example 3: Typical Offshore Platform Process.). and providing water discharge to the ocean. _____________________________________________________________________ Todd (1997) provided simulations with a different behavior from the pipeline in Figure 6. In Figure 6 Notz showed that the gas temperature increases from mile 30 to mile 45 with warmer (shallower) water conditions. 80-82. to dehydrate the gas to a water content below 7 lbm/MMscf before injection into the pipeline to shore. providing an oil phase which has a very low vapor pressure.pipeline dip along an ocean floor depression) or some nucleation site (e. water. etc. pp. a second cooling trend is observed due to a Joule-Thomson gas expansion effect.

Figure 7 . 1997) 3000 10% MeOH 2500 2000 1500 Separator Pipeline Hydrate Formation Curve Pressure(psia) 1000 500 0 30 35 40 45 50 55 60 65 Wellhead 70 75 Temperature(oF) .Typical Transport Pipeline Plotted on Hydrate Formation Curves (From Todd.

-u Main oil punp .Figure 8 - Typical (From Offshore Manning and Pbtform 1991) Schematic Thompson.

7 16.66 7150.91 100 100 100 107.99 474.54 100 100 100 106.87 1318.7 1019.78 2038.32 474.7 314.86 111.0664 1 0 1 0.67 3179.7 1019.9 74.1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 .Platform Processing Conditions (From Manning and Thompson.45 106.1821 1 0 0.96 171.2 32.87 1318.75 o Mol/Hr 12297.7 314.13 8020.7 314.6 0 0 0 0 144.89 23.44 167.99 7150.42 23.27 43.75 226.7 69.7 69.67 6676.23 23.65 869.7 69.Table 1 .9 95.7 314.18 21.22 106.7 314.93 104.45 111.9464 1 0 1 1 0.93 Frac.22 106.7 16.53 Mol Wt 105.65 8020.9 0 0 104667.7 1019.29 20.7 69.7 1019.7 69.94 151. 1991) Location Pressure(PSIA) 1019.7 74.47 1318.7 1019.43 97.09 43.7 314.83 53.13 175.87 1141.7 69.22 236.98 10058.7 1024.41 52.0275 0 0 0 111807.29 125.7 Temperature( F) 120 120 120 115.7 314.7 69.2 32.54 177.66 3156.99 0 0 0 0 1172.67 449.3 0 0 101141.2 28.86 115.16 0 0 0 199.7 69.7 319.67 474.21 200.78 10058.7 314.6 0 0 0 100000. Vap BPD @60F 0.7 1019.7 69.66 3179.8655 1 0 1 1 0.21 25.09 167.05 100 100 100 104.2026 1 0 0.7 69.94 285.32 3179.39 151.43 5395.1084 1 0 0.45 111.86 115.7 32.22 6902.9926 1 0 1 0.7 314.7 314.7 0 0 98533.64 54.42 23.9 18.7 16.79 125.94 27.27 280.76 2238.0504 0.42 23.

000654 0.1216 0.1060 0.001283 0.009932 0.0000 25.005897 0.1641 10058.0748 0.53E-05 0.248351 0.1991) #1 #2 Gas Out Inlet Fluid Comp.0665 0.005605 0.086336 0. Out 7th Sep.0422 0.0027 0.12895 0.001297 2.77 0 226.0185 0.1125 0.00197 0.1393 0.204668 0.0092 0.242716 0.1342 12297.44E-06 0 0 177.0003 0.0124 0.225381 0.1704 0.061975 0.0213 0.279249 0.1227 0.0000 0.005419 0.0137 0.0062 0.1051 0.000935 0.039283 0.0000 2238.0000 449.0937 0.032016 0.000456 0.108848 3.010048 0.251714 0.0121 0.027843 0.1232 0.00111 0.694509 0.22 0.0115 0.084829 0.0008 0.5605 0.03602 0.0020 0.179342 0.2058 8020.0009 0.0597 0.029695 0.3E-05 0.66 0.1108 0.2880 0.001304 0.98 0.22876 0. #21 Liq.218463 0.0000 474.13 0.767528 0.0022 0.0607 0.1522 0.1615 0.074892 0.2202 0. Out 1st Sep.002135 0.086334 0.115474 0.(Mol Frac.075325 0.0012 0.0408 0.0873 0.0000 0.0078 0.017143 0.1398 0. #3 Liq. #11 Gas Out 3rd Sep.0474 0.0388 0.0010 0.0000 0.0000 0.31 0.0063 0.014435 0.66 0.000854 0.0444 0.000395 0.0009 0.0120 0.2399 0.0009 0.001848 0.0418 0.0009 0.2472 6676.0553 0.22 0 200.0000 474.0001 0.0169 0.46 0.0385 0.0001 0.020328 0.0418 0.41E-05 0.004178 0.154435 0.23E-05 0.0562 0.0036 0.08717 0.0293 0. #26 Liq.0342 0.000169 9.170367 0.0043 0.0244 0.88 0 0 0 449.0140 0.0563 0.2 #16 Liq.051238 0.0714 0.0000 0.0544 0.0145 0.176941 0.154317 0.0133 0.0834 0.0000 0.66 0.0267 0.05984 0.0359 0.0092 0.005098 0.013479 0.1190 0.0000 0. Out 3rd Sep.0008 0.69145 0.062111 0.0005 0.57 . #27 Sales Gas #28 Liquid Line #29 Liquid Line #30 Sales Oil Nitrogen CO2 Methane Ethane Propane i-butane n-butane i-pentane n-pentane Hexane 248 F 340 F 413oF 472oF 657oF Total Mol/Hr o o 0.033794 0.3E-05 0.125021 0.239094 6902.048676 0.Table 2 .23 0.017764 0.75 0.1393 0.002091 0.081205 0.0360 0.0118 0.170392 0.009112 0.0040 0.0647 0.1438 0.137066 0.27E-05 0 0 1318.002404 0.0004 0.65 0.000398 2.077701 0.001281 0 0 23.71E-06 4.0000 0.001793 0.84E-05 0.0001 0.016941 0.199829 0.027327 0.0000 0.0287 0.003227 0 0 0 3156.0716 0.000467 0.0597 0.0004 0.2517 0.095217 0.0075 0. #9 Liq.Gas and Liquid Compositions on Platform (From Manning and Thomson.) 6th Sep. #12 Liq.000442 0.0996 0.032004 0.8705 0.207999 0.0000 0.0001 0.087314 0.0935 0.0611 0.020161 0.065133 0.6E-05 2.1615 0.1819 0.0023 0.0002 0.0407 0.0000 0. Inlet #25 Gas Out 7th Sep. Inlet #15 Gas Out 6th Sep.000649 0.081536 0.0160 0.2399 0.0004 0.0000 0.00999 0. #8 Gas Out 3rd Sep.0318 0.0073 0. #14 5th Sep.0598 0. #17 6th Sep.075951 0.0253 0.42762 0.2118 0.0402 0. Nitrogen CO2 Methane Ethane Propane i-butane n-butane i-pentane n-pentane Hexane 248 F 340oF 413oF 472 F 657oF Total Mol/Hr o o 0. #5 Gas Out 2nd Sep.8074 0.0000 0.0269 0.094344 0.1704 0.0000 2038.0015 0.0470 0.000398 0.0278 0.0033 0. Inlet #20 Gas Out 6th Sep.0001 0.1313 0.036754 0.) 1st Sep.2 6.98 0.0036 0.288001 0.42 1.1371 0. Out 2nd Sep.2789 0.130298 0. Out Comp.0368 0.027092 0.2308 7150.077535 0.0018 0.67 0.059332 0.0267 0.1995 0.0008 0.013199 0.0018 0.00128 0.0424 0.0440 0.077977 0.0005 0.046189 0.33 0 0 3179.096918 0 5395. #23 7th Sep.0510 0.0520 0.0000 0.018863 0.000249 0.0221 0.0491 0.0000 0.000354 1.000448 0.018329 0.0203 0. Out 6th Sep. Out 4th Sep.005551 7.0710 0.1094 0.78 0.089057 0.12715 0.0009 0.0747 0.119176 0.002365 0.0024 0.0416 0.1783 0.1002 0.32E-05 0.0005 0.0000 0. #6 Liq.000169 0.010736 0.002783 0.0287 0.003929 0.2789 0.04526 0.0000 869.3386 0.0407 0.0429 0.003338 0.000174 2.0155 0.0000 0.(Mol Frac.98E-05 8.0219 0.040401 0.0031 0.

4310 bhp compressors represent the largest cost on the platform.F.Note that water separation and gas dehydration are vital for hydrate prevention. hydrate formation is prevented due to insufficient water. pp. 300 psig.5% of the total oil production. so that point is very susceptible to hydrate formation. usually fed from the inlet gas passing through a control valve with a substantial pressure reduction. with capital cost on the order of $800-$1500 (1990 dollars) per installed horsepower. the process frequently shuts down. resulting in pipeline cooling and significant hydrate blockages in the production line at restart. 35-42) observe that when fuel and/or instrument gas lines are blocked due to hydrates. As a first approximation. operating at 1000psig. and separated from liquid again before re-combining the gas with the previous separator’s gas for injection into the export gas line. (1996. then inhibition might be considered in the pipeline design 11 . so an oil pipeline pressure greater than 15 psia will prevent a gas phase. Also instrument gas lines require similar pressure reductions from a header. methane. These compressors are powered by fuel gas which operates at a low pressure (about 200 psig). Texaco’s Todd et al. the engineer should first calculate the pressure at which hydrates form at the lowest deep ocean temperature (38-40oF). the engineer may do a rough estimation to determine whether the pipeline will operate in the hydrate region. Hydrate formation is not a significant problem in the oil export pipeline because relatively few hydrate formers (nitrogen. _____________________________________________________________________ II. cooled. propane. A One Minute Estimate of Hydrate Formation Conditions (Accurate to ± 50%) Assuming the pipeline pressure drop to be relatively small. The export pipeline gas water content is below its water dew point (9 lbm/MMscf) at the lowest temperature (39oF) so free water will not condense from the gas phase. Hydrate limits to pressure reductions through restrictions such as valves and orifices is shown in Section II.B. The oil is stabilized by flow through a series of four separators. particularly in winter months. The gas from each separator is compressed. In the process shown. so that even if the system cools into the hydrate pressure-temperature region shown in Figure 7. The additional oil obtained after cooling the compressed gas amounts to about 1. butanes and CO2) are present and the water content is low. and 2 psig before the export oil pipeline. so that if the pipeline pressure is greater. ethane. Pressure reductions after the fuel gas takeoff cause cooling. 55 psig.

indicating: • • • gas drying and/or inhibition is needed for ocean pipelines with temperatures approaching 39oF. the lowest formation pressure was 100 psig for a gas with 7 mole % C3H8. and they are intended as guides for the engineer for further action. Rule-of-Thumb 1 indicates that most offshore pipeline pressures greatly exceed the hydrate formation condition. a more accurate estimation procedure should normally be considered. using a Rule-of-Thumb the engineer might determine that a more accurate calculation was needed for inhibitor injection amounts. Where possible the accuracy of each Rule-of-Thumb is provided. Rules-of-Thumb will frequently be stated in bold type. or that further consideration of hydrates was unnecessary. 1998. A Ten-Minute Estimation of Hydrate Formation/Inhibition (Accurate to ± 25%). More accurate estimations of hydrate formation conditions over a broad temperature range are made by the method in the following section. Rulesof-Thumb are not intended to be “Absolute Truths”.8 mole % C3H8. Chapter 6) with an average formation pressure of 181 psia. and 12 . while the highest value was 300 psig for a gas with 1. These Rules-of-Thumb are based upon experience. hydrates will form in a natural gas system if free water is available and the pressure is greater than 166 psig. and hydrate formation pressures are dependent upon the gas composition. II. A pipeline pressure-temperature flow simulation should be done to determine the conditions between the wellhead and the platform separators. Rule of Thumb 1: At 39oF. Of the 20 gases. For example.C. In this handbook. Hydrate formation data were averaged for 20 natural gases (from Sloan.and operation. as in the case of warmer temperatures in shallower water. and are particularly sensitive to the amount of propane present. Such an approximation may indicate the need for more accurate calculations to determine the amount of inhibition required. and exceptions can always be found. (or between the platform and the onshore separators). Rules-of-Thumb. It should be reiterated here that hydrates can form at temperatures in excess of 39oF when the pressure is elevated. The first Rule-of-Thumb is given below for hydrate formation at ocean bottom temperatures. As a second approximation of hydrate formation the design/facilities engineer should perform two calculations: 1.

and 0.C and II. To the left of every line hydrates will form from a gas of that gravity. _____________________________________________________________________ Example 4: Calculating Hydrate Formation Conditions Using the Gas Gravity Chart Find the pressure at which a gas composed of 92.29% ethane.67 mol% methane.38% propane. II.14% pentane form hydrates with free water at a temperature of 50oF. As an alternative if a pipe flow simulation is not readily available. Step 1 in this calculation. 13 .338% n-butane.2. is one of the principal goals of this handbook. determining pressures and temperatures of vapor and aqueous liquid inhibited by various amounts (including 0 wt%) of methanol (MeOH) or monoethylene glycol (MEG). without hydrate formation. As we have seen in Example 2 of Section II. 0. perhaps done by the engineering staff at the home office. it is very likely that a long offshore pipeline will have hydrate formation conditions with free water present. as discussed in this and in the following section. while for pressures and temperatures to the right of the line. the engineer may wish to assume that contents of a long offshore pipeline will eventually come to the ocean bottom temperature at the pipeline pressure. the gas gravity is calculated and the temperature of a point in the pipeline is specified.182% i-butane. 0. Hydrate formation conditions such as those shown in Figure 6 should be calculated.1. In order to use this chart shown in Figure 9.C. Hydrate Formation Conditions by the Gas Gravity Method. The below methods (Sections II. The engineer then needs to specify the amount of inhibitor needed to keep the entire pipeline in the fluid region. The intersection of the above two lines determines the pressure and temperature at which hydrates will form in a pipeline.D) may then be used directly to determine the amount of MeOH (methanol) or MEG (monoethylene glycol) needed to prevent hydrate formation at those conditions. The simplest method to determine the hydrate formation temperature and pressure is via gas gravity. Step 2. enabling estimations of hydrate formation pressures and temperatures. defined as the molecular weight of the gas divided by that of air.A. the system will be hydrate-free The following example from the original work by Katz (1945) illustrates chart use. is beyond the scope of this handbook and should be considered as a separate. The pressure at which hydrates will form is read directly from the chart at the gas gravity and temperature of the line. 5. the flow simulation of the pipeline. 1. pre-requisite problem.

00 50.00 45.00 Temperature (F) .H rat Formati (From Katz 19591 2- 3- 4 J.00 75.00 40.00 I I I 55.00 80.00 I 70. 30.00 35.00 6o)oo I 65.a Fi ur 43- .

6 gravity gas as ±7oF or ±500 psig.603 by the procedure below: Component Mol Fraction Mol Wt Avg Mol Wt in Mix yi MW yi•MW Methane Ethane Propane i-Butane n-Butane Pentane 0.Solution: The gas gravity is calculated as 0.000 Gas Gravity = 16. and so should be used with caution for those gases with substantial amounts of CO2. but it requires some additional time as well as a computer.106 0.603 Mol Wt of Air 28.9267 0.Toper) oF. In addition. Section II.2.470 = = 0.W) (1) where: ∆T = C = W = M = hydrate depression. II.124 58. 2.867 1.609 0.097 58.196 0.0014 1. 1985) for the hydrate equilibrium temperature (Teq) and pressure (Peq) are maximized for 0. whose principle asset is ease of calculation.591 0. In the fifty years since the generation of this chart. or N2. and molecular weight of MeOH (32) or MEG (62).101 17.0138 0. H2S. (Teq .335 for MeOH.966 At 50oF . the hydrate pressure is read as 450 psia _____________________________________________________________________ The user is cautioned that this method is only approximate for several reasons.124 72. Estimating the Hydrate Inhibitor Needed in the Free Water Phase The above gas gravity chart may be combined with the Hammerschmidt equation to estimate the hydrate depression temperature for several inhibitors in the aqueous liquid: ∆T = CW M(100 .00338 0. 14 . constant for a particular inhibitor (2.00182 0. the estimated inaccuracies (Sloan.000 for MEG) weight per cent of the inhibitor in the liquid.070 44. Figure 9 was generated for gases containing only hydrocarbons.D provides one of the most accurate methods for calculation of hydrate conditions. more hydrate data and prediction methods have caused the gravity method to be used as a first estimate.151 14.470 Mol Wt of Gas 17.043 30.C.0529 0.

where xMeOH is mole fraction methanol in aqueous phase ∆T = −129. The equation was based upon more than 100 natural gas hydrate measurements with inhibitor concentrations of 5 . well within the hydrate formation region.25 wt% in water. Estimate the methanol concentration needed to provide hydrate inhibition at 450 psia and an ocean floor temperature of 39oF for a gas composed of 92. tested against 75 data points. 0. with the values: ∆T = Temperature Depression (50oF . The engineer may wish to provide an operational safety factor by the addition of more methanol. Solution: The gas is the same composition and pressure as that in Example 4.The Hammerschmidt equation was generated in 1934 and has been used to determine the amount of inhibitor needed to prevent hydrate formation. Inhibition is required since the pipeline operates at 39oF and 450 psia.603 and uninhibited hydrate formation conditions of 50oF and 450 psia. and 0. The accuracy of the Hammerschmidt equation is surprisingly good. with the gas gravity previously determined to be 0. the average error in ∆T was 5%.6 ln(1 − x MeOH ) (1a) _____________________________________________________________________ Example 5: Methanol Concentration Using the Hammerschmidt Equation. The weight percent of inhibitor needed in water phase is determined via the Hammerschmidt Equation (1).38% propane. M ∆T + C 32 × 11 + 2335 The methanol in the water phase is predicted as 13. 0.67 mol% methane. 1.182% i-butane.14% pentane.29% ethane.39oF= 11oF). 5.1 wt % to provide hydrate inhibition at 450 psia and 39oF for this gas.338% n-butane. M = Molecular Weight for Methanol (= 32) C = Constant for Methanol (= 2335) W = Weight Percent Inhibitor Rearranging in Equation (1) W = 100 M ∆T 100 × 32 × 11 = = 131 . as indicated in Example 5. For higher methanol concentrations ( up to 87 wt%) the temperature depression due to methanol can be calculated by a modification of Equation (1) by Nielsen and Bucklin (1983). _____________________________________________________________________ 15 .

psia 500 1000 1500 2000 Water Content.C. with an increasing amount of water production over the well’s lifetime. Water condensed from the hydrocarbon phases may be calculated. Then the water content of the outlet gas (Rule-of-Thumb 2) may be subtracted from the inlet gas to determine the water condensed per MMscf of gas. the lowest water content of the outlet gas is given by the below table: Pipe Pressure.0 7. The water content of condensates is usually negligible.3. While the Hammerschmidt equation enables estimation of the wt% MeOH (or MEG) needed in the free water phase. In Figure 10 the temperature of the pipeline inlet or outlet is found on the xaxis and water content is read on the y-axis at the pipeline pressure.0 5. An illustration of condensed water calculation using Figure 8 is given in Example 6 (Section II. Rule-of-Thumb 2: For long pipelines approaching the ocean bottom o temperature of 39 F. just as the inhibitor concentrations in the gas and condensate are multiplied by the flows of the vapor and condensate. When an inlet gas water content is not available a water content chart such as Figure 10 may be used to obtain the water content of both the inlet and outlet gas from the pipeline. if available. three other quantities are necessary to estimate the amount of inhibitor injected into the pipeline: 1. II. The engineer is cautioned not to use the water content chart at o temperatures significantly below 38 F. The amount of water condensed is the difference in the inlet and outlet gas water contents. inhibitor concentrations in the gas and condensate phases are usually counted as economic losses.4). but water condensed from gases can be substantial. Methanol recovery is done only rarely on platforms and is typically too expensive at onshore locations. multiplied by the gas flow rate.a Amount of Water Phase The water phase has two sources: (a) produced water and (b) water condensed from the hydrocarbon phases. At lower temperatures the actual water content deviates from the line due to hydrate formation. The amount of the free water phase is multiplied by the wt% inhibitor from the Hammerschmidt equation. 2. the amount of the free water phase. lbm/MMscf 15. the amount of inhibitor lost to the gas phase.II.0 9.C.5 An inlet gas water content analysis is used. 16 .C. and 3. Amount of Inhibitor Injected Into Pipeline. the amount of inhibitor lost to the condensate phase. The amount of produced water can only be determined by data from the well.3. marked on each line in Figure 10. Because hydrate inhibition occurs in the water phase.

Water Formation Curve (From McKetta and Wehe. 1958) .Figure 10 .

1 mole% of that in the water phase.C. when the methanol vapor loss can be substantially higher and the method of Section II. the water phase wt% inhibitor must be converted to mole % in order to use either chart.03% of the water phase mole fraction of MEG. The gas flowing 17 .C.4 illustrates methanol loss to the gas phase. Rule-of-Thumb 3: At 39oF and pressures greater than 1000 psia. while two other phases represent potential losses of methanol.3.3 should be used.II. the maximum amount of MEG lost to the gas is 0.b Amount of Inhibitor Lost to the Gas Phase. The Hammerschmidt equation only provides the amount of methanol needed in the free water phase at the point of hydrate inhibition. Rule-of-Thumb 3 is valid except for low water amounts.C. the amount of methanol in the vapor may be 0.4. The predominance of methanol’s use is due to this effectiveness. The amount of MeOH or MEG loss into the gas phase should also be considered using the following Rules-of-Thumb. The below sample calculation uses all of the concepts presented in Section II. Note that the data for Figures 11 and 9 were obtained in 1985 for the mole fraction ratio of inhibitor in the vapor over the aqueous phase. Rule-of-Thumb 5: Methanol concentration dissolved in condensate is 0. it is important to remember that methanol is a much more effective inhibitor than ethylene glycol on a weight basis.3. Two general Rules-ofThumb can be applied to inhibitor losses in the condensate. Figure 12 validates Rule-of-Thumb 4 for MEG. o Rule-of-Thumb 6: The mole fraction of MEG in a liquid hydrocarbon at 39F and pressures greater than 1000 psia is 0. _____________________________________________________________________ Example 6: Methanol Injection Rate.C. II. together with the fact that methanol easily flows to the point of hydrate formation.c Amount of Inhibitor Lost to the Liquid Phase. Example Calculation of Amount Methanol Injection.5 wt %. II. Even with low losses of MEG relative to MeOH in both the gas and the liquid. Rule-of-Thumb 4: At 39oF and pressures greater than 1000 psia. Example 6 in Section II.002 lb /MMscf. the maximum amount of methanol lost to the vapor phase is 1 lb MeOH/MMscf for every m weight % MeOH in the free water phase. m The methanol loss chart in Figure 11 shows that at typical offshore pipeline conditions.D. A sub-sea pipeline with the below gas composition has inlet pipeline conditions of 195oF and 1050 psia.C.

6s III 0 0 0 0 ZOOE-3 1000 8.70578 1.. 50 I t I I I III I I I I I I. 100 III..r Z. 1998) Temperature.9oE3 lfw) a b -7250. 80 1 I. = a + b[l/T(R)] -3.. 90 I...Figure 11 ......20 -6432..mE-3 1111.. 60 1 III 70 I.23 -5738..Methanol Lost to Vapor (From Sloan.I.....41233 psia 2000 psia 6. 40 I I...82227 3000 psia 5..z - InK. ...48 l.....lOE-3 . 1 isobaric Vapor Phase Distribution for Methanol in Hydrate-Foxming Systems ... OF 20 % 5 Ls 30 I.

I 0 1 I I 1 Bo 60 OF .Fimre 12 . 1972) xx)100 = 60 = 4020IO = 6= 42I 0.6 a4 =‘ = r QOI ’ I /I -40 -20 20 40 EOlJlLlBRlUM TEMPERATURE.Mono-Ethylene Glvcol Lost to Vapor (From Townsend and Reid.

12 72.60%. the hydrate temperature is 65oF at 1000 psia.0) C = Constant for Methanol (= 2335) W = Weight Percent Inhibitor 18 .25 bbl/day.79%. The pipeline produces condensate at a rate of 25 bbl/day. Solution: Basis: The basis for these calculations was chosen as 1 MMscf/d.09 58.0194 0.245 22.0079 0.2 MMscf/d.708 = = 0.07 44.01 44. propane =1. Step 1) Calculate Hydrate Formation Conditions using the Gas Gravity Chart Component Mol Fraction yi 0.855 0.19%.487 1. M = Molecular Weight for Methanol (= 32.through the pipeline is cooled by the surrounding water to a temperature of 38oF.0596 0.670 6.1419 1.966 Reading the gas gravity chart (Figure 9). n-butane = 0.0473 0. ethane = 4. The gas also experiences a pressure drop to 950 psia.MW Where:∆T = Temperature Depression (65oF .04 30. Find the rate of methanol injection needed to prevent hydrates in the pipeline.459 0. n-pentane = 0.15 28.73%.7160 0.0079 0. nitrogen = 5.01 Avg Mol Wt in Mixture yi•MW 11.000 Mol Wt MW 16.570 1.422 0. carbon dioxide = 14. Natural gas composition (mole %): methane = 71.784 mol wt air 28.96%.94%.708 Methane Ethane Propane n-Butane n-Pentane Nitrogen Carbon Dioxide Gas Gravity = mol wt gas 22. Produced free water enters the pipeline at a rate of 0. Step 2) Calculate the Wt% MeOH Needed in the Free Water Phase The Hammerschmidt Equation is: ∆T = CW 100M .79%. Gas exits the pipeline at a rate of 3.38oF= 27oF). with an average density of 300 lbm/bbl and an average molecular weight of 90 lbm/lbmole.

25bblH 2 O  42 gal  8. Rule of Thumb 2 states that exiting gas at 1000 psia and 39oF contains 9 lbm/MMscf of water in the gas.25 bbl/day to a basis of lbm/MMscf:  0. The inlet gas (at 1050 psia and 195oF) water content is read as 600 lbm/MMscf.34lbm     bbl  gal  day     1day   3.0% to provide hydrate inhibition at 1000 psia and 38oF for this gas.4 m 2  MMscf  . to calculate the water in the vapor/MMscf. The mass of MeOH in the free water phase per MMscf is: 27wt% = M lbm MeOH × 100% M lb m MeOH + 618.Calculate Mass of Condensed H2O In the absence of a water analysis. gas.Total Mass of Water/MMscf Gas: Sum the condensed and produced water 591 lbm + 27.0 wt% methanol is required to inhibit the free water phase. and the mass of water/MMscf was calculated at 618.Calculate Mass of Produced H2O Flowing into the Line Convert the produced water of 0.4 lbm = 618. use the water content chart (Figure 10). The total mass of methanol injected into the gas is calculated as follows: -Calculate Mass of MeOH in the Water Phase 27. Step 3) Calculate the Mass of Liquid H2O/MMscf of Natural Gas .4 lbm.Rearranging the Hammerschmidt equation W = 100 M ∆T 100 × 32 × 27 = = 27 M ∆T + C 32 × 27 + 2335 The weight percent of methanol needed in freewater phase is 27.4 lbm MMscf MMscf MMscf Step 4) Calculate the Rate of Methanol Injection Methanol will exist in three phases: water.4lbm H 2 O 19 . The mass of liquid water due to condensation is: 600 lbm _ 9 lbm = 591 lbm MMscf MMscf MMscf .2 MMscf  lb H O   = 27. and condensate.

the amount of methanol lost to the gas and condensate is approximately 11% of the total amount injected. In such cases. that maximum amount of MeOH lost to the gas is 27 lbm/MMscf.33 gal/MMscf at a MeOH density of 6. Computer Program for Second Approximation. Total MeOH Injection II. Slightly different Rules-ofThumb have been used. the amount of methanol in the condensate will be 0. as shown in section II. but these differences are insignificant. Since there is 27 wt% MeOH in the water. The method is made much more convenient for the engineer via the use of the below spreadsheet program.2 MMscf = 11.5. 20 .63 lbm/gal) _____________________________________________________________________ In the above example.D.005 × 300 lbm/bbl × 25bbl/d × 1d/3.Solving M = 228.4 lbm/MMscf (or 40.C. with large amounts of condensate it is not uncommon to have as much as 90% of the injected methanol dissolved in the condensate (primarily) and gas phases. Shuler (1997) of Chevron provided a computerized version (HYDCALC) of the above calculation method.7 lbm/MMscf -Calculate the Total Amount of MeOH/MMscf MeOH in Water = 228.C.7 lbm/MMscf = 267. However.6 of results of the hand calculation (Example 6) with the computer method (Example 7). The hand calculation example is provided for understanding of the second approximation. which is included with the disk in this handbook.7 lbm MeOH in the water phase -Calculate Mass of MeOH Lost to the Gas Rule of Thumb 3 states that the maximum amount of methanol lost to the vapor phase is 1 lbm MeOH/MMscf for every wt% MeOH in the water phase. as shown by a comparison in Section II. Since a barrel of hydrocarbon weighs about 300 lbm.5wt%.7 lbm/MMscf MeOH in Gas = 27 lbm/MMscf MeOH in Condensate = 11. the Rules-ofThumb should be replaced by a more accurate calculation. -Calculate the Mass of MeOH Lost to the Condensate Rule of Thumb #5 states that the methanol concentration in the condensate will be 0.

Use of HYDCALC to Find Amount of Methanol and Glycol Injection This spreadsheet problem is the identical problem worked in Example 6 by hand.Version 7.0 spreadsheet program and copy HYDCALC into a hard drive directory. The gas also experiences a pressure drop to 950 psia.Starting warm temperature.25 bbl/d. Cold Pipeline Temperature . Solution: Figure 13 on the next page is a copy of HYDCALC. Pipeline Inlet Temperature .Condensate flow in the pipeline measured in bbl/d. Start Excel® . Gas Flow Rate . highlighting the data input that is needed to run the program. _____________________________________________________________________ Example 7. with 21 . obtain access to a Microsoft Excel® . Once the above values are input. and blue. To use HYDCALC. In the below example. The red text signifies required User Inputs.C. Determine the rate of methanol and glycol injection needed to prevent hydrate formation in the pipeline.HYDCALC is an IBM-PC compatible spreadsheet that provides an initial estimate of pipeline methanol injection for hydrate inhibition. Produced free water enters the pipeline at a rate of 0. Formation Water Rate . All required data are provided in the example. Gas exits the pipeline at a rate of 3. with an average density of 300 lbm/bbl and an average molecular weight of 90 lbm/lbmole. composed of the following eight pieces of information to start the program: 1) 2) 3) 4) 5) 6) 7) 8) Pipeline Inlet Pressure .Starting high pressure Cold Pipeline Pressure . the user will see text in three different colors on a color screen.1 and Example 4.Temperature at the coldest part of the pipeline. Gas Gravity .black.Gas gravity.784 has inlet pipeline conditions of 195oF and 1050 psia. due to printing restrictions. calculated by the steps in Section II. Once the file is opened. A sub-sea pipeline with the a gas gravity of 0. the User Input and Calculations are both listed in black. The pipeline produces condensate at a rate of 25 bbl/d. HYDCALC displays calculations for both Intermediate Results (in black) and the amount of methanol or glycol to be injected (in blue on a color screen).Produced water flowing into the pipeline (bbl/d).0 and open the file HYDCALC.Pressure at the coldest part of the pipeline. Condensate Rate . The gas flowing through the pipeline is cooled by the surrounding water to a temperature of 38oF.Version 7.Gas flow in the pipeline measured in MMscf/d. A prescription for the use of this method is shown in Example 7. red.2 MMscf/d.

percent MEG needed in water phase Vapor to liquid composition ratio Methanol in gas MEG in gas Methanol into condensate MEG into condensate Methanol to protect water phase MEG to protect water phase TOTALS Methanol to protect water phase Methanol going to gas Methanol into condensate TOTAL Methanol Rate Methanol Injection Rate (pure MeOH @ 77F) Methanol Rate/MMSCF 626.5 22.77 0 37.4 gal/day gal/MMSCF gal/day gal/MMSCF CALCULATION WORKSHEET Water in hot gas Water in cold gas WATER CONDENSED Total Water CONDENSED in the line Total water (from above) Hydrate temperature of gas Freeze depression required Wt.0 P.5 1758 190.0 27. Shuler CTN 694-7572.===> pressure where hydrates .0 27.J.5 619.784 3.2 lb/day lb/day lb/day lb/day gal/day gal/MMSCF MEG to protect water phase MEG in gas MEG into condensate TOTAL MEG Rate MEG Injection Rate (pure MEG) MEG Rate/MMSCF 1735 0 22.0 59.===> starting high pressure .4 lb/day lb/MMSCF lb/day lb/day gal/day gal/MMSCF . PJSH CPTC 5/27/97 HYDCALC Version 2 INHIBITOR REQUIREMENT CALCULATION FOR A WET GAS FLOWLINE USER INPUTS (in red) Bottom Hole Pressure Cold Line Pressure Bottom Hole Temperature Cold Temperature Gas gravity Gas Rate Condensate Rate Formation Water Rate ?? Calculated Condensed Water Total Water to Treat 1050 950 195 38 0.2 190.===> temperature where hydrates SUMMARY OF RESULTS Methanol Injection Rate (pure MeOH @ 77F) Methanol Rate/MMSCF MEG Injection Rate (pure MEG) MEG Rate/MMSCF 134.9 65. percent methanol needed in water phase wt.xls disk 2 for Excel 7.25 5.2 6.9 42.Figure 13 .0 59.2 25 0.0 lb/MMSCF lb/MMSCF lb/MMSCF lb/day bbl H2O/day bbl H2O/day F F % Summary of Results 45.5 767 1735 lb/MMSCF lb/MMSCF lb/day lb/day lb/day lb/day 767 79 37.Example #6 Calculated by HYDCALC a:\excel7\hydcalV7.5 884 134.7 5.8 1983 5.9 psia psia F F MMSCFD bbl/day bbl/ H2O/day bbl/ H2O/day bbl/ H2O/day Inputs .7 5.6 % 0.===> starting high temperature .9162 lb/MMSCFper % in water 24.9 42.

3 HYDCALC Result 619. which are vital to their use. Calculated Quantity Water Condensed. II.8 239. Limitations. With such inaccuracies. lbm/MMscf MeOH in Gas.the exception of gas gravity. and pressure of Examples 6 and 7. For example.25 42. The amount of methanol injected is 42. The following section provides accuracy and limitations of both HYDCALC and the hand calculation methods. 22 .4 gal/MMscf. HYDCALC inaccuracies are those of the charts upon which HYDCALC is based. lbm/MMscf Total MeOH Injection.784. gal/MMscf Hand Method Result with Rules-of-Thumb 591 228. The major inaccuracies in the second estimation method are in the gas gravity hydrate formation conditions. while it is possible to obtain more significant figures with HYDCALC than with the charts in the hand method. which are only accurate to ±7oF or to ±500 psia.7 276.7 11. Using HYDCALC it was estimated that 27 wt% methanol was required in the water phase to inhibit the pipeline. both include inaccuracies. lbm/MMscf MeOH in Water. lbm/MMscf MeOH in Condensate. Gas gravity was calculated using the method described in Example 4 to be 0. Figure 13 on the next page displays all input data and results. the amount of methanol or glycol injection could be in error by 100% or more. Accuracy.4 40. The principal virtue of the second estimation method is ease of calculation rather than accuracy.2 gal/MMscf and the amount of glycol injected is 59. while measurements by Robinson and Ng (1986) show that only 20 wt% methanol was required for inhibition at the same gas composition. the inhibitor temperature depression ∆T is accurate to ± 5%. temperature.2 While the hand calculation and the computer program provide only slightly different results. The Hammerschmidt equation. _____________________________________________________________________ For ease of use. the engineer will turn to HYDCALC to perform the second approximation calculation.C.7 27 11. lbm/MMscf Total MeOH Injection.7 267. and Extensions for Second Estimation Method A comparison of the previous results using the hand calculation method and the HYDCALC method is included in the below table.6.7 24.

1. The method details are too lengthy to include here. As a minimum of a 386-IBM computer with 2 megabytes of RAM is required. The program may be executed either from the Windows or from the DOS environment. calculation of solubility of MeOH and MEG in the gas (Section II. In Section II. more accurate calculations. Appendix B is a User’s Manual with several examples of the use of HYDOFF.D examples are provided for the most accurate methods for the following calculations: • • • • calculation of hydrate formation and inhibition in water (Section II. A modification of the gas gravity method was proposed for sour gases by Baillie and Wichert (1987). Chapter 5). and calculation of solubility of MeOH and MEG in condensate (Section II. The simplest (and perhaps the most beneficial) use of HYDOFF is illustrated through Example 8. The most accurate method for hydrate formation conditions.4).D. If the HYDCALC results indicate that hydrate formation will occur without inhibition. II. together with the amount of methanol needed in the water phase.3).2).D.A second limitation is that the method was generated for gases without H2S. _____________________________________________________________________ Example 8: Use of HYDOFF to Obtain Hydrate Formation and Prevention Conditions.D. the engineer interested in program details is referred to the hydrate text by Sloan (1998. Most Accurate Calculation of Hydrate Formation and Inhibition. is available as the final estimation technique in a computer program.DAT from the accompanying 3.5 inch disk onto a hard drive. first load both HYDOFF.1).EXE and FEED. Find (a) the hydrate formation pressure of the below natural gas at 38oF and (b) the amount of methanol in the water phase to inhibit hydrates at 38oF and 1000 psia. HYDOFF is an IBM-compatible computer program provided on the disk with this handbook.D. A User’s Manual (Appendix B) and an example are provided with this handbook. II. Hydrate Formation and Inhibitor Amounts in Water Phase. HYDOFF. conversion of MeOH to MEG concentration in water phase (Section II.D. The program enables the user to determine hydrate formation conditions and the amount of inhibitor needed in the free water phase. the engineer should elect to do further.D. The 23 . which represents the case for many gases in the Gulf of Mexico. To use the program.

2).19%. the gas composition may be input as part of the program HYDOFF. When asked for another calculation input 1 for “No” then Enter.0473 Enter. Ethane 0. The use of FEED. The next screen asks for the number of components present (excluding water). 24 .DAT to reflect the gas composition of the problem. n-Pentane 0. n-butane = 0. 2.DAT program is done at the MSDOS prompt. press Enter 3. press Enter. Read the hydrate formation pressure of 229. However it is not necessary to use FEED.94%. From Windows or in the proper directory. The next screen requests a list of the gas components present. The next series of screens request the input of the mole fractions of each component Methane 0. then Enter. or 1 and Enter if you wish to enter the gas composition in HYDOFF by hand. and saving the result using the standard MSDOS editing technique. each input from the user is underlined: 1. Propane 0.DAT. (meaning hydrates will form at any pressure above 230 psia at 38oF for this gas. n-Butane 0. After reading the title screen. carbon dioxide = 14.DAT is simpler and should be considered for multiple calculations with the same gas. by changing the composition of each component to that of the example gas. and 9 (in that order. press 2 and Enter if you wish to use the data in FEED.1) and the Hammerschmidt equation (Section II. 10. Nitrogen 0. The remainder of this example is written assuming that the user will enter the gas composition in HYDOFF rather than use FEED. input 38. 2. and Enter.gas composition (mole %) is: methane = 71. At the “Options” screen input 2.60%. At the “Options” screen. Modification of the FEED.73%. Carbon Dioxide 0. Input 1. In the following solution.0596 Enter. propane = 1.0194 Enter. or type HYDOFF. 7. ethane = 4.) 11.7 psia. 6. n-pentane = 0. separating the entries by commas) and then Enter. 5. 8. 5.79%. At the FEED. nitrogen = 5.C. Input 7 and Enter. 7. 8. At the “Units” screen.0079 Enter. click on. 3. so the results provide a comparison with hand and computer calculations of the gas gravity method (Section II.DAT question screen. coded by numbers shown on the screen. 12.96% Solution: The gas in this example has the same composition as the gas in Examples 6 and 7.7160 Enter. For convenience with multiple calculations. At the screen asking for the required Temperature.DAT.0079 Enter. 9. input 1 then Enter.1419 Enter.79%.C. press 1 (to choose oF and psia) then Enter 4. the reader may wish to edit the program FEED.DAT.

At the screen asking for the required temperature. At the screen to enter the “WEIGHT PERCENT of Methanol. 15. Example 9 (Section II. Ng and Robinson (1983) measured 20 wt% of methanol in the water required to inhibit hydrates at 38oF and 1000 psia. as compared with 65oF determined by the gas gravity method. the solubility in the water is only slightly affected by pressure over the range from 1000-3000 psia at offshore temperatures. through a similar trial and error process.D. A comparison of the measured value with the calculated value (22 wt%) in this example and through the Hammerschmidt equation provides an indication of both the absolute and relative calculation accuracy. it may be multiplied by KvMeOH to obtain the mole fraction of methanol in the gas.5oF. and 1036 psia. In using HYDOFF.2 Conversion of MeOH to MEG Concentration in Water Phase. Equation (2) should be used for the free water phase only. Once the mole fraction of methanol in water is determined. For a conservative estimate the 3000 psia line is recommended: 25 .3.209+ 2. 38oF. Read the resulting hydrate condition of 22 wt% MeOH.” input 22. since they are all non-hydrate formers.D. One starting place for the trial and error process would be the amount of MeOH predicted by the Hammerschmidt equation (27 wt%) in Example 6. _____________________________________________________________________ II. and Enter.0. first determine the amount of methanol required using HYDOFF.D. The concentration of inhibiting monoethylene glycol (MEG) in the water phase can be determined from methanol (MeOH) concentration using a simple correlation of inhibitors: wt% MEG = -1. II. as in Example 8. Solubility of MeOH and MEG in the Gas. It may require some trial and error with the use of the program before the correct amount of MeOH is input to inhibit the system at the temperature and pressure of the example.0008(wt% MeOH) 3 (2) In order to use Equation (2). Figure 11 is a fit of recent measurements by Ng and Chen (1995) for KvMeOH defined as the methanol mole fraction in gas relative to water (≡ yMeOH/xMeOH in H2O). As can be determined by Figure 11. HYDOFF can also be used to predict the uninhibited hydrate formation temperature at 1000 psia at 58. input 38. No measurements are available for the uninhibited formation conditions of the gas in this example.13.052(wt% MeOH) 2+ 0. if components heavier than n-decane (C10H22) are present. 14. Insert the amount of methanol in Equation (2) to determine the amount of mono-ethylene glycol needed in water to inhibit hydrates. they should be lumped with n-decane.D.34 (wt% MeOH).5) provides a summary calculation of all the procedures in Section II.

90 .C. No pressure dependence is observed. with the exception that both MeOH and MEG injection are calculated for comparison of each inhibitor as well as with the less accurate method of Section II.D. it may be multiplied by KLMeOH to obtain the mole fraction of methanol in the condensate.D.5738×(1/T(oR)) (3) Figure 12 provides an estimation of monoethylene glycol dissolved in gas at 1000 psig.D. The fit for the solubility of methanol in condensates of methane.5×(1/T(oR)) (4) Similar measurements by Ng and Chen (1995) are shown in Figure 15 to specify the solubility for monoethylene glycol (MEG) in the condensate. Solubility of MeOH and MEG in the Condensate.4.706 . propane. and n-heptane is recommended: KLMeOH = exp (5. from the data of Polderman (1958). Best Calculation Technique for MeOH or MEG Injection.D.KvMeOH = exp (5.7266. via KLMEG defined as the MEG mole fraction in condensate relative to water (≡ xMEG in HC/xMEG in L L H2O).D. due to the absence of such compounds in typical condensates.20 . Ng and Chen (1995) measure a negligible MEG concentration in the vapor as a comparison.5404.5) provides a summary calculation of all the procedures in Section II. Once the mole fraction of methanol in water is determined. II. The 26 . and n-heptane (or methylcyclohexane) is recommended. Note that the K MEG values are two orders of magnitude lower than K MeOH values. II. since toluene is not in condensate: KLMEG = exp (4. propane. and the line for MEG solubility in methane. Example 9 (Section II. Figure 14 is a fit of measurements by Ng and Chen (1995) for KLMeOH defined as the methanol mole fraction in condensate relative to water (≡ xMeOH in HC/xMeOH in H2O). The following example is identical that of Examples 6 and 7.D.5. _____________________________________________________________________ Example 9: Most Accurate Inhibitor Injection Calculation. A sub-sea pipeline with the below gas composition has inlet pipeline conditions of 195oF and 1050 psia. In Figure 14 all lines are pressure independent and the toluene line should not apply.4×(1/T(oR)) (5) Example 9 (Section II.5) provides a summary calculation of all the procedures in Section II. As indicated in the figure the amount of MEG in the vapor is very small.

55142 -3242.91795 -5389.8E-3 l/T(R) .- 3 10‘23- 5 :_ ti blK mc= a + b[l/T(R)] a 3- .90062 -5404.Methanol Lost to Condensate (From Sloan.1E-3 2.45 5. 1998) Temperature (OF) 20 s-l 7- 30 40 50 60 70 80 90 100 0 115 130 1o-~_I’1’~““““““““‘~“““““~“““‘~ h 634- zi 5 g ‘- i ‘u ‘.OE-3 1.Figure 14 .73 3.43 2.b 0 [7 0 + Methane Propane n-Hcptane + Metime + Propane htiylcyclohexane + + Methane Propane Tolueoe + 5.9E-3 1.‘I.

1998) Temperature.9SE-3 “I”” MOE-3 l/T(R) I “‘I Las-3 I ” 1.Mono-Ethvlene Glvcol Lost to Condensate (Fmm Sloan.= a + b[l/T(Fi)] 0 f3 0 Mdlmw+Pmpm+ll-~ I’btbw+~+~~e -+Rupm+Tol\rar - a - b 4A9818 2. OF J!“““““.~“““““” 40 50 60 70 80 90 100 112 InK.Figure 15 .ooE-3 ” I ” 1.SOE-3 ” 1.7s3 .65872 -726638 -5211.86 I ” z.

34lbm     bbl  gal  day     1day   3. with an average density of 300 lbm/bbl and an average molecular weight of 90 lbm/lbmole.6 wt% in the water phase. The gas also experiences a pressure drop to 950 psia. Using Equation (2) the MEG concentration was calculated at 33.19%.2MMscf   lb H O  = 27.4 m 2  MMscf  . n-butane = 0. nitrogen = 5.25 bbl/d. Step 2) Calculate the Mass of Liquid H2O/MMscf of Natural Gas . Natural gas composition (mole%): methane = 71. Gas exits the pipeline at a rate of 3.gas flowing through the pipeline is cooled by the surrounding water to a temperature of 38oF. Produced salt-free water enters the pipeline at a rate of 0. carbon dioxide = 14. The pipeline produces condensate at a rate of 25 bbl/d.73%.4 lbm = 618.60%.Calculate Mass of Produced H2O Flowing into the Line Convert the produced water of 0.Total Mass of Water/MMscf Gas: Sum the condensed and produced water 591 lbm + 27. propane = 1.2 MMscf/d.96% Find the rate of both methanol and monoethylene glycol injection needed to prevent hydrate formation in the pipeline.25bblH 2 O  42 gal  8. The inlet gas (at 1050 psia and 195oF) water content is read as 600 lbm/MMscf. Step 1) Calculate the Concentration of MeOH and MEG in the Water Phase. The mass of liquid water due to condensation is: 600 lbm _ 9 lbm = 591 lbm MMscf MMscf MMscf .79%. In Example 8 the methanol concentration was calculated to be 22 wt% of the free water phase at 38oF and 1000 psia. to calculate the water in the vapor/MMscf. n-pentane = 0. The outlet gas (at 950 psia and 38oF) water content is read as 9 lbm/MMscf. ethane = 4.25 bbl/d to the basis of lbm/MMscf:  0.94%.Calculate Mass of Condensed H2O Use the water content chart (Figure 10).79%.4 lbm MMscf MMscf MMscf 27 . Solution: Basis: the basis for solution is 1 MMscf/d.

69 The mole fraction of MeOH in the vapor is yMeOH = KvMeOH•xMeOH in H2O or yMeOH = 0.4 lbm MeOH/MMscf in the water phase (b) In Step 1 33.7oR) by Equation (3).6. gas. where an scf is at 14.137.Step 4) Calculate the Rate of Methanol and MEG Injection MeOH and MEG can exist in three phases: water.137 = 0.4 lbm in Step 3.0004055 The daily gas rate is 8432 lbmol (= 3. The mass of MeOH in the free water phase per MMscf is: 22wt% = M lb m MeOH × 100% M lb m MeOH + 618.5 scf/lbmol).4 / 32 + 618. The distribution constant of MeOH in the gas is calculated at 38oF (497. and the mass of water/MMscf was calculated at 618.4lb m H 2 O Solving N = 313. and condensate.42 lbmol (= 28 .00296 (3) o o where R = F + 459.4 lb m MeOH / (32lb m / lbmol MeOH) 174.0 wt% MEG is required to inhibit the free water phase.7oR) = 0.6wt% = N lb m MEG ×100% N lb m MEG + 618.706 . and the mass of water/MMscf was calculated at 618.7 psia and 60oF).2 × 106 scf / (379.1 lbm MEG/MMscf in the water phase -Calculate Amount of (a) MeOH and (b) MEG Lost to the Gas (a) MeOH Lost to Gas.4lb m H 2 O / (18lb m / lbmolH 2 O) The mole fraction MeOH in the water phase is xMeOH in H2O = 0. The mass of MEG in the free water phase per MMscf is: 33. relative to the methanol in the water KvMeOH = exp (5.00296 × 0. The mole fraction MeOH in the free water phase is: mole fraction MeOH = 174. so that the MeOH lost to the gas is 3.4lb m H 2 O Solving M = 174. The total masses of MeOH and MEG injected per MMscf are calculated as follows: -Calculate Amount of (a) MeOH and (b) MEG in the Water Phase (a) 22.5738×(1/497.0 wt% methanol is required to inhibit the free water phase.4 lbm.

0004055 × 8432) or 109.9×10-5 lbmol/MMscf (= 0.2 lbm/MMscf (= 109.4lb m H 2 O / (18lb m / lbmolH 2 O) The mole fraction MEG in the water phase is xMEG in H2O = 0.1/ 62 + 618.5404.7 oR)) = 3.8 lbm/MMscf) (b) MEG Lost to Condensate.20 .0009617 The condensate rate is 26. Since the calculation basis is 1 MMscf/d. such an amount is negligible.0000038)) or 0.2 MMscf) so that the amount of MEG in condensate is 9. The distribution of MeOH in the condensate is calculated via equation (4) KLMeOH = exp (5.128).0061 lbm/MMscf) -Calculate the Total Amount of MeOH/MMscf and MEG/MMscf 29 .0 lbmoles/MMscf (= 25bbl/d×300 lbm/bbl×1 lbmol/90 lbm×1d/3.4 lbm/day. the amount of MeOH lost is 34.7oR)) = 0.04 × 10-5 (5) The mole fraction MEG in condensate is xMEG in HC = KLMEG×xMEG in H2O calculated as 3.0 lbmoles/MMscf (= 25bbl/d×300 lbm/bbl×1 lbmol/90 lbm×1d/3.04 × 10-5 × 0.137 = 0. In Figure 12 use the 50 wt% MEG line to determine the MEG lost to the gas is 0.0000038 × 26 / ( 1 .006 lbm/MMscf at 38oF and 1000 psig.1 lb m MEG / (62lb m / lbmol MEG) 313. The mole fraction MeOH in condensate is xMeOH in HC = KLMeOH×xMeOH in H2O or xMeOH in HC = 0.0.2 MMscf).4 lbm / 3.8 × 10-6.00702 × 0. -Calculate Amount of (a) MeOH and (b) MEG Lost to the Condensate (a) MeOH lost to the condensate.0009617 × 26 / ( 1 .0.0.00702 (4) where oR = oF + 459. (b) MEG Lost to Gas.128.7266.009617)) or 0.2 MMscf) so that the amount of MeOH in condensate is 0. The distribution of MEG between the aqueous liquid and condensate is given by KLMEG = exp (4. The mole fraction MEG in the water phase is calculated as mole fraction MEG = 313.90 .5×(1/497.4×(1/497.025 lbmol/MMscf (= 0.69. The condensate rate is 26. Ng and Chen (1995) measured a negligible concentration of MEG in the gas phase at conditions similar to those of this problem.(= 3.

177% i-pentane. 0.574% carbon dioxide.5 MEG 313.051% heptane. and 20% methanol in the water phase. 0.732% propane.1 0.112% hexane.2 0. While this pipeline passes through shallow water (a marsh) many of the principles illustrate applications to offshore pipeline design.2 gal/MMscf in the second estimation method. lbm/MMscf In Gas. As the gas moves down the pipeline.3 The example illustrates that for this gas condition. were superimposed on the hydrate formation curve shown in Figure 17.452% i-butane. lbm/MMscf Total. represents a considerable savings in the amount of MeOH injected (31. 0. (3) insulating the pipeline. so methanol must be added.11 33. 110 hydrate incidents occurred in the line during winter of 1995-1996 at a cost of $323.68% ethane. it begins to cool towards ambient temperatures. indicating that 25% wt% methanol in water is needed to inhibit hydrates. Hydrate formation conditions. (1996) of Texaco.MeOH In Water. 0.) _____________________________________________________________________ II. far from hydrate forming conditions. by Todd et al. the injection amounts of MeOH and MEG are comparable. Once the temperature reaches approximately 63oF hydrates will form.5 gal/MMscf versus 42.4 34. Despite large quantities of methanol injection for hydrate prevention. The figure shows pipeline conditions and the hydrate formation curves for various concentrations of methanol. Combinations of four alternative hydrate prevention methods were considered: (1) burying the pipeline. 30 . 3. consider the steps taken to prohibit hydrates in the Dog Lake Field export pipeline in Louisiana. are calculated via an earlier version of HYDOFF with 0 wt%. gal/MMscf 174. 1. Case Study 6: Prevention of Hydrates in Dog Lake Field Pipeline As a summary of the thermodynamic hydrate prevention methods. The more precise calculation shown here however..4 31. 0.114% n-pentane.732.029% octane.0061 313. and (4) methanol addition.517% nitrogen.E. (2) heating the gas at the wellhead.8 209. The Dog Lake gas composition is: 92. lbm/MMscf In Condensate. calculated using PIPEPHASE . lbm/MMscf Total. 0.1 mole% methane. 10%. The pipeline pressure and temperature.006 0. shown in Figure 16. 0. The details of each prevention measure are considered below.452% n-butane. Gas leaves the wellhead at 1000 psia and 85oF. 0. During the winter months hydrates formed in the line. 0.

Figure 16 .Dog Lake Field .Hydrate Curves (From Todd. 1997) 4000 20 wt% MeOH 10 wt% MeOH 3500 3000 Pressure(psia) 2500 2000 1500 1000 500 0 30 35 40 45 50 Temperature(oF) 55 60 65 70 Hydrate Formation Region 0 wt% MeOH Hydrate Free Region .

1997) 2000 1800 1600 1400 Pressure(psia) 1200 1000 800 600 400 200 0 30 Separator 25 wt% MeOH 20 wt% MeOH 10 wt% MeOH 0 wt% MeOH Pipeline Wellhead 40 50 60 Temperature(oF) 70 80 90 .Dog Lake Field .Figure 17 .Original Conditions (From Todd.

1. Burying the Pipeline. Some of the Dog Lake pipeline was built over a stretch of marsh. The exposure to winter ambient temperatures caused rapid reductions in the gas temperature. Burying the pipeline would protect it from low environmental temperatures due to the higher earth temperatures. Figure 18 displays the temperature increase in the pipeline after exposed areas were buried relative to the exposed pipeline in Figure 17. With pipeline burial, the need for methanol in the water phase was reduced from 26 wt% to less than 19 wt%. 2. Wellhead Heat Addition. Catalytic in-line heaters could be installed at the wellhead to increase the gas temperature to 125oF. Figure 19 shows the pipeline temperature increase caused by the combined prevention methods of burial and wellhead heating. Use of these two methods permitted the methanol concentration to be reduced to approximately 14 wt% to prevent hydrate formation in the line. It should be noted that heating may increase the amount of corrosion in the line. 3. Insulation. Insulation of exposed areas near the wellhead and battery would maintain higher pipeline temperatures, thereby reducing the amount of methanol needed for hydrate inhibition. Figure 20 displays the temperature increase in the buried and heated pipeline when exposed pipes were insulated. The pipeline is now outside the hydrate formation region, and methanol addition is no longer needed. 4. Methanol Addition. Continued methanol injection could be done at an cost of approximately $1.50 -$2.00 per gallon. The cost of methanol to an offshore platform cost $2.00 per gallon during the 1996-7 winter. Since methanol recovery may not be economical, methanol is normally considered an operating cost. This case study illustrates how combinations of pipeline burial, insulation, heating, and methanol injection can be used to prevent hydrates. The selection of the hydrate prevention scheme(s) is then a matter of economics, as considered in Section IV of this handbook. _____________________________________________________________________

II.F. Hydrate Limits to Expansion through Valves or Restrictions. When water wet gas expands rapidly through a valve, orifice or other restriction, hydrates form due to rapid gas cooling through Joule-Thomson expansion. Hydrate formation with rapid expansion from a wet line commonly occurs in fuel gas or instrument gas lines, as indicated in the platform Example 12 in Section II.F.3. Hydrate formation with high pressure drops can occur in well testing, start-up, and gas lift operations, even when the initial temperature is high, if the pressure drop is very large. This section provides methods to determine when hydrates will form upon rapid expansion. A rough estimation method (Section II.F.1) is followed by a more accurate

31

Figure 18 - Dog Lake Field with Burial
(From Todd, 1997)

2000 1800 1600 1400 Pressure(psia) 1200 Separator 1000 800 600 400 200 0 30 40 50 60 Pipeline 20 wt% MeOH 10 wt% MeOH

0 wt% MeOH

Wellhead

70

80

90

Temperature(oF)

Figure 19 - Dog Lake Field with Burial and Heating
(From Todd, 1997)

2000 1800 1600 1400 Pressure(psia) 1200
Sep. 20 wt% MeOH 10 wt% MeOH 0 wt% MeOH

Pipeline

1000 800 600 400 200 0 30 40 50 60 70 80 90 100 110

Wellhead

120

130

Temperature(oF)

Figure 20 - Dog Lake Field with Burial, Heating, and Insulation
(From Todd, 1997)

2000 1800 1600 1400 Pressure(psia) 1200 1000 800 600 400 200 0 30 40 50 60 70 80 90 Temperature(oF) 100 110 120 130 Separator Pipeline Wellhead
20 wt% MeOH 10 wt% 0 wt% MeOH MeOH

but resource intensive method (Section II.F.2), concluding with prevention techniques in Section II.F.3. Figure 7 is a schematic of the pressure and temperature of a pipeline production stream during normal flow with entry into the hydrate formation region. If the gas expands rapidly, the normal pipeline cooling curve of Figure 7 will take on a much steeper slope, but the hydrate formation line remains the same. Two rapid expansion curves for a 0.6 gravity gas are shown in Figure 21. Intersections of the gas expansion curves with the hydrate formation line gives the limiting expansion discharge pressures from two different high initial pressure/temperature conditions. In Figure 21, the curves specify the pressure at which hydrate blockages will form at the restriction discharge for an upstream pressure and temperature. Gas A expands from 2000 psia and 110oF until it strikes the hydrate formation curve at 780 psia (and 57oF) so that 780 psia represents the limit to hydrate-free expansion. Gas B expands from 1800 psia (120oF) to intersect the hydrate formation curve at a limiting pressure of 290 psia (42oF). In expansion processes while the upstream temperature and pressure are known, the discharge temperature is almost never known, but the discharge pressure is normally set by a downstream vessel or pressure drop. Cooling curves such as the two in Figure 21 were determined for constant enthalpy (or Joule-Thomson) expansions, obtained from the First Law of Thermodynamics for a system flowing at steady-state, neglecting kinetic and potential energy changes: ∆H = Q - Ws (6)

where ∆H is the enthalpy difference across the restriction (downstream - upstream), while Q represents the heat added, and Ws is shaft work obtained at the restriction. Offshore restrictions have no shaft work, and because the system operates adiabatically, both Ws and Q are zero, resulting in constant enthalpy (∆H =0) operation on expansion. Due to the constant enthalpy requirement, rapid gas expansion results in cooling, except at very high pressures, where heating occurs on expansion due to a compressibility decrease with temperature. The upstream pressure at which the system changes from heating to cooling upon expansion is called the Joule-Thomson inversion pressure. Rule-of-Thumb 7. Natural gases cool upon expansion from pressures below 6000 psia; above 6000 psia the temperature will increase upon expansion. Virtually all offshore gas processes cool upon expansion, since only a few reservoirs and no current pipelines or process conditions are above 6000 psia.

32

:: .I L Z E k 800 600 500 400 300 30 40 50 60 70 80 90 100 1 Temperature(F) .Figure 21 Hydrate - Gas Expmsion into Forrmtioo Region Katz. 1944) (From 2000 1500 1000 d .

Rule-of-Thumb 7 was determined by G. 23. with gas enthalpy-entropy charts by Brown (1945) to obtain the cooling line. Rapid Calculation of Hydrate-Free Expansion Limits. As indicated in Section II. To what pressure may a 0. The abscissa (or x axis) in each figure represents the lowest downstream pressure without hydrate formation. Hydrates will not form upon expansion to atmospheric pressure.6 gravity gas is to be expanded from 1500 psia to 500 psia. A 0.6 gravity gas at 2000 psig and 140oF be expanded without hydrate formation? Solution: In Figure 22 it is seen that there is no intersection with the 140oF isotherm. and 24 occur at an inlet pressure of 6000 psia.. It should be noted that the maxima in Figures 22. Example 10c. by the gas gravity chart (Figure 9) to obtain the hydrate formation line in Figure 21. Brown at the University o Michigan (1945) who constructed the first natural gas enthalpy . Cautioning that the charts applied to gases of limited compositions. the Joule-Thomson inversion pressure.6 gravity gas at 2000 psia and 100oF be expanded without danger of hydrate formation? Solution: From Figure 22. II.6 gravity chart (used for both hydrate formation and gas expansion) may have inaccuracies of ± 500 psia.F. The following three examples for chart use are from Katz’ original work. Katz provided expansion charts for gases of 0. What is the minimum initial temperature that will permit the expansion without danger of hydrates? Solution: From Figure 22 the answer is read as 99oF or above. read 1050 psia.6. This provides a further validation of Rule-of-Thumb 7 above. shown in Figures 22.1.C the 0. 0. _____________________________________________________________________ Example 10a Maximum Pressure of Gas Expansion. and 24 respectively. _____________________________________________________________________ Figures 22.G. How far may a 0.8 gravities. Accuracy limits to these expansion curves have been tested 33 . 23. Minimum Initial Temperature Before Expansion. and 0. Example 10b. Unlimited Gas Expansion. and 24 for gas expansion incorporate the inaccuracies of gas gravity charts from which they were derived.7. given the upstream pressure on the ordinate (y axis) and the upstream temperature (a parameter on each line). 23.entropy charts. Katz (1945) generated charts to determine the hydrate-free limit to gas expansion.

ffas Emansion of 0.6 6as Gravitv W6 (From Katz.1959) 10000 8 6 _ -I _ 4 2 1000 6 6 4 i ! _ _ _ _ _ _ Initial 1 2 _ _ - 100 100 2 4 6 6 1000 2 Pressure (psia) .Figure 22 .

Fimure Gas 23 10000 6 Exsansion of 0.7 ffas Gram NG (From Katz.- T ~ 7 I I I 2 _ 1 _ i I I -I- I I ‘_ I I L ~ _ _’ I I _ _ _ ! I I ~ I I - I I _ I I I I I I I I I I I I I I I I I I II/I 6 I I 2 4 6 6 1000 2 4 I 610000 100 F..inal Pwssuya fpsia\ .1959) _ _l _ I~ I -II ~ i I I I I I I ~ -II I I I I I I I I I I I I I I I I I I 6 - f _I_ _ _ I _ 1 I I _I_ I I -I- I I I I I I I I I I I _ I I I / -I- r .-/- .

_ I _..10()OOT . 1959) - --- r I -+-- -- _ _._ I I _ _ I I I I I I I I + I I _ I I - I 2 _ - I I I I - - - - l I I I I 2 - I I I 100 2 4 I I 6 I a 1000 Final Pressure (psia) .-~ - (From Katz.

which intersects the hydrate formation line. In the new method. and 3% C3H8 with free water in a pipeline. the first step is to generate the hydrate stability pressure-temperature line as in Figure 21. 23. For either condition. The computer program XPAND is included with this handbook for calculation of the second. Just as before. The user changes the outlet temperature guess until a value of ∆H = 0 is obtained. (1983) who found for example. In order to use the more accurate method.D. pressure. 7% C2H6 . _____________________________________________________________________ Example 11: Hydrate Formation on Expansion of a Natural Gas A simple natural gas consists of 90 mol% CH4 . or (b) 77oF and 2180 psia. Two initial inlet process conditions are considered for expansion across a valve: (a) 68oF and 2180 psia. The resulting discharge temperature and pressure is plotted to obtain the expansion curve. and gas composition. the intersection of an isenthalpic (∆H=0) cooling curve with the hydrate three-phase locus may be determined. is hydrate formation a possibility? Are there process limitations on the expansion from either initial condition to 1450 psia? 34 . using the method detailed by Sloan (1998. While this method requires more resources (namely time and an IBM-compatible computer) than the Joule-Thomson charts. II. the isenthalpic line is determined via a modern equation-of-state. Joule-Thomson expansion line. using the same principles indicated in Figure 21. using HYDOFF as indicated in Section II.1. For one inlet temperature and pressure. and 24. Later the amount of methanol injected to displace the hydrate formation curve to the left can be calculated.F. a series of such discharge points provides a curve which intersects the hydrate formation curve at the limiting temperature and pressure of expansion. it results in higher accuracy and provides an estimation of the amount of methanol inhibitor required. for an initial temperature.F. that the allowable 0. A more accurate computer method is available. More Accurate Calculation of Hydrate-Free Limits to Gas Expansion.3 at the close of this Section. pressure and gas composition. the program calculates the enthalpy change (∆H) for a specified outlet pressure and a temperature guess. given by Figure 22.by Loh et al. as illustrated in Example 12 in Section II. The expansion line is calculated with an equation-of-state. Appendix A).2.6 gravity gas expansion from 150oF and 3500 psia should be 410 psia rather than the value of 700psia. and the program HYDOFF replaces the gas gravity chart to predict hydrate formation conditions. The result may be compared with the Joule-Thomson result in Figures 22. Given an inlet temperature.

dehydrate the gas before expansion. A vapor-liquid equilibria flash calculation indicates that the highest temperature at which a hydrocarbon liquid can occur (the cricondentherm) for this mixture is -44oF.6oF. limit the final expansion pressure to a higher value than 1990 psia. isenthalpic (∆H=0) depressurization without heating from the surroundings.D as: T(oF) P(psia) 32 119 35 149 40 213 45 303 50 368 55 551 60 718 65 1117 68 1624 71 2509 77 4046 A semi-logarithmic interpolation of the above values gives the hydrate formation point at 70oF when the pressure is 2180 psia. First. the isenthalpic expansion system extends further into the hydrate region. The remainder of this example concerns the generation of Figure 25 and the processing implications. The result. A second. so the process will not form hydrocarbon liquid. The expansion program was written for a gas phase.4 55. as illustrated in Example 12: 1. plotted as line ABC in Figure 25 shows an isenthalpic intersection with the hydrate formation boundary at approximately 70. Only with subsequent heating at a constant pressure of 1450 psia. Using XPAND on the disk accompanying this handbook (see the User’s Manual prescription in Appendix B) the following isenthalpic line is obtained: P (psia) T (oF) for ∆H=0 2100 68. 3.Solution: Before doing any hydrate calculations. If the system at 68oF and 2180 psia has formed hydrates.0 2000 1800 1600 1450 62. If the system pressure is lowered to 1450 psia slowly and isothermally (with substantial heat input) hydrates will dissociate at 1537 psia. add inhibitor at the restriction inlet. results in much colder gas at 1450 psia. A similar calculation for the system initially in the fluid region at 77oF and 2180 psia shows the problem with isenthalpic expansion.2 46.9 39. but the initial conditions of 77oF and 2180 psia remains in the fluid (vapor-liquid water) region.8 As shown in Figure 25. 1990 psia. consider two means of depressurization. To prevent expansion into the hydrate region four options may be considered. Figure 25 shows the expansion conditions of both inlet conditions for the gas. the pressures and temperatures of hydrate formation are calculated using the program HYDOFF as in Section II. 2. to eliminate the possibility of encountering both vapor and liquid hydrocarbon phases. Therefore the initial condition of 68oF and 2180 psia is within the hydrate formation region. or 35 .5oF. one should confirm that this gas is not close to the hydrocarbon dew point. will the system become hydrate-free at 66.

2180 psia B A ∆H = 0 1500 ∆T = 0 1000 500 Hydrate Formation Curve 0 30 35 40 45 50 55 60 65 70 75 80 Temperature(oF) . 1998) 3000 Isenthalpic Expansion From 68oF. 2180 psia C 2500 Pressure(psia) 2000 ∆H = 0 Isothermic Expansion From 68oF.Figure . 2180 psia Isenthalpic Expansion From 77oF.25 Joule-Thomson Cooling Through Gas Expansion (From Sloan.

The mole fraction 36 .3. which may result in other. hydrate formation in a platform instrument gas line has caused system shutdown. ethane. using a process simulator package like HYSIM . and an isenthalpic flash should be performed to obtain the cooling curve. which is used to supply power to platform compressors. The inlet flowline was offgas from the first stage separator (see Figure 8.g. There are several limitations to XPAND. 68oF and 2180 psia) will only cause the downstream portion of the plug to progress further into the hydrate region. First.17 in Appendix C. In the initial part of the above example.4. Methods to Prevent Hydrate Formation on Expansion. larger hydrate problems. propane. subsequent cooling of the non-flowing pipeline into the hydrate formation region resulted in a pipeline blockage upon resumption of flow. or with significant amount of heavy components. Pipeline hydrate plugs are frequently porous. If there is a question whether the system might contain a liquid either at the inlet or discharge. heat the gas to a higher inlet temperature. it was seen that expansion from a condition which has a hydrate plug (e. XPAND was generated only for the first five common paraffins (methane. or PROCESS . the engineer may group components larger than pentanes into the “pentane plus” fraction of the gas. Frequently gas expansion causes hydrate formation in fuel gas lines and in instrument gas lines on a platform. Example 3) so the gas was saturated with water. With the above restrictions. Heat must be put into the system from the surroundings to dissociate hydrates.F summary of hydrate prevention during gas expansion. so that depressurization from one (downstream) side can result in Joule-Thomson cooling as gas flows through the plug. The field tests which confirm the above discussion are given in Case Studies C. normal butane. II. with four methods for hydrate prevention in a fuel gas line. _____________________________________________________________________ Example 12: Hydrate During Gas Expansion An offshore platform design required fuel gas at 300 psia and a rate of 0. it is limited to the vapor phase and will not account for expansion of a fluid containing any liquid amount. Expansion across a hydrate plug yields identical results to expansion across a valve. iso-butane. Secondly. ASPEN . and normal pentane) so XPAND cannot be used with nitrogen. acid gases (H2S or CO2). A control valve was placed on fuel gas line from the inlet flowline to provide the required pressure and flow of fuel gas. the engineer should calculate the hydrocarbon dew point.15 and C. The following example provides a Section II.02 MMscf/d from a high pressure flowline at 1500 psia and 100oF. In some cases.F.

they are plotted to determine the intersection with hydrate formation curves (including inhibited curves) generated by HYDOFF. Drying the Inlet Gas Ex12.0014 i-pentane.B4. Prevention via Methanol Injection Upstream of Expansion Ex12. Under the current design the initial temperature of 100oF will cause hydrates to form just downstream of the fuel gas control valve. This gas is identical with that in Example 4.053 ethane. 0.0018 i-butane. The expansion enters the uninhibited formation region at 53oF and final temperature after expansion is calculated to be 33oF.A2. Hydrate-Free Expansion Limits Using HYDOFF and XPAND Ex12. Parallel Expansions Ex12. 0.A2. Hydrate Prediction Using XPAND and HYDOFF. Figure 25 shows such intersections. Solution: The example solution is provided with the following steps: Ex12. Using the Katz Joule . temperature and gas composition to calculate the downstream gas temperature at a given discharge pressure. 23 and 24). XPAND was used to calculate the discharge temperature of the natural gas upon expansion.B1.B2. Is there a chance that hydrate formation might occur in the fuel gas line? If so. 2. parallel expansions. Hydrate Prediction Through Joule-Thomson Diagrams. Appendix B gives a step-by-step XPAND User’s Manual for the calculation in this example. 3. Hydrate-Free Expansion Limits Using the Joule-Thomson Diagrams Ex12. whose gravity is calculated as 0.Thomson expansion diagrams (Figures 22. Figure 22 provides an estimate that a 0. Prevention via Heat Addition to Two-Stage Expansion Ex12. 4. In Figure 26 note that the expansion line is curved. two stage expansion with intermediate heat addition.A1. 0.A1. 0. the minimum initial temperature required for hydrate-free operation can be estimated.composition of the components were: 0.D. Ex12.927 methane. For a comparison with 105oF inlet temperature requirement by the Katz 37 . methanol injection upstream of expansion. and drying the inlet gas. Once the expansion P-T values are obtained. requiring calculation of several temperatures and pressures along the expansion line.014 propane. which of the following ways could be used to prevent hydrates? 1.B3. using inputs of the upstream valve pressure.603. as done in Section II.0034 n-butane.6 gravity natural gas must have an initial temperature of 104oF to prevent hydrate formation during gas expansion from 1500 psia to 300 psia. and 0.

Figure 26 .Hydrate Formation Curve for Single Valve Expansion 1600 1400 1200 Pressure(psia) 1000 800 600 Gas Expansion Curve 400 200 0 30 40 50 60 70 80 o Temperature( F) 90 100 110 Outlet Hydrate Formation Curves 20 Wt% MeOH 10 Wt% MeOH 0 Wt% MeOH Inlet Hydrates No Hydrates .

The following calculations provide the pressure and temperature conditions in the system shown in Figure 24. Heat Addition with Two-Stage Expansion. In-line heaters could be installed to raise the temperature of the gas outside the hydrate formation region. the platform design had to be modified to inhibit hydrate formation.Joule-Thomson charts. In the case considered here. 3) parallel expansion. 2) methanol addition. a T3 of 68oF is required to maintain the final temperature at 44oF. Figure 28 suggests that heating before expansion through a single control valve may provide a more economical method to prevent hydrates on expansion. Figure 27 is a schematic of the two control valves and in-line heater design for the fuel gas line. and 4) drying the gas. Details of each prevention method are provided below.B. Four hydrate prevention methods were considered: 1) Heat addition to two stage expansion. For this example. Using XPAND the temperature of the gas at 675 psia is predicted to be 58oF at the first valve discharge. In our example. Figure 28 shows the gas expansion conditions and the HYDOFF hydrate formation curves. Figure 26 shows that more than 10 wt% methanol is needed in the free water phase to prevent hydrate formation. Hydrate Prevention After establishing that hydrates will form upon gas expansion. A single control valve and heater would save the capital cost of one control valve and may be a better alternative to prevent hydrates on expansion.B. Methanol can be injected into the fuel supply line upstream of the control valve to prevent hydrate formation downstream of the valve.B. Ex12. XPAND was used to estimate a value of T3 at the second valve inlet which provided a discharge value T4 outside the hydrate formation region. The cooler gas present after the first pressure drop facilitates heat transfer before the second valve. A better estimate of 12 wt% methanol in the 38 . In Figure 28. heat is added to the system (line 2) to raise the temperature to prevent hydrates upon gas expansion across the second control valve (line 3). two control valves are used with an in-line heater between them. Ex12. the pressure ratio (Pin/Pout) will be arbitrarily set at a value approximately equal across each control valve. Methanol Addition. Ex12. demonstrating that the gas is outside the hydrate formation region after the first pressure drop (line 1).2. providing 675 psia as the intermediate pressures after the first control valve. the inlet temperature using XPAND should be 108oF for hydrate-free expansion from 1500 psia to 300 psia. just above the hydrate formation region at the required pressure of 300 psia. The heat duty in the exchanger was defined by the temperature increase (T3-T2).1.

Figure 27 .Two Stage Gas Expansion with Heating 1st Control Valve In-Line Heater 2nd Control Valve P4= 300 psia T4= 44oF P1 = 1500 psia T1= 100oF P2= 675 psia T2= 58oF P3= 670 psia T3= 68oF Estimated Using HYDXPAND .

Two Stage Gas Expansion with Heat Addition 1600 1400 20 Wt% MeOH 10 Wt% MeOH 0 Wt% MeOH Inlet 1st Valve(T1) Hydrates 1200 Pressure(psia) 1000 800 600 400 200 0 30 40 50 60 70 Temperature(oF) 80 90 100 110 Outlet 2nd Valve(T4) Outlet 1st Valve (T2) Heating Line #2 Line #1 Inlet 2nd Valve(T3) Gas Expansion Curve No Hydrates Line #3 .Figure 28 .

16 lbm/MMscf = 29 lbm/MMscf.2.2. The distribution coefficient of MeOH in the gas is calculated at 33.02 MMscf 0.water phase was obtained through interpolation using XPAND and HYDOFF. Mass of MeOH Required in the Water Phase. Consequently.Water condensation with expansion. M = 0.58lbm H2 O × = MMscf day day Ex12.071. The total amount of methanol required for upstream gas injection is calculated through methods of Section II.079 / 32 + 0.706 .B. the total amount of water (W) condensed per day is: 29lbm H2 O 0.7oR) = 0.B. one can calculate the mass of free water in the pipeline due to dewpoint condensation from Figure 10 (45 lbm H2O/MMscf in the vapor at 1500 psia and 100oF and 16 lbm H2O/MMscf in the vapor at 350 psia and 33oF). Gas flows into the fuel line at a rate of 0.D. Mass of MeOH Lost to Condensate and Vapor.a.00263 (3) The mole fraction of MeOH in the vapor is yMeOH = KvMeOH•xMeOH in H2O or yMeOH = 0.000187 39 . the amount of methanol. The amount of free water that forms from the vapor is 45 lbm/MMscf. Ex12.079 lb m MeOH / (32 lb m / lbmol MeOH) 0. Since the gas is saturated with water.7oR) by Equation (3).58 lb m H 2 O / (18lb m / lbmolH 2 O) The mole fraction MeOH in the water phase is xMeOH in H2O = 0.2.079 lbm MeOH/day Ex12.B.00263 × 0.c. The mass of MeOH can be found by using the definition of weight percent wt % = M (lbm MeOH ) X 100% M ( lbm MeOH ) + W ( lbm H2 O) Solving for 12 wt%. relative to the methanol in the water KvMeOH = exp (5.b.03 oF (492.5738×(1/492.02 MMscf/d.071 = 0. The mole fraction of MeOH in the water is found by the equation: mole fraction MeOH = 0.

it is hoped that flow can be maintained in one fuel gas line without the need for hydrate inhibition.000187 × 52. It is good design practice to place both fuel gas and instrument gas lines downstream of a TEG drying unit or a molecular sieve adsorption tower. with injection before the control valve as shown in Figure 29.B. The capital cost is doubled however.B.” 40 .d. 41) stated in their classic study of hydrate formation and prevention: “The only method found to be completely satisfactory in preventing the formation of hydrates in gas transmission lines is to dehydrate the gas entering the line to a dew point low enough to preclude formation of hydrates at any point in the system. The design of a drying unit is outside of the scope of this handbook. Conditions of hydrate formation on parallel gas expansion are exactly the same as shown in Figure 26.g. _____________________________________________________________________ Of the above four design methods to prevent hydrates in fuel gas lines.0 × 104 scf / (379. so that the MeOH lost to the gas is 0.3.7 lbmol (= 2. 1991).079 lbm) = 0. No condensate is formed in the pipeline.393 lbm MeOH/day (0. If one control valve becomes plugged with hydrates and shut down. Ex12. p. Ex12. Drying the Inlet Gas. consequently there is no MeOH lost to the liquid hydrocarbon phase.314 lbm) condensate (0).The daily gas rate is 52. the second gas line is then opened while the first line is depressurized for hydrate dissociation.5 scf/lbmol)).B.06 gal/day) injection required to inhibit the fuel gas line. and water (0. Manning and Thompson. This solution technique addresses the effect of hydrate formation rather than its cause. If the gas inlet is dry. Ex12. the most satisfactory from the standpoint of expense and operating practice is to provide dry inlet gas with a fuel gas line downstream of the TEG dryer. In this manner. and there is the risk that the parallel valve may become hydrated before the plug is removed from the initial line. Total Mass of MeOH Needed. As Deaton and Frost (1946.2.7) or 0. but it is readily available in standard texts on gas processing (e.0098 lbmol (= 0.4.314 lbm/day. Operating personnel sometimes suggest that fuel gas lines be placed in parallel to provide more than one gas expansion as shown in Figure 30. Parallel Gas Expansion. hydrate formation cannot form due to insufficient water. The total amount of MeOH injected is the sum that in the vapor (0. and should be considered less than optimal operating practice.

Figure 29 .02 MMSCF per day 0. P1=1500 psia T1=100oF P2=300 psia T2=33oF .Single Valve Gas Expansion with Methanol Injection Control Valve Gas Inlet of 0.393 lbm MEOH/day .

Figure 30 .Parallel Gas Expansion P1=1500 psia T1=100oF P2=300 psia Flowline #1 T2=33oF High Pressure Flowline P2=300 psia T1=100oF P1=1500 psia Flowline #2 T2=33oF .

changes in upstream pressure due to throughput changes. placed in the lower end of the tubing string to cause a large pressure drop to be taken deep in the wellbore. thus preventing hydrates from forming across the expansion. so that small crystals are stabilized for some time 41 . and 6. the anti-agglomerant method which uses a surfactant to stabilize the water/hydrate phase as small emulsified droplets within a liquid hydrocarbon. while with the newer methods (5 and 6) the system is allowed to exist within the hydrate stability zone.The study of gas expansion without hydrate formation suggests two additional Rules-of-Thumb. using either a glycol dehydrator or a molecular sieve adsorption process. Thermodynamic inhibition (methods 1 through 4) prohibit hydrate formation altogether.g. To use this Rule-of-Thumb it is necessary to be able to dry the gas. the kinetic inhibition method of preventing sizable crystal growth for a period exceeding the free water residence time in a pipeline. decrease the pressure. Where drying is not a possibility. The warm downhole reservoir heats the gas before it expands. 2. Rule-of-Thumb 8. e. Rule-of-Thumb 9. or 4. 3. it is always better to take a large pressure drop at a process condition where the inlet temperature is high. increase the temperature. One application of Rule-of-Thumb 9 is the bottom hole choke. Two additional. insert a component to attract water molecules. provided in Texaco’s Reliability Engineering: Gas Freezing & Hydrate Study. discussed at the beginning of Section II: 1. Hydrate Control Through Chemical Inhibition and Heat Management There are four classical approaches to hydrate inhibition. new inhibition techniques have been commercialized and are gaining industrial acceptance: 5. such as an alcohol or glycol. II. which typifies instrument or fuel gas applications. in order to prevent hydrate formation in unusual circumstances. a handbook for field personnel by Todd et al. It is always better to expand a dry gas than a wet gas. stated below.G. The majority of bottom hole chokes are installed in high pressure gas wells that producer a low amount of liquids. (1996). A bottom hole choke is a device with a restricted opening. remove water from the system. Rule-of-Thumb 8 is illustrated by the previous example.

In the future innovative methods of heat management through heating and insulation may provide thermodynamic protection against hydrates. and elimination of some environmental concerns.a Methanol.3 summarizes the chemical inhibitor use guidelines. The downhole methanol injection point is placed at the well depth for which the well temperature and pressure are predicted to cross into the hydrate formation region.G. as illustrated in Sections II. there are successful commercial instances of kinetic control.1 Inhibition with Methanol or Monoethylene Glycol II. Section II. while offshore methanol concentrations can exceed 50 wt% if the pressure is high. Section II. Hydrate inhibition abilities are less for larger alcohols (i. a commercial program such as WELLTEMP can be used to predict the flowing temperature and pressure (in an identical manner to that used with PIPEPHASE or OLGA in Example 2 of Section II.D.2 discusses design and operation with kinetic inhibitors.1 discusses design and operation with thermodynamic inhibition chemicals (methanol and monoethylene glycol).G.G. Of all hydrate inhibitors. The methanol amount needed in free water of either wells or flowlines may be determined using Hammerschmidt’s equation or HYDOFF. (1996): (1) under-inhibited systems form hydrates faster than systems without inhibitors.e. Methanol is also the best and most cost effective of the alcohols. Typically the free water concentration of methanol in onshore pipelines is about 20 wt%. A recent finding is that under-inhibition with MeOH is worse than no inhibition for two reasons. Proportions of methanol dissolved in the vapor or oil/condensate phases are calculated via the 42 .G. methanol is the most widely used.C.1. a small operating cost reduction. While thermodynamic inhibitors are the standard practice offshore.A).G. The incentive for newer kinetic control methods is a substantial capital cost reduction by the elimination of the need for offshore platform equipment. II.) Typically methanol is vaporized into the gas stream of a pipeline. For methanol injection into wells. significant amounts of methanol are also dissolved in the vapor and oil/condensate phases. Section II. Section II. and (2) hydrates stick to the pipe walls more aggressively when insufficient methanol is injected. Usually the flowing well conditions are warm enough to prevent hydrate formation.4 shows the methods of heat management to retain a high inlet temperature in the fluid region.G.period without growing to larger masses. then dissolves in any free water accumulation(s) to prevent hydrate formation. for both well production and well testing conditions. While hydrate inhibition occurs in the water phase. and II. methanol > ethanol > isopropanol. as measured by Yousif et al.

443 4.78 4. % MeOH Loss to Oil. bpd Produced Water. wt% Oil Production.412 0. $MM Total Cost with Platform. MMscf/d Injected MeOH.81 Capital and Operating Cost Calculations 16.7 13.10 13.4 9. bpd Gas. Methanol loss costs can be substantial when the total fraction of either the vapor or the oil/condensate phase is very large relative to the water phase.430 0.14 8. Makogon (1981.3 5.593 15 7. Norsk Hydro workers (Stange et al. As an evaluation scenario.59 48.11 Low Water (Early Life) 30 20 48.456 0. T able 3. for (a) high water production in late field life. The use of methanol in the North Sea has become so expensive that alternatives to methanol injection are considered.72 7. Costs were determined for methanol recovery on the platform for eight cases of methanol in the produced water.03 4.914 1.D. M ethanol 1994 C osts w O ith ffshore Platform R ecovery Case Amount of MeOH in H2O.224 1.176 0.537 4. Figure 31 shows a block flow diagram for methanol recovery and injection.797 6. 1989) indicated that North Sea methanol usage may surpass the ratio given by Makogon by an order of magnitude. _____________________________________________________________________ Case Study 7.188 14. and are usually taken as operating expense losses.813 3. bpd MeOH Loss to Gas. with methanol return lines 40-60 miles to deepwater subsea wells. p. 133) noted that in 1972 the Soviet gas industry used 0.25 2.191 14.188 57 960 15.31 5. Sample economics for methanol are provided in Section IV and in the following Case Study 7.99 43 . $MM/yr. lbm/d MeOH Loss to Gas.53 5.498 15 4.668 23.35 1.29 2.C and II. Table 3 shows results for four cases: 20wt% and 30wt% methanol in the free water phase. % Installed Cost on Platform. High Water (Late Life) 30 20 13. lbm/d MeOH Loss to Oil.977 5.802 3.196 57 1.3 kg of methanol for every 1000 cubic meters of gas extracted. shallow water platform was designed solely for methanol recovery in 100-150 feet of water.39 4. and (b) low water production in early field life. Methanol Recovery from the Water Phase Paragon Engineering (1994) performed a study for DeepStar (DSII CTR 2211) of the impact of methanol recovery on offshore systems.20 20. $MM Operating Cost.methods of Sections II.8 17. a conventional.

200 48. w.Figure 31 . w. Fac.800 200 MeOH Rec.Methanol Recovery and Injection (From Manning and Thompson.600 3. MeOH Rec.3 56.d) Gas Treating Dehydration Compression & Metering Oil/Gas to Sales Pipeline Max. Facil. MeOH Min. Gas Flow (MMSCFD) 15.800 Water Flow (BPD) 14.4 Oil Flow (BPD) 13.d) Subsea Well & Template . (BPD) 7. (%) 99. 1991) Shallow Water Platform (150 ft.5 91 Oil/Gas/Water Separation Oil Oil Treating Pumping Metering Water 50 miles to Platform 12” Production Pipeline 4” Methanol Re-injection Water Treating Methanol Storage Methanol Recovery Facilities Water Overboard Deepwater (4000 ft.380 MeOH Inj. Rec.

Consequently. However in the methanol column the overhead may be almost pure methanol. and an Amoco Netherlands recovery unit (12% MeOH losses). The salt solubility limit in MEG is frequently exceeded. MEG is seldom used to dissociate a hydrate plug unless the injection point is vertically above a hydrate plug (as in a riser or a well).G. MEG also has a higher molecular weight and a lower volatility than methanol. Paragon Engineering also reported methanol losses which were greater than anticipated in North Sea recovery systems from three Conoco facilities (4-5 gal MeOH lost/MMscf). Monoethylene glycol injection is used when the required methanol injection rate exceeds 30 gal/hr. MEG is most applicable for small water fractions when gas and oil/condensate fractions are very high.b Monoethylene Glycol. Rule-of-thumb 10 was obtained from Manning and Thompson (1991. a Norsk Hydro recovery unit (29% MeOH losses). exchangers. MEG’s low vapor pressure requires that it be atomized into a pipeline. In addition MEG losses to the vapor and oil/condensate phases are very small relative to methanol. Due to it’s high viscosity and density. Environmental concerns have a major impact on recovery. The bottoms methanol concentration was less than 1000 ppm so that water could be dumped overboard. Methanol can be recovered from the condensate via a water-wash and subsequent distillation. mono-ethylene glycol (MEG) dominates pipeline injection over di-ethylene glycol (DEG) and tri-ethylene glycol (TEG) because MEG has a lower viscosity and is more effective per pound. Salt also concentrates in MEG regenerator bottoms (due to low salt vapor pressure) when salt water is produced in the well stream inhibited by MEG. 44 . MEG is retained with the water phase and provides no hydrate protection above the water level. so MEG may be recovered and recycled more easily on platforms.1. Of the glycols. Unlike methanol. but this is also seldom done. 86). After injection. Figure 32 shows a MEG recovery unit that appears very similar to the methanol recovery block diagram in Figure 31.D.In all cases methanol was recovered as the overhead product from a 40 tray distillation column. The MEG injection amount may be calculated using methods in Sections II. _____________________________________________________________________ Methanol recovery is possible from the vapor phase. using a cryogenic recovery process. II.. while in the glycol regenerator MEG is recovered with water (typically at 60-80 wt%) at the bottom. Rule-of-Thumb 10. methanol is normally used for flowline plugs. p. but this is seldom done due to the expense involved. resulting in salt precipitation and fouling of column trays. and other equipment.C and II.

1991) Wellstream Water Free Water Knockout Glycol Inj.MEG Recovery and Regeneration (From Manning and Thompson. Nozzle HXER Gas Bypass Valve Choke Residue Gas Low Temp Separator Water Vapor Lean Glycol Filter Glycol Pump Glycol-Oil Separator Oil to Stabilizer Rich Glycol Fuel Gas Glycol Regenerator Glycol-Glycol HXER .Figure 32 .

G.B. II. the choice seems to depend upon (a) plug location. MEG is principally used for hydrates in wells and risers. and (c) properties of the plug in question. (b) fluid effects. Section 3. Kinetic Control by Anti-Agglomerants and Kinetic Inhibitors The reader is referred to the text by Sloan (1998.G. In a comprehensive set of experimental studies.a) -easy to recover -for plugs in wells and risers -low gas &condensate solubility -high viscosity inhibits flow -salt precipitation and fouling -remains in aqueous phase Disadvantages A step-wise list of considerations before injection of methanol and monoethylene glycol are provided in Table 5 at the end of Section II.1. Ng et al.1. Major problems with use of MEG are high viscosity in long lines and salt precipitation upon regeneration. and only a few good examples of commercial application exist. MEG dominates BP’s inhibition use in the North Sea.II.3. Methanol usage (principally in flowlines and topside on platforms) predominates in the Norwegian sector of the North Sea.c Comparison of Methanol and Glycol Injection. (1987) determined that methanol inhibited hydrate formation more than an equivalent mass of glycol in the aqueous liquid. While there is no robust strategy to discriminate between the use of methanol and MEG. In contrast.2. The table below provides a summary. Methanol use is much more prevalent than MEG in the United States. Table 4.G. At the time of this writing. With some inhibitors. the kinetic inhibition area is changing rapidly with substantial research and development. Methanol and Monoethylene Glycol Attributes Comparison Hydrate Inhibitor Advantages Methanol (MeOH) Monoethylene Glycol (MEG) -easily vaporized into gas -for flowline & topside plugs -no salt problems -costly to recover -high gas & condensate losses -too little is worse than none -costly in condensate product (See Table 13 Section IV. 45 .3) for the theory of hydrate prevention using the two new techniques of anti-agglomeration and kinetic inhibition. substantial advantages are claimed for combinations of anti-agglomerants and kinetic inhibition.

As surfactant molecules.a Anti-Agglomerants. with subsequent cooling and restarting. a surfactant emulsifier has been added to the gas condensate system to cause the water to be suspended as small droplets in the condensate. but hydrates are prevented from agglomerating to larger hydrate masses capable of plugging pipelines. Coal slurry transport technology provides a maximum ratio of coal : liquid vehicle of 40:60. and both gas and water are consumed.G. et al. The above rule-of-thumb is founded on two bases: 1. With this inhibition mechanism.II. 2. In the upper diagram hydrates form large black masses and can grow to a size to plug the pipeline. the water-in-oil emulsion may invert to an oil-in-water emulsion. causing a lower surface tension between oil and water. a surfactant causes the water phase to be suspended as emulsified droplets.” Rule-of-Thumb 11. 46 . If the water phase is external. while the other end attracts oil. The maximum water to oil ratio (volume basis) for the use of an anti-agglomerant is 40:60 on a volume basis. “the difference in plugging behavior is attributed to the type and amount of natural surfactants present in the oil or condensate. (1994) present Norsk-Hydro data in Figure 34 as an example of anti-agglomerant behavior in a multiphase pipeline that did not exhibit plugging when the initial water-to-oil ratio (WOR) was below 60% (volume). With excess oil. In general oils with little tendency to form stable emulsions have been observed to form hydrate plugs more easily than oils more prone to form stable emulsions. Surfactant chemistry is complex and a different surfactant may be required to emulsify water with each oil (or condensate). Even though hydrates are formed. hydrates will grow beyond small droplets. Lingelem. Antiagglomerant inhibitors are particularly effective in preventing hydrate pluggage or flow stoppages such as shut-ins. similar to a non-transportable coal slurry.2. In contrast. The Norsk-Hydro authors suggest that behavior such as in Figure 34 illustrates a “natural” anti-agglomerant mechanism because. Other multiphase oil pipelines (not shown in Figure 34) commonly plug with minimal WOR. Higher ratios increase the risk of having a non-transportable hydrate phase. the emulsion may be reversed and water will be the external phase. At higher WOR than 40:60. plugging was observed above 60% WOR with less than 10 wt% methanol in the free water. hydrate droplets form. Figure 33 shows a schematic of the method for anti-agglomeration. anti-agglomerants have one water-attractive end. However with excess water. In the lower portion of Figure 33. Use of anti-agglomerants requires a substantial oil/condensate phase. even with hydrate formation. their suspension may provide acceptable flow properties such as low pressure drops.

Anti-Agglomorants in Pipeline (From Sloan.Figure 33 . 1998) Without Anti-Agglomerantes Condensate Hydrate Plug Condensate With Anti-Agglomerantes Condensate Hydrates in Suspension .

Figure 34 .Anti-Agglomerantes Effectiveness in Various Amounts of Water (From Lingelam et al. No Plugs 80 Plugs 70 60 Watercut % 50 T = 0-4 oC P = 70 bar 40 30 20 10 0 0 5 10 15 Wt% MeOH . 1994) 100 Not Tested 90 No Hydrate Hydrate.

Undocumented reports from Shell report an inhibition chemical which provides inhibition at an order of magnitude lower concentration than the IFP chemical. and recovery. as predicted by the gas 47 .3. emulsion breaking. while it increases rapidly without inhibitor in Figure 35. Specific surfactants must be formulated and tested as emulsifying agents for each composition of condensate. Figure 37 shows the most common measure of kinetic inhibitor performance. While there is evidence that the presence of a liquid hydrocarbon phase aids inhibition. some environmental concerns persist. and 0. for a recombined crude. respectively. without being condensate specific. The last case is shown with and without anti-agglomerant inhibition in the Figures 35 and 36. The line marked Lw-H-V represents the hydrate formation line. especially for deep.b Kinetic Inhibition. kinetic inhibitors prevent hydrate crystal nucleation and growth without emulsifying in a hydrocarbon phase.2. and the need to recover the expensive dispersant additive. and environmental considerations. Prevention of nucleation prevents hydrate crystals from growing to a critical radius.At the French Petroleum Institute. Significant technology was transferred from earlier studies of enhanced oil recovery. 0. inhibiting progress to larger crystals. Kinetic inhibition of hydrate growth has a different mechanism than that of anti-agglomerants.G. Yet the method holds great promise. Behar et al.3. the need to break emulsions. this additive allows the hydrates to form before taking them into the condensate phase. However the loop pressure drop (an indicator of hydrate formation in a closed system) remains at a low value with inhibition (Figure 36). II. Many surfactants have been shown to promote hydrate formation. Economics should include such factors as surfactant cost. There is not a published commercial example of the use of an anti-agglomerant in an offshore hydrates application. Small amounts of surfactant are required relative to traditional inhibitors like methanol. (1994) indicate that 1 wt% of an emulsifier is equivalent to 25 wt% methanol. Weaknesses of the method include toxicity concerns. and performance are not in the open literature. properties. (1994) provided three performance examples of an anti-agglomerant inhibitor in a two inch pilot loop. Anti-agglomerant chemicals are proprietary and chemical structures. Reportedly. and a gas saturated condensate with WOR ratios of 0. indicating hydrate formation even with anti-agglomerant inhibition.1 ft3/ft3 respectively. Behar et al. A low pressure drop indicates that the effective viscosity is small and that the fluid components flow readily. Growth inhibition maintains hydrates as small crystals. The next decade will undoubtedly see major advances in these chemicals. a gas saturated oil. highly subcooled systems and shutdown with cold restart situations. The gas consumption increases in both cases.

Hydrate Formation with Plugging (From Behar et al.5 2 Pressure Drop (Psia) 50 40 30 Temperature Pressure Drop 1. 1994) 70 WOR = 0.Figure 35 .1 Ft3/Ft3 60 Gas Consumption Temperature (oF). Gas Consumption (mMol) 4 3.5 20 10 0 0 10 20 30 40 Time (min) 50 60 70 80 Plugging 1 0.5 0 .5 3 2.

1994) 70 Gas Consumption 60 Temperature Temperature (oF).5 0 200 50 100 Time (min) 150 .Figure 36 .Anti-Agglomerants Preventing Plugging (From Behar et al. Gas Consumption (mMol) 4 3.5 3 2.5 Pressure Drop (Psia) 50 40 WOR = 0.1 Ft3/Ft3 30 Pressure Drop 2 1.5 20 10 0 0 No Plugging 1 0.

Figure 37 . 1994) 10000 Pressure (psia) 1000 ∆T (Tsubcooling) E il qu ib m riu L e(l w in V H- ) Cooling 100 Hydrate Onset (Tonset) Teq Start Experiment 10 20 40 60 80 100 Temperature (oF) .Subcooling as a Measure of Kinetic Inhibitor Performance (From Shuler.

subcooling (∆T) is the measure of the lowest temperature that the system can be operated relative to the hydrate formation temperature at a given pressure. As indicated on the figure. Each of the chemicals has a polyethylene backbone. otherwise crystal growth is blocked. Recent results suggest that water residence time can be as long as 30 days without hydrate formation. Kinetic inhibitors are commonly polymers with several chemical formulas shown in Figure 38. if the amount of inhibitor adsorption decreases (due to depletion by multiple small hydrate crystals) the distance L between polymer strands increases. The object of kinetic inhibition is to maintain the operating condition of a pipeline as far as possible to the left of the Lw-H-V line without formation of hydrate plugs during the residence time of the fluids in the flow line. 9. In order to continue growing. however ∆T does depend upon the polymer. resulting in a smaller subcooling ∆T. The value of ∆T appears to be pressure independent. frequently within a five. when the lowest temperature of the pipeline is at least 3oF less than the maximum subcooling (∆Tmax) with a good kinetic inhibitor.4 wt% VC-713 in a 17 day test in a North Sea pipeline. Several companies have adopted the use of PVP in onshore fields with a small subcooling (∆T) and short residence time. and alcohol present. the pendant group penetrates specific sites (cages) of a hydrate crystal surface while the polymer backbone extends along the surface. glycol. resulting in an increased subcooling ∆T performance. the crystal must grow around the polymer. In Figure 37. Adsorption of three kinetic inhibitor polymer strands are shown on a hydrate crystal surface. The “filled stars” on each polymer strand represent the pendant groups which dock at the “empty star” sites on the hydrate crystal surface. Figure 39 is a schematic of one type of kinetic inhibition. If the amount of polymer adsorption increases.. such as may occur in a pipeline (Figure 7). the distance L between the strands decreases. As the inhibitor adsorbs on the hydrate crystal..4 48 . One of the first kinetic inhibitors developed was polyvinylpyrrolidone (PVP). a polymer whose structure is shown in Figure 38. 1995). 1995) and Texaco (Notz et al. Conversely. Initial field tests of kinetic inhibitors were reported by ARCO (Bloys et al. connected to pendant groups typically containing an amide (-N-C=O) linkage. The maximum value of ∆T is determined by a laboratory and/or pilot plant experiment. diameter. The pipeline (8 in.or seven-member ring.C) or by HYDOFF (Section II. molecular weight. the subcooling ∆T is directly proportional to the liquid-crystal surface tension (σ).D). with hydrate formation to the left and non-hydrate conditions to the right of the line.3-0.gravity curve (Section II. The horizontal line in Figure 37 represents a cooling curve for hydrate forming mixtures. and the amount of salt. Bloys reported the effectiveness of 0. and the pipeline is operated at a smaller value of ∆T. but inversely proportional to the length (L) between polymer strands.

Formulas of Some Kinetic Inhibitors (From Sloan. 1998) PVCap H3C ‘N’CH3 vc-713 .Fkure 38 .

Polymer Adsorption in Hydrate Crystal (From Larsen. 1994) 4σ ∆T ≤ C⋅L ain Ch Su er rfa ce lym L Po L Cr ys tal .Figure 39 .

The trials included extensive periods of 49 . Three trials were carried out.. 1996). Notz further reported that PVP (at less than 1 wt%) was effective in replacing methanol (at concentrations from 10 to 60 wt% in free water) resulting in savings of as much as 50%.5 bbl/MMscf condensate and 0. At the time of the trial the maximum flow rate was 195MMscf/d. 1997).km long) had a flow rate of 20 MMscf/d. THI) in flowlines in the West Sole gas export lines (Argo et al. PVCap. with water phase residence times up to 30 days. Rule-of-Thumb 13 comes from commercial use of kinetic inhibitors.2 bbl/MMscf condensed water at a subcooling between 1oC and 9oC. (1995) indicated successful use of polyvinylpyrrolidone (PVP) in several wells and flow lines in Texas and in Wyoming. as indicated in the below case study. Rule-of-Thumb 12. 1996 British Petroleum (BP) initiated continuous commercial use of kinetic inhibitors (called threshold hydrate inhibitors. 0. but marginal for retrofits of systems with traditional inhibitors such as monoethylene glycol. all of which were successful. PVP may be used to inhibit pipelines with subcooling less than 10oF for flow lines with short gas residence times (less than 20 minutes). a handbook for field personnel by Todd et al. _____________________________________________________________________ Case Study 7: North Sea Use of New Inhibitors On July 22. Texaco’s Notz et al. Bloys suggested that economics were very favorable for new developments. This followed from an extensive set of field trials carried out in the Ravenspurn to Cleeton wet gas line (Corrigan et al. Kinetic inhibitors more effective (but more expensive per pound) than PVP (illustrated by the other chemical formulas in Figure 38) have a seven-member ring pendant group in place of the five-member PVP pendant ring. For the purpose of the trial the flow rate was cut back to 90mmscf/d to put the line as far into the hydrate region as possible (16oF of subcooling). BP began THI use in a 16 inch I. See Texaco Case Studies C. Rule-of-Thumb 13: VC-713. Rule-of-Thumb 12 comes from Texaco’s Reliability Engineering: Gas Freezing & Hydrate Study.14 in Appendix C. and co-polymers of PVCap can be used to o inhibit flow lines at subcooling less than 18 F.. 13 mile long pipeline from three Ravenspurn platforms to Cleeton.D. (1996) which reflects Texaco operating kinetic inhibitor practice with approximately 30 flow lines from their Brookeland field.13 and C. concluding that PVP was in routine use in some Texaco fields. The better kinetic inhibitors provide additional subcooling with long water residence times.

The THI pumping rate per platform is 2-3 liters/hr of solution which contains about 15wt% active ingredient. Currently two lines (24 inch and 16 inch I. but nonetheless represents a severe test for kinetic inhibitors. Estimate the production rates of gas. 3. It should be emphasized that. 35 miles long) from West Sole A.3 bbl/MMscf with 250 MM scf/d total produced from the 3 West Sole platforms and the remainder from the Hyde platform. 2. and water analyses during a field drill test.G.B. (1996) for further details. See Corrigan et al. confirm the prediction with experiment(s). Due to the low amounts of water and condensate. _____________________________________________________________________ Table 5. and the lines are 11oF inside the hydrate region at operational conditions. Obtain an accurate gas.. The below protocol provides preliminary steps for such experiments. Generate the hydrate pressure-temperature equilibrium line with several prediction methods. The gas is very lean producing very little condensate. experimental data should be obtained. The THI dose rate was 3000-5000 ppm based on the free water phase.D. and water phases over the life of the field. this is an atypical case.shut-in. modified from the original suggestions by Edwards of BP (1997) and T R Oil Services (Grainger. Estimate how these compositions will change over the life of the field.3 bbl/MMscf. Water production from all four West Sole platforms is 150-200 bbl/d. condensate. 50 . particularly if kinetic inhibition is being considered. A typical water production rate was 1. The condensate rate is also 0. Record the existing or planned procedures for dealing with an unplanned shutdown.6 bbl/MMscf with a line pressure of 1088 psia and a low temperature of 48oF.3. Guidelines for Use of Chemical Inhibitors Table 5 is a stepwise protocol to determine whether the use of inhibitors might be suitable. before field application. up to 7 days with successful restart. The target injection rate is 3000 ppm based on the free water phase. or about 0. 1997). _____________________________________________________________________ II. If the operating conditions are close to the hydrate line. Guidelines for Use of Kinetic or Thermodynamic Inhibitors 1. and C and Hyde are being inhibited with THI. Water content is low and free water comes mainly from condensation. Water residence times can be as long as 2-3 weeks. record the current hydrate prevention strategy. Provide a generic description of the chemistry of the scale and corrosion inhibitors used. If the field is mature. oil.

12. (b) methanol. Determine the water residence times in all parts of the system. e) Determine the storage and injection deployment methods. safety. Determine the water production profile over field life (see Table 6 example). List the parts of the system which require protection. resulting in points of hydrate formation. and emulsification tendencies. and health impact of the chemical. d) Determine the minimum. Design the system hardware to measure: (a) temperature and pressure at pipe inlet and outlet (b) water monitor for rates at receiving facility. 6. Consider the pipeline topography along the ocean floor to determine where water accumulations will occur at dips. Simulate the pipeline pressure-temperature profile using a simulator such as OLGA or Pipesim to perform hydraulic and heat transfer calculations in the well. and separator over the life of the field. Perform economic calculations (capital and operating expenses) for four options (a) drying. maximum. especially in low points of the pipeline. and pour point ( should be >15oF). (c) monoethylene glycol. seals. 8. h) Determine the compatibility with the process downstream including cloud point. viscosity ( should be <200 cp at lowest T). 9. 7. 5. If ∆T > 14oF. consider the use of kinetic inhibitors. foaming. including fluid separators and water handling facilities. Estimate the subcooling ∆T (at the lowest temperature and highest pressure) relative to the equilibrium line over all parts of the system. etc. 10. and (d) kinetic inhibitors.4. If ∆T < 14oF. flow lines. 51 . Determine if inhibitor recovery is economical. 11. and average dosage of inhibitor. and (c) the below chemical check list a) Has the inhibitor been tested with systems at the pipeline temperature and pressure? b) Consider the environmental. consider the use of standard thermodynamic inhibitors or anti-agglomerants (no one has used antiagglomerants commercially as of January 1. g) Determine compatibility with other production chemicals. 1998). density. f) Determine the material compatibility with gaskets. c) Determine physical properties such as flash point (should be < 135oF).

so that maximum inhibitor injection rates may be required.a and in Figure 10. One Scenario for Pipeline Water Over Field Life 1. Only fluid measurements can assess this difference. At the beginning of field life. At the end of field life there may be 10 times as much water. Because the amount and concentration of pipeline water depends heavily upon produced water. water produced down the line (if there is no upstream separation facilities) will increase. 4. but the condensed water amount may be sufficient to dilute the solution to low salt concentrations. Edwards also provided one possible scenario for water production over a field life. As an example.C. _____________________________________________________________________ Hydrate inhibition occurs in the water phase and is dependent on the amount of water production and the salt concentration. _____________________________________________________________________ 52 .3. However. Over a field lifetime. Both produced water and condensed water may be substantial. At field mid-life. 2. but low dosages of chemicals are required by low amount of water production. so that only a small amount of condensed water can be responsible for hydrate problems. The field may be operating with a large subcooling ∆T.At an early stage in the inhibitor design process it will be worthwhile to consider obtaining laboratory data and involving a service company to provide field support of process hydrate inhibition. given in Table 6. 3. Both the increase in water salinity and the pressure decline of the field may take the production fluids outside the hydrate P-T region. but it is mostly saline production. in mid-life the pipeline requires inhibition. The second source of water. Total water may double or triple. there are counter examples of fields which begin producing water early in their life. _____________________________________________________________________ Table 6. The pipeline initially operates with a low inhibition need. in the final stages of life. The below scenario for a North Sea pipeline indicates a nonintuitive situation. typical salt concentration from produced water may vary from 0% to the reservoir concentration. condensed water. reservoir engineers should provide the best estimate of produced water and salt concentrations over the life of the field. water production may be low. can be estimated from gas water content as illustrated in Section II. the pipeline does not require hydrate inhibition. one BP field is forecast to dip into and out of the hydrate formation region over its life.

which has a temperature around 40oF. When the reservoir fluid flows through a deep ocean pipeline with an outer temperature at 40oF. with the temperature drop being due to expansion.b. particularly when the system is re-started. the temperature can quickly cool into the hydrate region as determined by the heat transfer coefficient (U) between pipe and ocean.723 bbl/d.3 BTU/hr-ft2-oF. The upper lines represent the pipeline temperature with no heat loss through the pipe wall. particularly at the higher pressures (densities) necessary to make pipeline transport economical. The pipeline in the figure was assumed to be 50% buried and had a water flow of 1. the separator temperature is 70oF or 50 oF. respectively. at various values of U. At the low ambient temperatures. the temperature drops dramatically. fluids at the wellhead are typically at temperatures from 175oF to 212oF. If the pipeline were shut-in. In such cases. _____________________________________________________________________ Case Study 8. _____________________________________________________________________ The temperature profiles in the above case study are for a flowing pipeline. The retention of reservoir heat is one of the most efficient means of hydrate prevention. making 53 . from Aarseth (1997). so that heat will flow into the hydrates from the ocean.4. However. Hydrates can easily form at these temperatures. With overall heat transfer coefficients of U = 0.c.d. hydrate problems are particularly severe and blockages may occur. In Figure 40 the lowest. Heat Management The discussion in this section has been excerpted from DeepStar reports CTR A601-a. the pipeline may be depressurized to achieve a hydrate equilibrium temperature just above 32oF. Pipeline Temperature with Heat Loss Figure 40 (from DeepStar Report CTR 223) shows an offshore pipeline temperature as a function of length.G. and from discussions with Statoil researchers. and an oil flow of 22. with heat loss through the pipewall. If hydrates form in an insulated pipeline. It is concluded that a lower heat transfer coefficient is needed to prevent hydrate formation. the system would rapidly cool to the ambient conditions represented by the dashed line at the bottom of Figure 40.76 MMscf/d.II. a gas flow of 30.527 bbl/d. Because all reservoirs contain water and because water acts as a heat sink due to a high heat of vaporization.17 and U = 3. CTR 223-1. the insulation is a hindrance or barrier which prevents heat flow from the ocean. between the pipeline inlet temperature (140oF) and a separator 50 miles away. dashed line shows the temperature of the ocean with length.

Pipeline Temperature vs. 1995) 160 140 Pipeline Temperature (oF) 120 100 80 60 Ambient Conditions 40 20 0 0 50000 100000 150000 Pipeline Length (ft) 200000 250000 300000 U=3.Figure 40 .17 Btu/(hr ft2 oF) Little Heat Loss Through Pipewall .3 Btu/(hr ft2 oF) Heat Loss Through Pipewall U=0. Change in Heat Conductivity of Pipeline (From Deepstar CTR 223.

The pipe-in-pipe (PIP) system (Figure 41b) is the most thoroughly tested of the three types. heat control systems through pipeline insulation or heating may be laid with the pipeline from a barge. Figure 41c. 2. The minimum overall coefficient achievable with a non-jacketed system is 0. the pipeline depth. The degree of insulation depends upon the thermal gradient in the earth along the pipeline route. With a 3-4 inch insulation layer. a gas flow of 30. when each line has a water flow of 1. On the other hand. and the water temperature. currently at water depths of up to 5.76 MM scf/d.3. As a consequence it is good operating practice to inject large quantities of MeOH or MEG into the pipeline before a planned shut-in. but insulation alone offer no protection for long-term shut-ins. pipe-in-pipe systems. the PIP system can provide an overall heat transfer coefficient (U) of 0. Overall heat transfer coefficients as low as 0. and an oil flow of 22.723 bbl/d. The nonjacketed system (Figure 41a) consists of an insulated pipe with a coating. (b) pipe-in-pipe. II.527 bbl/d. Expenses for providing a trench and burial system for pipelines may be very high. all in an outer casing. and (c) bundled flowlines.1 BTU/hr-ft2-oF can be achieved.0. sometimes aided by a reflecting screen in the annulus. Pipeline insulation and heating methods are given consideration in design. particularly at great depths.000 ft. burying the pipeline to provide heating and insulation by the ocean floor. In this system the flow pipe is within an outer pipe. The addition of a second flowline can reduce the insulation thickness required to 54 . Pipeline burial is a good means of providing pipeline insulation and protection.3 BTU/hr-ft2o F (CTR A601-a) and costs are typically $50-$300/ft.G. and bundling systems. Figure 42 (from DeepStar Report II CTR 223) shows the increase in temperature at the platform riser as a function of insulation thickness. Bundles are fabricated on shore in lengths up to 10 miles and towed to their offshore position. heating the pipeline.6 BTU/hr-ft2-oF. with either insulation or vacuum between the two pipes. using non-jacketed insulation. Hydrates can be prevented in pipelines by three types of heat control: 1. shows a bundled line with two or more flowlines and a start-up water line with an insulator. Figure 41 shows the three categories of insulated pipelines: (a) non-jacketed.14 . or 3.a Insulation Methods.hydrate dissociation much more difficult. with two pipelines flowing together compared to an individual flow. insulating the pipeline. for pipes with diameters between 8 inches and 12 inches.

PiFeline Insulation Methods (From Deenstar CTR A601-a. 3 in. 1995) Insulation Insulation (Max.Fipure 41 .) Steel Flowline A) Non-Jacketed Insulation System B) Pipe-in-Pipe Insulation Svstem .

76 MMSCF/D gas. and 1.527 Bbl/D water Two Pipeline Flows One Pipeline Flow 0.723 Bbl/day oil & condensate.6 0.8 2 Insulation Thickness (inches) .2 1.6 1.Figure 42 .8 1 1. 30.Riser Temperature vs. 1995) 110 Flow to Each Pipeline 105 100 Temperature (oF) 95 90 85 80 75 70 0.4 1. Thickness (From Deepstar CTR 223.4 22.

Figures 43 and 44 (from DeepStar Report CTR A601-a) compare the cost of the three above types of insulation for water depths of 6000 ft.000 and 50. Many of these guidelines result from Section III on Hydrate Remediation.D) which represents the gas. and the platform. (c) direct electrical heating for 50-60 km long lines (shown in Figure 46) in which the pipeline is the primary conductor with a current return line at 1m in parallel to the pipeline. and direct heat thereafter. II.H. over 60 miles at oil production rates of 25. It should be noted however. Before embarking on a hydrate prevention design. If possible the hydrate formation curve should be verified via an independent prediction or hydrate formation experiment. DeepStar Report CTR A601-c concludes that pipeline heating will be very expensive. with current flowing through 3 cables outside of pipe but within insulation.000 bbl/d. The Chevron/Conoco Britannia project will start in the North Sea in 1998 using a bundled line to heat fluids. or the second flowline will provide a higher riser temperature for a given insulation. Design Guidelines for Offshore Hydrate Prevention The below hydrate prevention paradigm is a collection of Rules-of-Thumb which provide general guidelines for offshore design. it is imperative to have a reliable hydrate equilibrium curve (Sections II. The three common means of heat management are (a) bundling hot water lines (for 10 km and return) in production lines to prevent hydrate formation (b) Combipipe (shown in Figure 45) for induction heating.C and II.obtain a given riser temperature. oil/condensate. heating a hydrate plug can be very dangerous. with corrosion protection. respectively. heating may be the only option to clear a hydrate plug.b Pipeline Heating Methods.” Yet as noted in Section I. bundled flow lines are more cost effective.).” In the future Statoil will use heating more extensively in order to reduce the amount of methanol or other chemicals used. flow lines and platform at the worst case (usually during winter months) over the life of the field. If an average U = 0. These design Rules-of-Thumb are for hydrate prevention in the three parts of the system where hydrates most often occur (shown in Figure 47): the well. II. 1. Estimate the 55 . and water compositions over the life of the field. “where pipeline depth precludes depressurization below the hydrate formation pressure. “at least 1MW of power is required for a 20oC (36oF) increase of a 10 inch pipeline 15 miles long.G.3 BTU/hr-ft2-oF is required with a flowline pressure of 4000 psia. 2.3. Bundles will be used in 1998. Simulate the pressure-temperature profile in the well. DeepStar Report CTR A601-b concludes that. the pipeline. that such heating tools are in the planning stage and commercial use has yet to be documented.

4 0. 1995) 900 800 700 600 Cost($/ft) 500 400 300 200 100 0 0 0.5 0.000 BOPD) (From Deepstar CTR A601-a. Overall Heat Transfer Coefficent (Depth . Rate .3 U-Value (Btu/hr-sqft-oF) 0. Prod.25.Figure 43 .6000ft.2 0.Cost vs.1 0.6 14" Non-Jacketed 2x10" Non-Jacketed 14" PIP 3x8" PIP 3x8" Bundled 3x8" Vacuum Tube 3x8" Non-Jacketed 2x10" PIP 2x10" Bundled .

Prod.50. Overall Heat Transfer Coefficent (Depth .5 0.000 BOPD) From Deepstar CTR A601-a. Rate .Cost vs. 1995) 1200 18" Non-Jacketed 2x12" Non-Jacketed 18" PIP 3x10" PIP 3x10" Bundled 3x10" Non-Jacketed 2x12" PIP 2x12" Bundled 1000 800 Cost($/ft) 600 400 200 0 0 0.6 .6000ft.2 0.1 0.Figure 44 .4 0.3 U-Value (Btu/hr-sqft-oF) 0.

Pipe Hot Water Input Line Insulation Flowline Thermal Insulation Pipeline Pipeline Insulation Cold Water Return Heating Cables Pipewall with Corrosion Protection .Heating Through Bundling and Combi-Piping A) Bundled Pipeline B) Combi.Figure 45 .

Direct Electric Heating Electric Current Pipeline 1 meter Current Return Wire Electric Current .Figure 46 .

Transport Pipeline. and Platform COMP.Depth 6000 ft Well with X-Mas Tree Transport Pipeline (2-60 miles in length) Platform Export Flowline Mudline Downhole Safety Valve Bulge from Expansion or Topography . Ocean Riser .Offshore Well. DRY SEP.Figure 47 .

II.F). Avoid unnecessary bends.3. etc. Design large pressure drops with either dry gas or expansions at high temperature points in the process.A) and Joule-Thomson expansions across restrictions (e. Account for both normal cooling (e.) provide for frequent pigging and consider placing methanol injection prior to the accumulation points. 3. 6.g. Alternatively dual production lines should be used to provide for depressurization of wellheads from the upstream side of a pipeline plug. Consider providing a heater prior to the platform choke and separator. Where large expansions of wet gas are unavoidable. upslopes in lines.g. Optimally. chokes.water residence times at all points in the system. Hydrate crystals in a line may be considered to accumulate (and plug) wherever light sand particles might accumulate. As a second best method. 8. Where pipeline topography ensures water accumulations (e. determine the type of hydrate inhibition. A riser tube radius should be from 20-80 ft. 5. provide for depressurization through a wellhead service line (for corrosion. safe remediation often implies depressurization from both ends of a hydrate plug. and control valves as in Section II. 9. Provide hydrate remediation methods (see Section III for justification) in the design.2.G. such as at blind flanges at turns. Choose the inhibition method with regard to both prediction ability and operating experiences. such as chemical inhibitor injection (Sections II. Hydrates may form in systems with subcooling ∆T’s less than 2-4oF. Eliminate subcooling points of likely hydrate formation. Estimate the subcooling ∆T (at the lowest temperature and highest pressure) at each point in the process relative to the hydrate equilibrium curve.g.G. at choke valves) provide methanol injection capability upstream of the restriction. Eliminate points of water accumulation.4). II. or heat management (Section II.G. such as upslopes in pipelines or “S” configurations in risers. or hydrate inhibitor injection) with bypass capability for checkvalve(s) at the point of injection. in wells. Design pipelines to minimize buckling and protrusions from mudlines which might promote cooling. Where subcooling is unavoidable. Bend radii less than 5 times the pipe diameter should be avoided to facilitate coiled tubing entry. multiple access points in a pipeline (see b) are invaluable in locating and remediating hydrate and paraffin plugs.G. As a minimum 56 . particularly Table 5). 4. a) For pipelines.1.g. in pipelines as in Example 2 of Section II. 7. Eliminate points of hydrate accumulation from a mechanical perspective. screens and filters. (e. With a high probability hydrates will form over the system lifetime. upstream of restrictions etc. elbows. paraffin.

C.1. 57 . c) In wells.3 indicates that normal well lubricators can be used at the swab valve with careful balancing of pressure. With the accurate location of the plug ends. and (e) pig launching. (c) injection of hydrate inhibitors. (d) coiled tubing entry.a spare flange and valve should be provided at the wellhead or manifold. or coiled tubing. b) Subsea access points should be considered at the well manifold and at 4 mile intervals along the pipeline. depressurization.B. as shown in Figure 48.C. hydrate remediation occurs by approaching one end of a plug via chemical injection. Such access points will facilitate (a) the location of a hydrate (b) venting of excessive fluid head from plugs in deepsea lines. or depressurization. heating.b). heating. remediation may be done through chemical injection. d) On the platform hydrate plugs may be located using tools such as a thermocamera (see Figure 54 of Section III. Case Study 16 in Section III.b) Technology is not yet available for location of the end of plugs or the safe heating of plugs in ocean pipelines.1. so that depressurization can be done via connection to offshore production vessel (see ARCO Case Study 14 in Section III.

Fiqure 48 - (From Pre-Installed Deepstar A-208-1. Functions Entry I Tubing Inject Fluid Into Pipeline Vent Fluids From Pipeline .Hydrate Renoval . Access 1995) Ports on PipeLine Yorkover Vessels \ access Port Coiled -Surface -suLxeo.

No pipelines were abandoned or replaced due to a hydrate plug. individual case studies are anecdotal in nature. etc.15. However since every hydrate plug is unique. Fortunately three systematic studies of hydrate plugs provide substantial guidelines for remediation.. In 1994 Statoil purposely formed/removed over 20 hydrate plugs in a 6 inch gas/condensate line over a 9 week period (Case Studies C. The section is organized to provide answers to the following questions: III. shut-in. 58 .III. which was abandoned in 1995 due to low production problems with combined waxes and hydrates.D. In all recorded instances1 pipeline plugs due solely to hydrates were successfully removed and the system returned to service. Rule-of-Thumb 14: Hydrate blockages occur due to abnormal operating conditions such as well tests with water. dehydrator malfunction.25. resulting in three significant tests (Case Studies C. In addition to those case studies in the body of the handbook.16. DeepStar IIA Report A208-1 Methods to Clear Blocked Flowlines (December 1995) was compiled by Mentor Subsea to document 16 hydrate blockage cases and 39 paraffin blockage cases.C.6. loss of inhibitor injection. 1997) formed and dissociated hydrates in a Kerr-McGee field line. See Case Study C. How Can Hydrates be Detected? III. Table 7 provides an overview of Appendix C case histories. supplemented by the literature and personal interviews relating to hydrate blockages.17 in Appendix C). Much of the information in Section III on hydrate remediation was excerpted from the above three systematic studies. How do Hydrate Blockages Occur? III. What Remediation Questions Remain to be Answered? 1 An exception was the LASMO Staffa subsea field in the North Sea. Hydrate Plug Remediation Perhaps the best way to remove a hydrate blockage in a flow channel is to use the experience of those who have removed similar blockages.26.27) with extensive instrumentation at five pipeline points. Appendix C details 27 case histories of hydrate removal in flow lines.A. How Can Hydrate Plugs be Removed? III. as is sometimes the case for paraffin plugs. In -February 1997 SwRI (Hatton et al. During 1995-6 uninhibited plug formations were studied as baselines for new inhibitors. A very large number of anecdotal studies is required before detailed remediation Rules-of-Thumb can be stated with confidence. start-up. for further history on this field.B. which included a 1 mile flowline replacement.

MeOH . Chevron Canada 6" Gas cond. Lines 4. Export 0 Winter Complete None Shut in for Several Days Depressurize Heat w/ Welding Rig 6. WD (ft) 200 ft Time Extent of Control Method Operations Restriction before Plug before Plug None Flowing Removed? Depressurize Current Prev. MeOH Vary Flow Rate Remove Restriction @ Flow Meter MeOH during Winter 5. Chevron Wyoming 4" Gas Cond. MeOH 9. Texaco GC 6 3/4" Gas 600 ft 1992 Partial None Flowing Depressurize Inj. MeOH 8. MeOH Inj. 0 Winter Complete Heating Tape & Insulation 3. Lasmos North Sea 8" Multiphase ? 1994 Complete MeOH Flowing Replaced 2km Same as before Depressurize after 24 Hours S/I MeOH Inj. Chevron GOM Gas Lift Inj. Method Gas Dehydration MeOH Inj. MeOH Gas Dehydration Inj.Table 7 Summary of Hydrate Blockage Experiences in Appendix C Field/ Region GC 29 Line Size 16" Line Type Gas Cond. Placid 1989 Complete blocked section Planning to abandon 7. 2. MeOH Gas Dehydration Occasionally Inj. Case/Operator 1. MeOH Inj. Texaco North Sea 1/4" Instrament Valve Complete None Flowing Inj. MeOH Heat Gas 0 Winter Complete None Flowing Flowing Depressurize Heat MeOH Inj. Texaco GB 189 2-3/4" Gas 725 ft 1995 Complete None Flowing Depressurize Inj. Chevron Oklahoma 4" Gas Sales 0 1995 Partial None Depressurize Inj.

MeOH 17. MeOH Continue MeOH Inj. Field Test Depressurize MeOH Inj. Statoil Tommeliten 6" Gas Condensate 11. 12. Dehydrate Cond. Export 1978 Complete MeOH Pigging Pig Stuck Depressurize MeOH Inj.E.5 km 1994 Complete MeOH Field Study Depressurize Inj. Marathon EB 873 - Gas Export 800 ft 1995 partial Inadequate MeOH Flowing Inject more MeOH Maintain MeOH Inj. Philips Cod N. - 1994 Complete MeOH Inj. Texaco East Texas 4"-6" Gas 0 1995 Complete MeOH Field Test Depressurize Comb. Statoil Tommeliten 6" Gas Condensate 11. Statoil Tommeliten 6" Gas Cond. (Experimental) North Sea 16. Method MeOH Injection 10. Ensure Proper MeOH Inj. of KI and MeOH 13.Case/Operator Field/ Region Line Size 16" Line Type Gas Cond. of KI and MeOH 15. Oxy North Sea - Gas Condensate - - Complete MeOH Flowing Depressurize MeOH Inj. Elf Norge N. Frigg 1990 Depressurize Inject MeOH 11. Flowing/ Shut-in/ Re-start Depressurize Inj. . WD (ft) - Time Extent of Control Method Operations Restriction before Plug before Plug Partial MeOH Flowing Removed? Current Prev. Texaco Wyoming - Gas 0 1995 Complete MeOH 14.5 km 1994 Complete None Field Study Depressurize 18. Comb. Sea 16" Gas & Cond.

America - Well Well Well NA NA NA 1989 Complete 1989 Complete 1993 Complete None None None Drilling Drilling Testing Coiled Tubing Hot Glycol 24.Case/Operator 19. Exxon 23. Amoco Field/ Region North Sea Line Size - Line Type Gas Export WD (ft) NA Time Extent of Control Method Operations Restriction before Plug before Plug Complete None(Dry) Flowing Removed? Current Prev. Kerr-McGee Wyoming Gas/Condns Land Gas/Condns Land Gas/Condns Land . Method Ensure Dehydration Drain Manifold of Water before Start-up - - Depressurize MeOH Inj. Kerr-McGee Wyoming 27. Petrobras Brazil - Manifold NA - Complete Ethanol Start-up Depressurize Ethanol Inj. 21.Exxon Gulf of Mex 4" 4" 4" Well NA 1993 Complete 1997 Complete 1997 Complete 1997 Complete Methanol Methanol Methanol Methanol Shut-in Shut-in Shut-in Shut-in Abandoned Depressurize Depressurize Depressurize 25. Exxon California Gulf of Mex S. 20. Exxon 22. Kerr-McGee Wyoming 26.

1 Concept of Hydrate Particle and Blockage Formation. Chapter 3).b) relative to the hydrate formation line. Hydrates can form with subcooling ∆T’s less than 2-4oF.D. The rate of hydrate formation region is a function of the degree of subcooling (∆T see Figure 37 in Section II. Section II. 59 . 1998.06 mole %) or water in the bulk gas (< 4%). high reservoir temperatures prevent hydrates.A. hydrates with such a low degree of subcooling will form more slowly than in systems which have a subcooling of 10oF or more.2. the system temperature and pressure must first enter into the hydrate formation region. present to serve as nucleation centers. The system temperature and pressure at the point of hydrate formation must be within the hydrate stability region.III.G. or (c) the platform. etc.namely in (a) the well. In gas/condensate or gas/oil systems. Due to the hydrate formation barrier at the interface. because this 85:15 ratio is far in excess of the solubility of gas in the bulk water (< 0. which can form hydrate particles and agglomerations to build up and obstruct pipe flow. In an turbulent system such as a pipeline. with insufficient water to form hydrates.A. Diffusion through the solid is extremely slow and hydrate fissures or cracks provide the only means for further contact of the water and hydrocarbon. natural gas hydrate particles have water as an occluded phase. In order for hydrates to form. Infrequently. All natural gas hydrates are approximately 85 mole% water and 15% natural gas. platform export lines are dry. When hydrate particles occur in a static system. (b) the pipeline. a solid hydrate shell forms an impenetrable barrier at the hydrocarbon-water interface which prevents further contact of the hydrocarbon and water phases. gas is the occluded phase within a hydrate shell. particularly in industrial systems with contaminants like sand. Rule-of-Thumb 15: In gas-water systems hydrates can form on the pipe wall. hydrates frequently form as particles which agglomerate and bridge as larger masses in the bulk streams. weld slag. However.F). How Do Hydrate Blockages Occur? Figures 3 and 47 in Section II each show a simplified offshore process between the well inlet and the platform export discharge.A illustrates hydrate prevention design where virtually all hydrates occur . Hydrate formation always occurs at the hydrocarbon-water interface. Before the well. Such a build-up is one major concern of this section. as determined by the methods of Sections II. either through a normal cooling process (Example 2 and Figure 6 and 7) or through a Joule-Thomson process (Section II.C. when gas is bubbled through water. This exceptionally low mutual solubility is the result of water hydrogen-bonding (see Sloan. high agitation rates provide for surface renewal. and II. III.

.25. The Statoil experience suggests that Figure 49b represents the more common case in hydrate formation. Figure 49a from Lingelem et al.27) and the multitude of Statoil studies which suggests a high porosity. there are two schools of thought about hydrate formation. (1) the gradual buildup of hydrate formation on the walls.15.Rule-of-Thumb 15 was obtained through multiple studies on flow loops/wheels at Statoil’s Research Center in Trondheim. while some oil/water systems convert to hydrates almost immediately with fairly low water conversion. C. Such an open hydrate mass has the unusual property of transmitting pressure while being a substantial liquid flow impediment. hydrate plugs are much less permeable to liquid than to gas. 60 . This slow buildup of hydrates along the wall may be characterized by the gradual increase in line ∆P witnessed in 2 of 3 DeepStar field tests in a Wyoming gas-condensate line (Hatton et al. 1996). but practically all water might be transformed to hydrates. In a black oil system. In gas systems. Hydrate particles anneal to lower permeability at longer times.. 1997). Because liquid surface tension is much higher than that of gas by about a factor of 1000. some plugs can have porosities considerably higher than 50% while other plug porosities can be considerably lower. resulting in the less porous plugs seen in a few. often only a small amount (less than 5 volume %) of water forms hydrates. Such results are fluid dependent.7 . bridging hydrate structure may be the norm (See Case Studies C. Figure 49b shows the case of hydrate formation as agglomerating or bridging particles in a condensate or oil system.26. and C. C. Plug porosity is determined by forming conditions and fluid effects. In an oil/condensate system. porous structure. In Statoil’s Tommeliten Field blockages formed from a hydrate slurry with < 1 volume % of the water present. but all the water and condensate are trapped in the open. and C. other oil systems are more difficult to convert. thoroughly instrumented DeepStar field tests (See Case Studies C.17). Rule-of-Thumb 16 was obtained through both field and laboratory studies at Statoil’s Tommeliten Gamma field and SINTEF’s research center (Berge et al. porous system and can form a blockage (Urdahl. the light hydrocarbon liquid above the water prevents splashing and causes hydrate particle formation and agglomeration at the liquid-liquid interface.16.11 × 10-15 m). Rule-of-Thumb 16: Agglomeration of individual hydrate particles causes an open hydrate mass which has a high porosity (typically >50%) and is permeable to gas flow (permeability to length ratio of 8. water may splash or adsorb on the pipe wall where hydrate nucleation and growth may occur. Norway. However. providing the open. (1994) of Norsk Hydro is a schematic of the case of hydrate formation along the wall periphery in a gas system. 1997).

Figure 49a . 1994) Gas Pipeline Flow Hydrate Water .Hydrate Accumulation in Gas Pipeline (From Lingelem et al.

Hydrate Accumulation in Condensate Pipeline (From Lingelem et al.Figure 49b . 1994) Initial 1 Hour 3 Hours 5 Hours Condensate Pipeline Partial Plug Complete Plug Hydrate Plug .

g. It is often unavoidable to design and to operate hydrate-free systems. should also be minimized. and C. subcooling will occur with pipeline protrusions from mudlines so dips in pipelines should be minimized. depressurization or mechanical removal. It is apparent from the small number of studies however.26. Figure 50b shows the more typical case of multiple spikes in ∆P before the final plug forms. At the left. short radius bends.A. such as “S” configurations in pipelines or risers. screens and filters. In such cases it is important to identify likely points of hydrate formation. upslopes in lines. Points of water accumulation. inhibitor injection. so that the downstream side of the plug may be in the hydrate formation region at the lower temperature.2 Process Points of Hydrate Blockage.The state-of-the-art of hydrate studies in field pipelines is too small to determine the causes and frequency of either type of hydrate buildup. flow through the plug will cause Joule-Thomson cooling just as in Example 11. at orifices/valves) should be avoided.27 detail safe techniques for depressuring one side of a hydrate plug in DeepStar Wyoming field studies by SwRI (Hatton et al. 1996) and provides both technical and safety reasons for depressuring a plug from both sides. upstream of restrictions etc. 1997). Figure 50a shows the gradual increase in ∆P which would occur if hydrates formed an ever-decreasing annulus as shown in Figure 49a. The porosity/permeability of hydrate plugs largely determines their remediation. heating. these spikes indicated that particles are forming blockages and releasing. III. Hydrate particles in a line may be considered to accumulate (and plug) wherever light sand particles might accumulate. Large pressure (e. Figure 50 shows two types of pressure drop (∆P) increases which occur with hydrate blockage of lines. Where pipeline topography ensures water accumulations (e. if a hydrate plug is depressurized from only one end.. However. etc. such as at blind flanges at elbows.25. Case Studies C.g. For example. as depicted in the agglomeration of particles in Figure 49b.) one may consider providing pigging inhibitor injection points to accommodate the accumulation. C. The above conceptual picture of hydrate formation reinforces field experiences regarding points in the process shown in Figure 48 where hydrate formation occurs. 61 .. that a wide range of hydrate porosities may be attained. so that hydrate prevention (or dissociation) can be addressed in the original design or in system operation through dehydration. For example. This effect has been observed at the Tommeliten field (Berge et al.

Pipeline Pressure Drops Due to Hydrates 50a) Atypical 50b) Typical Pipeline Pressure Drop Time Pipeline Pressure Drop Time .Figure 50 .

1. as deposition on the periphery of the pipe wall causes a gradual increase in line pressure drop. paraffin. prior to final blockage. and break. agglomerate. With paraffins the pressure buildup is more gradual. or acoustic sensors) can be used as indicated in Section III. Separator contents and pig returns provide the best indication of pipeline contents and should be regularly inspected. or some combination of these? Such questions are more easily answered with line access. so treatment for the more solid plugs should be considered as when hydrate and wax treatments fail. and Section III. Frequently only heating or mechanical means are available to detect the plug source. all of which can affect the flow and pressure drop. Techniques to Detect Hydrates. Separator discharges and the pig trap provide valuable information about line solids such as hydrates. gas/oil ratio. hydrates usually cause a series of sharp spikes (Figure 50b) in pressure as hydrate masses form. this group has more field experience in hydrate remediation than any other at present.B. Section III. Pressure changes immediately before the blockage should be studied in addition to such things as fluid slugging. With the exception of hydrate formation from gases without oil/condensate (with a typical pressure drop schematic in Figure 50a). and choke setting. gamma ray densitometers. etc. When partial or complete blockages are observed in flowlines. etc. who contributed through in-depth interviews (July 13-15. wax. In this section on detection of hydrate blockages. water cut. solid blockages of scale. scale. perhaps by an order of magnitude. are less readily detected and removed than hydrates or paraffins. A less direct flow indicator is line pressure drop buildup. questions always arise about the plug composition. When blockages occur in wells it may be difficult to distinguish the cause. by Paragon Engineering and Southwest Research Institute (SwRI) (April 1996). thermocamera. 1997).III. sand. Is the blockage composed of hydrates. and may be used as an early warning of future problems. Paraffin and Hydrate Detection Systems. Pressure drop increases are usually more noticeable than flow rates changes.1 considers early warning signs of hydrates. as on a platform where a number of detection devices (e. scale. rust.B. reservoir pressure. even when blockages are not a problem.2 considers methods to determine the center and length of the plug. A significant amount of material in this section was obtained from DeepStar IIA Report A212-1.B. sand. In flowlines and in wells. sand. which differs for hydrates and for paraffins. 62 .B. Another major resource was the Statoil Hydrate Research/Remediation group. Indications of the blockage composition are obtained through combinations of (1) separator contents and pig (sphere or ball) returns as direct indicators and (2) line pressure drop as an indirect indication.g.

Each method is discussed in the following paragraphs.1. early indicators of well formation are least developed. is wholly inadequate for reasons given in Section III. Unfortunately no indicator gives a single best warning of hydrate formation.g. (August 1994) provides a tutorial of this technology. There are four methods for warnings of hydrate formation in a subsea pipeline: (1) pigging returns. Rule-of-Thumb 17.B.B.b) are discussed independently below.1. with the debris swept from the pipeline into a “pig trap”. accompanied by a high pressure drop.a. such as the Norsk Hydro oil shown in Figure 34 and accompanying discussion in Section II.a Early Warnings in Subsea Pipelines. A lack of hydrate blockages does not indicate a lack of hydrates. Inc.C. Mohr Research and Engineering. (2) changes in fluid rates and compositions at the platform separator.1.a) and platform (Section III. the engineer turns to Section III. by H. etc. However. For example hydrate particles may occur when they have been suspended in an oil or condensate with a natural surfactant.1. that hydrate formation becomes a problem. Periodically a flexible plastic ball or cylinder called a “pig” is pressure driven through pipelines to clear them of condensed matter. Hydrates in a well are most often announced by abrupt flow blockages. Of the three portions of the offshore process where hydrates form blockages. (3) pressure drop increases.G. and (4) acoustic detection. but without problems (Urdahl. The pig’s trip is initiated via a “pig launcher” and ended by a “pig catcher or receiver”.B. 63 . When hydrates form without warning in a well.2.O. the well temperature is high enough to prevent hydrate formation. testing.III. providing notice of the need for corrective action. Frequently the pressure drop in a line. 1997) before a blockage in January 1996. Pipeline/Flowline Pigging Strategies. there is a significant need for better hydrate detection. Early Warning Signs for Hydrates. shut-in. In normal operation however. A detailed DeepStar II CTR 6401. Frequently hydrates form but flow (e. increased methanol injection. beginning gas lift. Instead a suite of indicators should be used to provide the best early warning before blockages occur.a.” Early warning methods in the subsea pipeline (Section III. commonly thought to provide the best warning. e. Frequently hydrate particles are found in pig traps before hydrate blockages occur in pipelines. even with the methods listed in this section. Statoil’s Gullfaks subsea installation may have undergone several start-ups with hydrate present. It is only during abnormal operations such as start-up. III. “Techniques to Remove Hydrate Blockages. in an oil with a natural surfactant present) and can be detected in pigging returns.1.B.B.g. (1) Pigging Returns.

Pigging returns should be carefully examined for evidence of hydrate particles. Hydrate masses are stable even at atmospheric pressure in a pig receiver or catcher discharge. The endothermic process of hydrate dissociation causes released water to form an ice shell, which provides a protective coating to inhibit rapid dissociation (Gudmundsson and Borrehaug, 1996). However, it may be very expensive to provide pigging, either via a mobile pigging vessel over the well or from the well head without round-trip pigging capability. Such costs make examinations of pigging returns an infrequent luxury. (2) Changes in Fluid Rates or Composition at Platform Separator. When the water production rate is small it may be possible to monitor the rate of water production as an indication of hydrate formation. If the water arrival decreases appreciably at the separator, hydrates may be forming in the line. _____________________________________________________________________ Case Study 9. Separator Water Rate as an Indicator of Hydrate Production. In a controlled experiment, British Petroleum formed hydrates in a 14.5 inch I.D., 13.7 mile long gas line in the southern North Sea. Corrigan et al. (1996) reported that prior to the trial water arrived at the separator in the amount of 1.3 bbl/MMscf. The test was started at the time marked “Day 1” in Figure 51. After methanol injection was stopped, the separator water arrival stopped completely after about 30 hours (no increase in water volume), while gas flow rates remained steady and pressure drop did not change. The first significant increase in line pressure drop (to 2.4 bar in Figure 52) was observed 46 hours after the start of the test. A further rise in ∆P to 3.3 bar was noted after 3 days. Seventy-four hours after the start of the trial, large fluctuations in the gas flow rate were observed that were concurrent with further increases in ∆P. A large slug of liquid, presumed hydrates, arrived at the slug catcher at the trial conclusion. BP estimated 50 metric tons of hydrate were formed before methanol injection was resumed. _____________________________________________________________________ The above case study is evidence that separator water rate provides an early indication of hydrate formation in a gas line with almost no oil/condensate and little water production. When water production is substantially higher, it may be difficult to monitor changes in separator water arrival for an early warning (Todd, 1997; Austvik, 1997). Statoil’s Gjertsen (1997) suggested that changes in gas composition provide an early indication of hydrate formation. In a rich gas field in the Norwegian sector of the North Sea, chromatograms showed a removal of hydrogen sulfide (H2S) from sour gases as hydrates form. Hydrates particularly denude H2S from natural gases, due to

64

Figure 51 - Water Production for Wet Gas Line
(From Corrigan et al, 1996)

300 Volume (barrels) in slugcatcher vessel
Water arriving as slugs - water simultaneously being processed from slug catcher

250
Sphere Arrived

200

Water processed from slug catcher

150

High DP MeOH Injected

100

Water arrival @ 0.6bbls/mmscf

Hydrate slug entering slug catcher

50

Water processed Start of Trial

0 0 1 2 3 4 Time (days) 5 6 7 8

Figure 52 - Differential Pressure Due to Hydrate Blockage
(From Corrigan et al, 1996)

70
High DP due to hydrates. MeOH Injected. High DP maintained while hydrate melts, slug flow.

60 Differential Pressure (psi)

50

40
Normal line DP at a flow rate of 9 mmscf/d

30

20

10 0 1 2 3 4 Time (days) 5 6 7 8

the near-optimal fit of H2S in the small hydrate cavities (see Sloan, 1998, Chapter 5). The same statement is not true about the other acid gas, carbon dioxide. (3) Pressure Drop Increases. Pressure drop (∆P) will increase and flow rate will decrease if the pipe diameter is decreased by hydrate formation at the wall in a gas line. Since ∆P in pipes is proportion to the square of turbulent flow rates, the change in ∆P is more sensitive than the change in flow. With hydrates however, a large restriction may be necessary over a long length before a substantial pressure drop occurs. For example, if a hydrate decreased the effective pipe diameter from 12 to 10 inches over a 1000 foot section, the ∆P would only increase 0.05 psi with 10 MM scf/d of gas operating at 1000 psia and 39oF. In addition, the ∆P trace usually contains substantial noise, making it difficult to observe trends. Statoil’s Austvik (1997) suggested that, while a gradual pressure increase in hydrate formation will occur for gas systems, a gradual pressure increase is not typical for a gas and oil/condensate system. In gas and oil/condensate systems, Statoil’s experience is that, without advance warning the line pressure drop will show sharp spikes just before blockages occur. Figure 52 shows the BP field experiment (Corrigan et al., 1996) with methanol stoppage in a North Sea gas pipeline with little condensate or free water; in that figure step changes and spikes in ∆P are more prevalent than a gradual increase. In contrast, recent DeepStar Wyoming trials (Hatton et al., 1997) show both gradual and spiked pressure drops, in a gas-condensate field. In Case Studies C.25, 26, and 27 the pressure built gradually upstream of a plug, while pressure spikes downstream indicated hydrate sloughing from the wall, with agglomeration and bridging downstream. However, the DeepStar tests had five pressure sensors spaced at intervals of a few thousand feet. As indicated in the calculation two paragraphs earlier, with only two pressure sensors at either end of a line, severe hydrate wall buildup must occur in order to sense a significant pressure drop, due to the dampening effect of the gas. Most pipelines are likely to experience hydrates as sudden, extreme pressure drops. (4) Acoustic Sensing Along Subsea Pipeline. DeepStar IIA Report A212-1, Paraffin and Hydrate Detection Systems, by Paragon Engineering and SwRI indicates: “The only hydrate crystal detection instrumentation suitable for subsea use identified by this survey is sand monitoring instrumentation...In a limited number of laboratory tests, the Fluenta acoustic sand monitor has detected hydrates. However, a detailed study using the Fluenta monitor has not been conducted.” A typical acoustic sensor from Fluenta is shown in Figure 53. Over 280 units have been installed to detect sand impingement on pipe by clamping the unit onto the flow line downstream of a 90o elbow or 45o bend. At flow rates as low as 3 ft/sec the

65

Figure 53 - SAM

400s Pwtide

Detector

(From Deepstar IIA A212-1,1995)

Underwater Electronic

Mateable Connection

Stainless

Steel

Pad

Cable

Length

-

TBO

two methods are suitable for detection of hydrates on a platform. While this blockage is obviously not an “early warning. Statoil’s hydrate group provided a thermocamera picture of a hydrate plug. the low temperatures enable portable thermometers to be used in detecting plugs and potential plug points topside.” the picture is indicative of the instrument’s ability. etc. and may be diver-assisted or ROV installed with an underwater cable. this unit has yet to be field tested in a subsea application. particularly at points where hydrates might form but a thermocouple is typically not provided. A thermocamera is a hand-held device which measures the infrared spectral transmission as an indicator of system temperature. inhibitor injection etc.unit can detect 50 micron sand particles. The initial background note of the Paragon Engineering and SwRI (April 1996) study presets a caution which still exists: “This survey did not identify any proven hydrate or paraffin deposition measurement instrumentation for subsea multiphase flow lines or any other type of fluid transmission lines. As hydrate deposits build and as restrictions cause gas expansion. A thermocamera enables determination of temperature variations in the system. variations in wall thickness. After location of low temperatures the engineer can determine whether the system is in the hydrate formation region. such as downstream of a valve.” III.1. (6) Gamma-ray Densitometer with Temperature Sensing. However. Acoustic sensors quantify the “hail on a tin roof” sound typical of hydrate particles impinging on a wall at a pipeline bend. For gas transmission lines. the thermocamera is typically used topsides on a platform with air between the detector and the suspected hydrate plug. pipe roughness. The transmission of gamma-rays to the sensor is a function of the density of the pipe 66 . external pipe walls. In addition to the above four types of subsea early warning systems.b Early Warnings Topside on Platforms.B. to consider corrective actions such as insulation. The thermocamera is very sensitive to pipe coating. (5) Thermocamera. ultrasonic instrumentation has worked in specific applications and for single-phase liquid or gas lines. Since water absorbs infrared transmission. Such units are rated for water depths of 4000 ft. and (6) gamma-ray densitometer with temperature sensing. heat tracing. just beyond a short radius bend in a topside riser. The original color picture provided better temperature discrimination than the black and white reproduction presented here. an acoustical/pigging system has been proposed. where piping and equipment are more available: (5) thermocamera. A gamma-ray densitometer uses an emitter and sensor on opposite. as shown in Figure 54.

Thermocamera Picture of Hydrates in Horizontal Portion of Riser Topside (From Austvik. Statoil) .Figure 54 .

The temperature sensing requirement makes it difficult to use the densitometer subsea. at best gamma-ray measurements indicate changes in conditions which could be hydrates. The two objectives of locating the plug are: (1) to determine the distance from the platform from a safety perspective. by Mentor Subsea (12/95).1 should be first considered to see if they apply.C. b) Pressure location techniques: reductions.2. by Paragon Engineering and SwRI (4/96). and is commonly used in the chemical industry for level control in high pressure. non-visual systems. A high density and low temperature mass in the pipeline is likely to be hydrates.contents. Additional methods to determine hydrate blockage locations are: a) Filling the line/well with an inhibitor or mechanical/optical device. so the methods involve both art and science. and (3) Hydrate Plug Decomposition Test Program by SwRI (Hatton et al.B.d. 10/97)] were supplemented by Tommeliten field experiments by Statoil. Detection of Hydrates Blockage Locations. (2) A212-1 Paraffin and Hydrate Detection Systems. A recommended composite blockage location method is given in III. In combination with the temperature downstream of the densitometer (such as at the platform start-up heater as shown in Figure 55) hydrate formation can be discriminated. In this section three DeepStar reports [(1) A208-1 Methods to Clear Blocked Flowlines. whereas a slug of high density but without a temperature drop is probably water. fluctuations. which results in heat being removed from the condensed phases and lower temperatures. due to high hydrate plug velocities damaging thermowells. and (2) to determine the plug length. and c) Measuring internal pressure through external sensors. Unfortunately there is no precise way to locate the blockage.b and Rule-of-Thumb 16. with accompanying discussion. This technology is over 50 years old. The early warning methods of Section III. even small pressure reductions cause hydrate dissociation. The efficiency of hydrate blockage location schemes is governed by the topology of the system and by the hydrate porosity shown in Figures 49a.. As shown in the blockage removal Section III. increases.2. Hydrates are indicated by a low temperature in addition to an increase in density.B. III. whereas the water temperature is similar to that of gas. 67 . Because densities of hydrates and water are very similar gamma-ray densitometry alone cannot discriminate between the two.B.

/Dehydration Platform .Platform Use of Gamma Densitometer Thermocouple Gamma Densitometer line Start-up Heater Platform Choke From Pipe Gas 1st Stage Separator To Comp.Figure 55 .

the well had to be shut-in for two days due to bad weather. ____________________________________________________________________ Case Study 11. In each of the following case studies. _____________________________________________________________________ Rule-of-Thumb 18: Attempts to “blow the plug out of the line” by increasing the pressure differential will result in more hydrate formation and perhaps line rupture due to overpressure. 68 . When a hydrate blockage is experienced. Methanol Lubrication into an Export Line. The well contained 4-5wt% CaCl2 completion brine. The export gas was insufficiently dehydrated and water condensed at a low point in the line. The inhibitor injection volume enables the determination of blockage location relative to the platform. ____________________________________________________________________ Case Study 10. Filling the Line/Well with an Inhibitor or Mechanical/Optical Device. of water. particularly when the blockage is close to the platform. inhibitor is usually injected into the line from the platform in an attempt to determine the plug distance from the platform. Monoethylene Glycol Lubrication into Well Tubing.2. The hydrate blockage was removed by venting from the platform and injecting methanol down the riser.a. the operator was fortunate to reach the hydrate plug with an inhibitor. Both may be incorrect since hydrate accumulations push substantial liquids ahead of the plug. Hydrates completely melted after a total of twenty to thirty 55 gallon drums of methanol were used. but methanol was not injected prior to shut-in. to several hundred feet above the seafloor. given the line size and a knowledge of liquid retention within the pipeline.75 inch gas export line from a platform at Garden Banks Block 189 in 725 ft. Such a volumetric determination assumes the plug to be impermeable to the inhibitor and that the liquid hold-up in the line is known (or negligible). it is common to fill the line with an inhibitor. the higher density glycol (and sometimes brine) is preferred.III. When hydrates block a flowline. Since the density of methanol is low. An operator experienced a blockage in a multi-phase flow stream in the Gulf of Mexico. from two hundred feet below. A gas hydrate plug formed which held a differential pressure of 1000 psi without movement. The blockage and the line topology may prevent the inhibitor flow from reaching a blockage far from a platform. There is some disagreement about whether methanol or glycol should be lubricated into the line. After hydrocarbon flowed from the well for a few hours. Texaco reported a restriction in a 12.B. where hydrates rapidly formed. extending inside tubing inside a deepwater riser connection between the platform and the seafloor. and both are used. In most cases this method is ineffective. for safety reasons. The well was being cleaned in preparation for production.

in this case.A coiled tubing (see Section III.. See Case Study 15 (Section III. 1 mile-long line in the Gullfaks field. ____________________________________________________________________ Case Study 12. Figure 57 shows an flowline obstruction one-third the way between the platform and the well.b. Heating a hydrate blockage is not recommended. (2) back-pressurization. However. Pressure Location Techniques: There are three pressure techniques to locate a hydrate blockage which are performed on the platform side of the plug: (1) pressure reduction.B. and the GOR was 100-360 scf3/scf3. III. It was concluded that the plug was located mid-way in the pipe. for safety reasons shown in Figure 2b and accompanying discussion. With the well shut in. With low porosity plugs patience may be required. Depressurizing the Blockage for Location. the water rate was 16. unless the end is determined. Over a 25 hour period. 69 .1. ____________________________________________________________________ For hydrates in a well. The normal line operating pressure was 2420 psia and the hydrate equilibrium pressure (at the low temperature) was 261 psia.C.000 ft3/d. and (3) pressure fluctuations. The normal oil rate was 18.C. Statoil has used a broach similar to that shown in Figure 56. A similar wireline heating tool has been used by Statoil for hydrate dissociation in wells.000 ft. or fiber optics may be used to locate a plug.242 ft3/d. from the platform and requires mechanical intervention in the flowline. Figure 58 shows blockage upstream and downstream pressure response (note expanded scale).d. Each technique has advantages and disadvantages. this detection method is currently limited to the first 10. Jetting operations took two days. heating from one side of the blockage may be a viable option. However. Pressure Reduction.D. as illustrated in the following case study.) for the removal of this Statoil plug.4) was run down the tubing string and ethylene glycol was jetted to remove the blockage. when the hydrate end is discernable. If the pressure is suddenly decreased downstream. the downstream pressure at the platform was rapidly reduced to 1670 psia. In January 1996 Statoil experienced a hydrate blockage in a black oil system in a 6 inch I. and the entire remedial operation took one week to complete. the rate of downstream pressure recovery should be one-half the rate of upstream pressure decrease. This simple technique takes advantage of hydrate porosity by decreasing the downstream pressure and monitoring the rate of pressure recovery and the rate of pressure decrease of the upstream side of the plug. In a flowline a wireline. the hydrate blockage can be located and dissociated with the same tool. coiled tubing.2. the upstream pressure decreased about 73 psi while the downstream pressure increased the same amount. lowered on a wireline to determine the blockage depth. reach rod.

rmine Hydrate Location in Well (From S tatoil) .Figure 56 .Wireline Broach to Dete .

Hydrate Location In a Pipeline Distance L Plug Upstream Downstream 2/3 L 1/3 L .Figure 57 .

1997) 2420 1760 1750 2400 Subsea Pressure (psig) 1740 1730 1720 Topside Pressure (psig) 2380 2360 1710 1700 2340 1690 Subsea Pressure Topside Pressure 1680 1670 1660 0 5 10 15 20 25 Time (hours) 2320 2300 .Figure 58 .Pressure Change Used to Estimate Plug Location (From Gjertsen et al.

6 gravity gas. documented experience in hydrate remediation. blocking flow for a 0. The disadvantage of the method is that it does not give any idea of the length of the blockage. none of the injected gas condenses.2oF. prefers the above method of plug location. From these pressure values. This method consists of pumping a known amount of gas into the pipeline and measuring the change in pressure over time. or how multiple plugs may affect this location determination. averaging about 3psig/hr. constant temperature throughout the pipeline. ____________________________________________________________________ Example 13. 3. Pressure Increase. Before hydrate dissociation can begin to take place. An offshore 16 inch ID gas pipeline is in full production when a hydrate plug occurs. pressure recovery was very slow. The method locates the blockage center and the relative volumes upstream and downstream of the blockage(s). as shown in the following method.Two points should be emphasized about this case study: (1) safety and (2) rate. no liquid in the pipeline. 2. who may be inclined to discount a slow changes. causing the apparent plug porosity to be about 1000 times smaller than that for gas flow. 4. Back-Pressurization to Determine Plug Location. to prevent safety problems associated with a plug projectile (Section I) propelled by a high differential pressure. an estimate of volume can be obtained through PV=ZnRT. how close the blockage is to the platform (due to the unknown plug porosity). the approximate location of the plug end should be obtained to determine the best remediation method and evaluate safety concerns. This slow rate may not be noticed if pressure is not carefully monitored by platform personnel. The slow rate of pressure change was thought to be due to the fact that most of the line contained liquid. the small diagnostic pressure reduction was made from one side of the plug. ____________________________________________________________________ Statoil. the company with the most methodical. The line is shut-in and the pipeline cools to the ambient temperature of 39. To locate a complete pipeline blockage one method is to measure the pressure increase as metered amounts of gas are injected at the platform. One standard location procedure is back-pressurization. 70 . Statoil locates the plug-platform proximity by inhibitor back-injection (see Rule-of-Thumb 18) or by back-pressurization. no porosity of the plug. The following assumptions are made for the problem: 1. First. Second. well above the hydrate dissociation pressure. The rate of pressure increase is correlated to the rate of gas input to determine the length for a given diameter line between the platform injection point and the blockage.

9 of the GPSA Engineering Handbook (1994)) n = value obtained from data (data table below) P = corresponding pressure for n (data table below) R = 10.9)=3637 ft 3 V= → P (400) The first estimate of the pipe volume down stream of the plug is 3637ft3. The pipeline volume is estimated as: ZnRT (.76 minutes when 297 lbmoles of gas have been pumped into the line.58 600 3664 2 144.5.2oF. the heat of gas compression is dissipated rapidly.915)(297)(10.01 1500 3663 5 Avg Volume (Platform to Plug 3658 ZnRT P 71 .) are measured and these data can be used to estimate the pipeline volume downstream of the plug via the equation: PV = ZnRT → V = where Z = gas compressibility as a function of P. 850 psia. so that the pipeline pressure slowly increases.915 from Figures 23-7.9 of the GPSA Engineering Handbook (1994).8.73 (Universal Gas Constant in units of psia.76 400 3637 1 96.39 850 3667 3 198. The gas compressibility is estimated at 0.89 lbmole/min into the pipeline.T. and gas composition. A reciprocating pump on the platform is used to inject gas at a rate of 4. oR.8. ft3) T = 498. The first data point calculation is as follows: A line pressure of 400 psia is attained after 60. and 6. Estimated Pipeline Volumes Between Platform and Plug Data Point # Time (Minutes) Pressure Est Volume (psia) (ft3) 60. 600.g. lbmol.87oR (seafloor temperature) Five data points are averaged to estimate the volume of the pipeline between the hydrate plug and the platform.73)(498. 400. etc. The heat of compression is assumed to be dissipated in the ocean and the entire temperature remains at 39. the pipeline is initially at atmospheric pressure. The time required for the pipeline to attain even increments of pressure (e.61 1100 3662 4 300. Values obtained through an equation-of-state or from gas gravity compressibility charts (Figures 23-7.

4. bends. as shown in Figure 59a. ____________________________________________________________________ Back-pressurization has been implemented many times in the field and is probably the method of choice of many operators.B. the estimated location of the plug is 2620 feet (= 3658ft3/1. However these analyses have not been successful to date due to two factors: 1. which are usually unknown and may occupy portions of a pipeline. there are several disadvantages which cause significant inaccuracies. The average approximation for the volume after the hydrate plug was 3658ft3. Because hydrate plugs are frequently porous (>50%) and permeable.396 ft  4 4   Since the pipeline volume = (length)(cross-sectional area). they transmit flow and act as a “leak” in a system considered to be a closed (i. III.This same calculation is summarized for four other data points.d. in the above table. The liquid hold-up in the line must be known. A technique recently developed is to measure hoop strain of the pipe as a function of line pressure to determine the location and type of blockage. the method of back-pressurization should be supplemented by other methods. Due to the above inaccuracies.B. or when the hydrate plug has accumulated liquid in front of it. The gas compressibility must be well-known in order to determine the pressure and volume rate increases.396ft2) away from the platform.c Measuring Internal Pressure through External Sensors. This is particularly a disadvantage when significant elevation changes result in unknown liquid holdup profiles. no permeability) 2. Pressure Variation.06in 2   144in 2  =1. 3. acoustic response is a function of the relative amounts of gas and liquid.2. Both methods involve measurement of sound wave travel time or frequency changes from the platform to the blockage. The pipeline cross-sectional area is A=  1 ft 2  πD 2 π 16 2 2 = =201. as listed in the Section III. 2. and by a flexible plug. The cross-sectional area of the pipeline is calculated. valves. reflected pulses are dampened by walls. The location of multiple plugs cannot be addressed by this method. Pressure pulse travel time and pressure frequency response methods to locate a hydrate blockage are discussed in DeepStar IIA Reports A208-1 and A212-1. The 72 . as follows: 1. However.e.2. in order to estimate the pipeline length between the plug and the platform. only the plug located nearest the point of injection can be determined. An ROV places a metal caliper clamp on 25% of the pipe circumference using magnets.

5 Relative Distance (km) ViscoHard Elastic Clear Visco .Hydrate Plug Detection through Strain Measurement (From Deepstar A208-1. Pipeline Length 2.Elastic Clear .5 3 3. Hydrates are present where very little strain occurs in the pipeline. A graph of strain vs.5 4 4. 59b) 8 7 Strain/Pressure(bar) 6 5 4 3 2 1 0 1 1. 1995) 59a) Hydrate detection device which measures the amount of strain a pipeline undergoes under high pressure. pipeline length is shown below.Figure 59 .5 2 Strain vs.

use a mechanical device to determine plug location. Use a simulation to determine at what length the contents of the pipeline enter the hydrate formation envelope during normal operations. III. This will provide an approximation of the plug initiation point. Back-pressure the pipeline and monitor the pressure increase for a measured volume of gas input. This method was successfully used in the North Sea on an 8-inch. Use the rate of pressure change at wellhead and platform to determine the center point of plug(s). etc. 75 psig) is obtained at each point. Results of the strain gage are shown in Figure 59b for 20 points at various lengths along a line blocked with paraffin. sensed by the pipeline caliper. 3. The signal is transmitted to a work boat at the surface. 15 km long flow line. 1. 4. Recovery and deployment of each measurement required 1-2 hours. This calculation should be done during initial line design. relative to gas input. 14. 73 .B. Do not decrease the pressure on one side of the plug below the hydrate formation pressure. Estimate the distance from platform to plug by the rate of pressure change. Estimate the hydrate formation temperature and pressure of the blockage relative to the conditions of the pipeline.platform end of the flowline is pressurized inducing a hoop strain. Depressurize the platform end of the plug to about 2/3 of the pressure between the normal operating pressure and the hydrate formation pressure. This may be inaccurate due to pipeline elevation changes. this method yet to be used to locate a hydrate. The internal pressure causes a hoop strain that results in an outward movement of the caliper which varies with the wall deposits of the pipe. Lack of hoop strain across a section of pipe would indicate a blockage. Monitor the rate of pressure increase at the platform and the pressure decrease at the wellhead for the lesser of (a) either 24 hours or (b) until a significant pressure change (e. The map in Figure 59b was in agreement with the contents of the flow line when it was replaced. but with flow blockage the entire pipeline will cool into the hydrate stability region. between visco-elastic plugs (points 15-18 and 3-13) at either end. Due to necessity for ROV deployment. so a combination of the above methods are indicated below for best results. Use this technique with method 2 to determine volume before the plug. Confirm the simulation with a linear interpolation between the wellhead and platform temperature and pressure.g. With available resources. Points 13. 2. Recommended Procedure to Locate a Hydrate Plug.2. Fill the riser with inhibitor to attempt to determine the distance between the platform and the plug. for a given compressibility and simulated liquid retention volume. and 15 are shown to be blocked with hard plugs.d. There is no one precise method to locate the hydrate plug. or relative volumes at each end of the plug(s). 5.

the preferred method to dissociate hydrate plugs is to depressurize from both sides.C. III. and (c) total blockage with a liquid head. thermal methods which involve direct heating (Section III. drilling. weeks. When dissociating a hydrate plug.4).C. 2.1). and mechanical methods with coiled tubing. chemical methods such as injection of methanol or glycol (Section III.3). a shut-in will cause the entire line to rapidly cool into the hydrate region. Depressurization of Hydrate Plugs. Rule of Thumb 19.C.C. (Section III. (b) total blockage without substantial liquid head. from both a safety and technical standpoint. Four techniques to remove a hydrate blockage are listed in order of frequency: 1. results in “thrashing” without significant effects on plug removal. After a deliberate dissociation action is taken.C. it should always be assumed that multiple plugs exist both from a safety and a technical standpoint. 4. who are accustomed to producing results on a continuous basis. Techniques to Remove a Hydrate Blockage. etc.1.2). Measurements such as pressure drop across the plug are continuously monitored and changed deliberately. only after some time has passed to gain assurance of initial method failure. Often it is suggested that corrective actions be changed almost hourly when immediate results are not observed. and low lying points of water accumulation will rapidly convert to hydrate at the water-gas interfaces. hydraulic methods such as depressurization (Section III. Rapidly changing corrective actions. the most effective inhibitor. Combinations of the above methods are simultaneously tried. The following discussions concern only the final two cases.C. It is assumed that any indication of a partial blockage will be promptly treated with massive doses of methanol. Typical times of days or weeks are required for plug removal as indicated by Appendix C case studies. Applications of the above methods can be further divided into three cases: (a) partial blockage.III. 3. or months. Rule of Thumb 20. While one plug may cause the initial flow blockage. Depressurization is particularly difficult when the deepwater liquid head on the hydrate 74 . The “waiting” aspect of plug removal is frequently the most difficult for platform operating and engineering personnel. the time required for hydrate dissociation is usually days. both confidence and patience are required to observe the result over a long period of time. Regardless of the method(s) used to dissociate the hydrates. This section shows that.

If the pressure is reduced extremely slowly. III. Figure 60 shows the pressure-temperature conditions of a pipeline hydrate plug at point A in the two-phase (H-V) region. for example to -110oF for a methane hydrate depressured to atmospheric pressure. Radial hydrate dissociation controls plug removal. causing heat influx from the ocean to melt the hydrate at the pipe boundary. over 20 hydrate plugs were intentionally formed and removed from a 6 inch North Sea line in the Tommeliten Gamma field.C. The dissociation temperature at the hydrate front is determined by the pipeline pressure.). the pressure-temperature conditions are illustrated in Figure 60. When hydrates form. in which liquid water has converted to hydrate. predicted by the methods of Section II. Joule-Thomson (isenthalpic) cooling (line AB) at the hydrate may worsen the problem. Heat flows radially into the pipe. permeable hydrates easily transmit gas pressure while still acting to prevent free flow in the pipeline. With rapid or extreme pressure reduction. then the question arises. When the pressure was decreased at both ends of a highly porous hydrate plug. Pressure reduction is accompanied by a temperature decrease at the hydrate interface. In both laboratory and field studies these plugs were found to be very porous (>50%) and permeable. If the pipeline is rapidly depressured without heat transfer. Porous. the hydrate equilibrium temperature will decrease far below 32oF.plug is greater than the dissociation pressure. Before that point is addressed.a Conceptual Picture of Hydrate Depressurization. while to the right only fluids can exist. isothermal depressurization (line AC) results.C and II. In this case water from dissociated hydrate will rapidly convert to ice below the solid-liquid line (I-LW-H shown in Figure 60). Because the lowest ocean temperature (39oF) is well above the ice point of 32oF. When a hydrate plug occurs in an ocean pipeline. The depressurization results in a uniform hydrate dissociation temperature which is in equilibrium with the LW-H-V line pressure in Figure 60. ice formation (which could block flows) is not a normal operating concern. a conceptual picture of hydrate provides some key points in the dissociation process. Pipeline depressurization reduces the hydrate temperature below the temperature of the ocean floor (39oF for depths greater than 3000 ft.D. causing dissociation first at the pipe wall as shown in Figure 61. To the left of the three phase (LW-H-V or I-LW-V) lines hydrates or ice can form. because the pipe diameter (less than 75 . Usually an intermediate pressure reduction rate causes the hydrate interface temperature to be significantly less than 39oF. “How will the ice plug dissociation rate compare to the hydrate dissociation rate in an ocean pipeline?” In 1994-1997 field studies. If ice formation occurs with hydrate dissociation. the pressure decreased throughout the entire plug to an almost constant value. flow is blocked so that the plug temperature rapidly decreases to the ocean floor temperature of 39oF at the pipeline pressure.1.

Figure 60 . 1997) I-Lw-H A ∆H = 0 Pressure -H Lw V B HYDRATES I-Lw-V V I-H- ∆T = 0 C NO HYDRATES ICE Temperature .Isethalpic and Isothermal Plug Dissociation (From Kelkar et al.

Radial Dissociation of Hydrate Plug A) Pipeline Cross Section Heat B) Pipeline Longitudinal View Water Heat Heat .Figure 61 .

Of course some plug dissociation occurs at the ends. In the above conceptual picture. a partiallydissociated plug will move down the pipeline when the line is re-started. but only by an average of about 1oF per 100 ft. and II. indicating that one of the most important aspects of plug removal is patience to allow time for total dissociation. but due to much smaller dimensions the radial dissociation (which occurs simultaneously along the plug length) controls blockage removal.) is typically at least an order of magnitude less than the length of a hydrate plug (frequently more than 50 ft. If a line is insulated. Figure 62a shows an inner hydrate core enclosed in a water layer. The second blockage by the plug can be more compact than the first. depression. The water layer is adjacent to the pipe wall. or other obstruction. 1990. which results from hydrate melting. Because hydrate plug detachment occurs first at the pipe wall. to the hydrate dissociation temperature (set by the line pressure to a point just above the ice point) where it remains uniform throughout the hydrate layer. As a result. An inner hydrate core is surrounded by an ice layer. Alternatively. the radial disappearance of the two-phase water+hydrate boundary (X1) determines the disappearance of the final solid and eliminate the flow obstruction. This phenomena relates to Rule-ofThumb 19. deep ocean water so that the pipe wall temperature is constant at 39oF. As diagrammed in Figure 62 when the temperature of the hydrate is lower than that of the ocean floor. The radial dissociation concept presents a contrast to previous longitudinal dissociation concepts of non-porous hydrates. to a lower hydrate 76 . Figure 63b shows the temperature profile from 39oF at the pipe wall. of buried depth. only to result in a later plug at a pipeline bend.D. the pipe wall temperature will be greater than 39oF. Figure 62 shows a cross section of a pipeline hydrate plug that has been depressured to provide an equilibrium temperature just above 32oF.. The cross section in Figure 63a shows a hydrate plug dissociation when the pressure is too low. Such a pressure corresponds to about 450 psia for a pure methane gas.) in a pipeline. heat flows radially into the system. Figure 62b shows the temperature profile from the ocean temperature of 39oF at the pipe wall. et al. to 32oF at the water-ice interface. hydrate dissociation becomes much more difficult because the insulation which prevented heat loss from the pipe in normal operation will prevent heat influx to the pipe for hydrate dissociation. causing dissociation along the entire length. as predicted by the methods of Sections II. but much lower for a natural gas.C. DeepStar Report CTR IIA A208-1.2 ft. for example if there is substantial momentum on impact at the bend. that is enclosed in a water layer adjacent to the pipe wall. if the pipe is buried in the ocean floor. 1995). it is assumed that the pipeline is exposed to turbulent. in which depressurization from both ends was supposed to result in dissociation progressing from the plug ends toward the middle (Yousif.

Figure 62 .Hvdrate Dissociation with Water Present _ Water To= 40°F - Hydrate T. = 33°F Water To= 40°F Wall ‘5 x? 4 Moving Boundary Wall .

T.= 40°F v-v~*FiMoving Boundaries x 1 .

as in Case Study 14. There are two reasons for the preferred method of two-sided hydrate plug dissociation: 1. while only 17 days would be required for dissociation of a hydrate plug to water if the pressure was maintained at 450 psig. there are two two-phase boundaries: a slowly dissociating water-ice boundary (X 1). this suggests that plugs should be dissociated as soon as possible to take advantage of higher porosity. If this is impossible. 2.dissociation temperature (set by the line pressure) at the ice-hydrate interface.b Hydrate Depressurization from Both Sides of Plug. where it remains uniform throughout the hydrate layer. For a single plug. if available. 85 days are required for radial dissociation of an ice plug. Plug permeability may decrease considerably during the first hours after plug formation. while an ice plug removal must rely on heat influx alone.C. Two-sided dissociation eliminates the Joule-Thomson cooling which may stabilize the downstream side of the plug. depressurization through a service line for injecting inhibitors at the well head. Hydrate removal is accomplished by both depressurization and heat influx from the surroundings. For example. We are particularly interested in the rate of progress of X1. twosided dissociation is more than twice as fast as single-sided dissociation. In some cases. and a second. Gulf of Mexico Plug Removal in Gas Export Line. _____________________________________________________________________ Case Study 13. particularly for plugs of low porosity/permeability or for very long plugs. As a result. As a result an ice plug may dissociate more slowly than a hydrate plug. rapidly dissociating ice-hydrate boundary (X2). a hydrate plug should be dissociated through a second production line. Hydrate dissociation to a low pressure almost always results in an ice problem which may be more difficult to remove than the initial hydrate. These calculated results are based upon the radial dissociation model of Kelkar. et al. it may be worthwhile to connect a floating production vessel to the manifold or wellhead for depressurizing the upstream side of the plug. dissociation from both sides eliminates the safety concern of having a projectile in the pipeline. For the above reasons. (1997) in which radial dissociation prevails. III.1. since any solid phase constitutes a flow obstruction in a pipeline. which determines the disappearance of the final solid (ice). With radial dissociation along the plug. in this case provision should be made for removing or bypassing the check valve in the service line at the well head. Austvik (1997) noted some exceptions to radial dissociation. if a 16 inch line containing only methane is depressured to atmospheric pressure. A hydrate blockage in the export line from Shell’s Bullwinkle platform in the Green Canyon Block 65 to the Boxe platform was reported in DeepStar Report A208-1 (Mentor 77 .

the line was depressured on both sides of the plug. The reasons were: 78 . without condensate. After complete removal of the hydrates. it was not dehydrating gas as designed. Plug Formation Setting The gas field is located in the southern North Sea and consists of three subsea wells. After production was restarted. The entire remedial operation required 36 hours to complete. and condensate is then pumped through a 22 mile. page 52). Gas gravity was 0. _____________________________________________________________________ When depressurization cannot be easily achieved from both sides of a plug. gas. The MEG in the pipeline is recycled and piped back to the manifold via a 3 inch pipeline piggybacked to the export line. but complete blockage of the pipeline had occurred during shut-down. A graphical representation of the field is shown in Figure 64. The major cost was the lost production time.Subsea. Seawater temperature was 50oF at the base of the platform in 1400 ft. then more costly steps may be required to balance the depressurization to ensure platform safety. insulated export pipeline to a processing platform where water is removed from the condensate. of water. flowing into a subsea manifold with a capacity of four well inputs. consequently mono-ethylene glycol (MEG) is injected into the manifold and wellheads to thermodynamically inhibit hydrates. The well’s gas compositions. 39. During the shut-in period the gas dehydrator was partially filled with water. The inhibited water.7. Flow rate was 140 MMscf/d at an inlet pressure of 800 psi. It was hypothesized that the blockage was a result of a hydrate plug. as indicated in the following case study. Then methanol was circulated into the line to accelerate the hydrate dissociation rate. Gas hydrates formed during a re-start after the platform was shut down due to a hurricane. 22 mile long pipeline between a North Sea gas field well and platform. trenched. and wet gas entered the export riser. since the dehydrator was not cleaned out properly. temperature.000 ft. The 12 inch. line was un-insulated line. Blockage On April 14th. causing water condensation and hydrate formation. To remove the blockage. The liquid slug was remediated. and pressure promote hydrate formation. A complete hydrate blockage formed in less than one hour. This case study is a remediation summary of hydrate blockage in an ARCO 16 inch. the dehydrator was cleaned. inspected and restarted properly. _____________________________________________________________________ Case Study 14: Removal of North Sea Hydrate Plug by Depressuring Both Sides. 1996 an unusually large liquid slug over-ran the platform primary separator causing a temporary shut down. just past the base of the export riser at a low spot. 1995.

16” Export Pipeline Well Manifold Well Fourth Intake . 1996) Host Platform Well 36 km .Offshore Platform and Manifold (From Lynch.Figure 64 .

27 formed low-porosity. consequently a delay of approximately eight weeks was needed to locate a suitable rig. Will the remediation process effectively depressurize the pipeline? 2. The time required for hydrate removal could be twelve weeks. Depressurization Method Initial Ideas Three questions were raised to determine a proper depressurization method.15. process engineers. safety management. The blockage’s proximity to the platform posed serious safety concerns. and C.980. 1. Slow depressurization was required to remove pressure build-ups in the hydrate plug(s). From the rig. consultants. The 3 inch MEG inhibitor line had ruptured. the pressure differential would cause a projectile to form which could destroy the riser piping and damage the platform. What is the cost of equipment and modifications? 3. Modification: A spool piece would have to replace a non-return valve on the manifold’s fourth well intake. if gas became trapped within multiple plugs. The projectile would be lifethreatening to workers on the platform and result in costly damages to the platform itself.17 in Appendix C. Consequently. recovered during depressurization at the platform.16.000 79 . Projectiles could form due to dissociation. and diving specialists proposed three potential depressurization methods. They were: 1) Jack-up Rig. two DeepStar field trials C. did not contain MEG inhibitor. the pipeline was exited the mudline allowing contents to be rapidly cooled by ocean currents. and C. In contrast however. attach a high pressure riser to the manifold’s subsea tree and flare exiting gas via the rig’s flare stack. Several methods were considered. Method: Tow a jack-up rig to the site. low-permeability plugs which would transmit pressure very slowly and withstand high pressure drops. Through back-pressurization. At this location. Time Required: A drilling rig was not currently available.• • • • The pipeline free water. How much time is needed to complete the remediation? Based on these questions. C. the blockage was found to be 150 meters away from the platform.) The liquid slug which shut down the compressors probably was caused by a partial hydrate plug pushing a fluid front down the pipeline as it moved.26. This had also been observed for several Statoil hydrate plugs (see Tommeliten Field Case Studies C. depressurization had to be done through both the platform and the subsea manifold to ensure safety. Pipeline depressurization was necessary to dissociate the hydrate. causing hydrate formation. Slight decreases in pressure determined that the blockage had some porosity. If only the blockage’s platform side was depressured. Estimated Cost: $1. however it had to be done on both sides of the hydrate plug.

Feasibility: Substantial modifications to the platform made this remediation method costly and impractical. expected to be higher than the other methods based on the large amount of modifications that were required. To further complicate the matter. flexible riser. and coordination requirements between the diving rig and the FPSO. A valve skid containing both emergency shutdown valves (ESDV’s) and a MEG injection valve was also needed. a method of injecting methanol was needed to prevent future hydrate growth. 2) MEG Injection Line Method: Connect the subsea manifold’s spare fourth flange to the 3inch MEG pipeline and flare gas at the platform. All parties were educated about the tasks involved. which had limited storage space. 3) Floating Production and Storage Vessel (FPSO) Method: Connect a FPSO with a processing plant and flare to the subsea manifold’s fourth flow loop and process the exiting gas. It was deemed unusable in any circumstance. consequently the required time was expected to be 6-8 weeks. The immediate availability of a FPSO and diving rig allowed modifications to begin. Estimated Cost: $1. process.906. The flexible riser and the manifold would be connected with a spool piece. Modification: The platform required no modifications. Figure 65 is a schematic of the design. useful in the absence of other methods. Time Frame: A FPSO was available for immediate use.000. Modification: Subsea work would require a spool piece installed between the two pipelines. Feasibility: This method proved to be the most feasible. The permits were 80 . Secondly. Establishing Procedures/Permits It took approximately two weeks to develop potential remediation processes. Government permits were applied for at the Health and Safety Executive Pipeline Inspectorate (HSE) and the Department of Trade and Industry Oil and Gas Office (DTI) for additional gas flaring and well modification. Procedures were then written to firmly establish the processes required for the pipeline depressurization. Time Required: Six to eight weeks. The platform (while in operation) required significant modification to connect the MEG pipeline to its flare stack.Feasibility: The large amount of time required to locate a jack up rig made this an ineffective remediation method. all of the MEG currently in the pipeline would need to be stored on the platform. It was estimated that the FPSO could be at the site and begin within two weeks. Procedures considered the safety. Estimated Cost: Unknown. A diving rig was required to do the subsea work. The connection between the manifold and FPSO would be made through a high-pressure.

1996) Collar Buoy FPSO FPSO process and flares exiting gas from the manifold 280 meter High Pressure Riser 5 Ton Clump Weight Valve Sled 16” Export Pipe Manifold .Figure 65 .Preliminary Remediation Set-up (From Lynch.

Due to the sandy ocean bottom. Spool pieces were used to allow riser intake from the side of the ship deck. of the high pressure riser via a tugger rigged with a dead man’s anchor. The valve skid was placed on a concrete mattress and then stabilized with gravel bag supports coupled with Tirfors.expedited by local agencies to prevent delay in hydrate removal. The MEG in the riser provided some buoyancy. control of gas pressures from the deck of the FPSO. consequently it required some modification to process the 1300 psig pipeline gas. It proceeded to deploy 920 ft. The valve skid contained ESDV’s and a MEG injection system for the pipeline. This insured that no movement would transfer from the flexible riser to the valve skid. chain blocks. This design enabled a safe. Initial design placed choke valves in the riser to reduce pressure for the quick-release valve. The fourth well intake was then modified with a spool piece for connection with the high-pressure riser. the FPSO and diving rig were being equipped for the operation and moving to the field. Figure 66 is a figure of the subsea valves and their attachment to the manifold. 81 . The FPSO could only process gas at 600 psig. In the meantime. An innovative new quick-release valve was developed with a standard valve weak link with three additional hydraulic jacks for manual release. it became necessary to provide a foundation for the valve skid. and ground anchors. of 1 inch piping to maintain the minimum process temperature required by the FPSO. Additionally. This complicated the design because current quick-release valves could not withstand pressures of 1300 psig. Two weeks were required to prepare procedures and permits for depressurization. a quick-release valve (QVD) was needed to enable the FPSO to escape from the riser in case of an emergency. A five ton clump weight was placed at the bottom of the riser with a buoyancy collar attached to the surface. The diving rig then inspected the flexible riser route to ensure that is was clear of debris. The buoyancy of the riser prohibited pipeline intake through the FPSO’s moonpool. simplified. The valve skid was now ready to be put in place. A description of the system is shown in Figure 67. This valve could withstand 1500 psig of pressure. Depressurization of the Pipeline Operations The divers first task was to manually locate the subsea manifold’s fourth intake and to isolate it from any trees or flow loops. however this caused control problems and was deemed impractical. consequently the line was anchored through concrete mattresses. The riser was also steam traced with 1000 ft. allowing choke valves to be placed on the ship’s deck which simplified control issues.

Valve Sled with Manifold Interface (From Lynch. 1994) 6” Manuli Riser ESD Valves Manifold ME GI nje ctio Valve Sled Existing 1500 PSI Flange nL ine .Figure 66 .

This design easied pipeline control tremendously.Design with High Pressure Quick-Release Valve (From Lynch. 1996) Initial Design Final Design Low Pressure Quick-Release Valve FPSO FPSO High Pressure Quick-Release Valve Choke Valves Choke Valves The High Pressure QR Valve allowed choke valves to be placed on the deck of the FPSO.Figure 67 . .

These formed as a result of gas pockets suddenly releasing as the plug was dissociated. One gas well was opened and the platform flow high to maintain low pressure. The first 12 hour night shift reported 7000 ft3 of water received from the separator. Overall the modification and installment procedures required one week before pipeline depressurization could begin. As the graph illustrates. Note the slight pressure increases that occurred during depressurization. Above normal amounts of MEG were added to the system before pipeline start-up. Throughout the whole operation. Depressurization Twenty three days were required to completely dissociate the pipeline hydrate. hydrates will continually dissociate. To prevent ice formation. The pressure was monitored for 12 hours after the hydrate was thought to be dissociated. Recommissioning the Pipeline After the hydrate was dissociated. Ice formation was prevented through use of the hydrate equilibrium curve (Figure 69) for the field. maintaining the equilibrium temperature at that given pressure. The pipeline had to be re-commissioned carefully to prevent reformation of hydrates. This causes significant problems because ice melting might have required significantly more time. Back-pressuring also proved beneficial in determining the location of the plug. Determining the Pipeline Minimum Pressure Reducing pipeline pressure too much could result in ice formation. there remained significant amounts of free water in the pipeline. preventing hydrate formation. At constant low pressure. Heat transfer between the ocean and the pipeline was slow because the line was trenched and insulated in the sea floor. Consequently. no equipment failure occurred and the operation progressed smoothly. the pipeline pressure could not drop below 175 psig. the water which would result 82 .Figure 68 is a complete picture of the FPSO attachment to the subsea manifold. No pressure variation was noticed so the flexible riser was recovered and the depressurization apparatus dismantled. Dissociation was slightly facilitated by occasional back-pressuring which drew methanol into the plug. than hydrate dissociation. the equilibrium pressure at 320F was 200 psig. All valves and risers were tested and shown to be in working order. the FPSO reduced the pipeline pressure to 185 psig to maximize hydrate dissociation without ice formation. The high intake caused a high gas velocity which facilitated rapid water removal. Figure 70 shows the pressures in the pipeline throughout the depressurization process.

1996) FPSO Sea Surface Chute/Disconnec t Umbilical Manuli Hose Collar Buoy Strops Manuel Ball Valve 34 km 16” Export Pipeline Hose Clamp Manifold Clump Weight Safety Valves .Complete FPSO/Manifold Interface (From Lynch.Figure 68 .

Figure 69 .Hydrate Formation Curve (From Lynch. 1996) 1400 1200 1000 Pressure (psig) 800 600 400 200 0 30 35 40 45 50 55 60 65 Temperature (oF) Hydrates No Hydrates .

Figure 70 .Pressure of Manifold and Platform During Hydrate Remediation (From Lynch. 1996) 450 400 350 Pressure (psig) 300 250 200 150 100 50 0 0 2 4 6 8 10 Time (days) 12 14 16 18 20 Platform Manifold .

On top of this. and recommendations are provided in Example 14. However the situation has been evaluated in light of most of the case studies in Appendix C. if the gas is not vented. The procedure and methodology followed could be applied to many different situations. _____________________________________________________________________ III. However. This example abstracts an in-depth study of fluid removal as a preliminary step to depressurizing lines done in DeepStar Report A208-1 by J. Figure 71 provides a timetable of the remediation process. and excellent resources helped in removing the hydrate plug.from a 1. The high flow rate of gas was maintained until the water contained 40% MEG. Figure 72 shows the Lw-H-V equilibrium conditions for the Hercules and Jolliett fluid conditions in a 50 mile pipeline in 4000 ft. When a blockage occurs.25 mile long (non-porous) hydrate plug. After gas venting the pressure is still 1000-1300 psia. of water in the Gulf of Mexico. Hydrate prevention is key in preventing significant economic and production losses. The cost of depressurizing the pipeline was almost 3 million dollars. Conclusions The remediation team removed the hydrate plug efficiently. due to lack of production. ____________________________________________________________________ Example 14. a factor of 5-6 times greater than the 83 . clear objectives. This case study shows the potential financial loss that can result from hydrate plugs. They achieved a monumental task in a very short period of time. the removal of fluids from each side of a hydrate plug may be difficult.c Hydrate Depressurization from Both Sides of Plugs with Significant Liquid Heads.C. Communication. ensuring that the line was fully inhibited. Despite the efficient remediation effort. relations between the buyers and producers were tested. Fortunately. good initial relations between the two reduced the impact of the disruption. without counting lost production. Davalath (December 1995). preventing more severe economic losses. When depressuring a multi-phase deepwater pipeline the hydrostatic pressure (or head) of the liquid against the face(s) of the plug may be higher than the hydrate dissociation pressure. the temperature rapidly decreases to 40oF with a pressure between 2000-3000 psia (a subcooling of 30-33oF).1. Results similar to those of Case Studies 13 and 14 may not be applicable to very deep ocean plugs. The pressures and intakes were then returned to normal operating levels. Methods of Fluid Removal in Plugged Deepwater Lines. To date there is little documented experience for depressuring plugs with liquid heads in deepwater lines. the economic impact of the hydrate plug was substantial.

Figure 71 . FPSO Modifications Subsea Installation FPSO Transit FPSO-Manifold Hookup Depressurization of Line Dissociation of Plug Pipeline Unblocked MEG Injection w/ production Full Production Resumed 6/6/96 6/2/96 01 APRIL 08 15 22 4/14/96 29 06 MAY 13 20 27 JUNE 03 10 17 . 1996) TASK NAME Orwell Pipeline Blocked Attempts to move plug Development of Jack-up Rig Development of FPSO Decision Made Development of Detailed Design HAZOP/Safety Study FPSO-Manifold InterfaceFab.Schedule for Complete Plug Remediation (From Lynch.

Hydrate Formation Conditions (From Deepstar A-208-1.Figure 72 . 1995) 3500 Hercules 3000 2500 Jolliet Cool Down Conditions Before Venting Gas at Platform HYDRATES Pressure (psia) 2000 1500 1000 500 Required Pressure to Dissociate Hydrate Plug Shut-In Conditions After Venting Gas NO HYDRATES 0 20 30 40 50 60 70 80 Temperature (oF) .

000 bbls in an 8 inch line and 26. Multiphase Pumping to Surface (Figure 73) at a rate of 5000 BOPD to remove liquids in 3-6 days 2. If there are no access points. Of the seven options summarized in Table 8. handle large liquid volume on workover vessel deploy separator/pump hardware subsea extremely slow: 21 days to remove 12.000 bbls in a 12 inch line 50 miles long. The techniques listed in Table 8 were considered for liquid head removal. Launch a gel or foam pig followed by nitrogen Issues/Limitations temporary deployment. the volume to be removed would be 12. to about 150 psia where the equilibrium temperature is 25oF.000 bbl from 8” line. the line will have to be hot-tapped. Assuming only 70% of the pipeline volume is filled with liquid. however. those with gas lift were eliminated due to low liquid removal rates. access point must be large enough to introduce pig 84 . Combine subsea separator with gas lift 6. slightly inside the ice formation region. To initiate hydrate dissociation.equilibrium pressure (200 psia) at the ocean floor temperature (40oF) with a subcooling of 22oF. Multi-phase pumping with gas lift 5. Displace with nitrogen from platform 7. All of the options in Table 8 require that the plug location be determined and that the pipeline have access points in order to remove the pressurizing liquid and plug. the hydrostatic head must be removed below 200 psia. Gas lift pipes on each side of plug (Figure 74) 4. the entire volume from the platform to the manifold must be removed.C. Techniques to Remove Liquid Head Above a Hydrate Plug Option for Removing Liquids 1. electrical submersible pump. None of the depressurization options were recommended.000 bbl from 12 inch line similar issues to Option 1 too slow. Subsea separator. Table 8. so that a 15oF temperature gradient will cause heat to flow from the ocean to the hydrate.4 on mechanical removal. 25+ days to remove 26. multiple access ports at 4 mile intervals were recommended with use of coiled tubing as described in Section III. In a worst-case scenario. The figures in the example indicate that workover vessels need to be positioned above the plug. vent gas & pump liquid to surface 3. similar issues to Option 2 requires large volumes of N2 at high P gel pigs separate gas and liquid.

Fiaure 73 - Pipeline Depressurization -Multiphase Pump Option (From Deepstar A-208-1. 1995) Methods Ft. Hydrate PLug 1 RCiV .

.r F ure 74 (From Deepstar A208-1.' 1995) 4000 Ft.

With multiple plugs. unblocked flowline. and depressurization techniques should be similar to depressurization through one side of a plug. 1.C. becoming a severe safety problem (see Section I) as well as damaging equipment.d. JouleThomson cooling of gas flow may cause the downstream end to progress further into the hydrate stability region. If a substantial liquid head is present. or Multiple Plugs without an Intermediate Access Port. it is assumed that there are multiple access points to the pipeline. this is difficult because flow is restricted. Depressurizing One Side of Plug(s). The overriding safety concern is that a plug might dislodge from the pipe wall to become a projectile which can rupture a line or vessel. there are two major concerns for plug removal: (a) that the plug may dislodge and be propelled in the pipe. substantial gas may be trapped between the plugs. This method would require access points along the pipeline to locate the plug and remove the liquids to the parallel pipeline.1. A similar procedure can be used with multiple hydrate plugs when liquid heads exist on each side of the plug. ____________________________________________________________________ Table 9. DeepStar A208-1 presents Figure 75 to illustrate the situation to remove two hydrate plugs without an intermediate access point. _____________________________________________________________________ III. and that proposed in DeepStar Report A208-1. Rule of Thumb 20 indicates that multiple hydrate plugs should be assumed to exist in a shut-in line. in Guideline for Prevention and Safe Handling of Hydrates (1994). In this case. Procedure for Depressurization of One Side of a Hydrate Plug. The procedure in Table 9 was slightly modified from that proposed by the Canadian Association of Petroleum Producers . The following depressurization procedure attempts to address both concerns.An alternative to pumping the fluids to the surface is to discharge the fluids into a parallel. and (b) because the plug is porous and permeable. While depressurization is most often used for hydrate it is normally preceded by attempts to place inhibitor adjacent to the blockage. so that the general position of the plug(s) can be located by pressure differential. the procedure to reduce the pressure could be one of the seven discussed in Example 14. Table 9 gives a procedure for depressurizing one side of a hydrate plug. 85 . When there is only the option to depressurize one side of a hydrate plug. Depressurize the line by removing the fluids at a slow rate though access ports on each side of the plugs.

Suggested Procedure to Remove Multiple Hydrate Plums Pump rl (From Deepstar A-208-1.1995) r-l Pump Depressurize at Slow Rate Hydrate Equilibrium _______________________ _______ ______________________ Pressure ___ ____--. _---.Fipure 75 . Mamtam Pressure Slightly Below Hydrate Equilibrium Pressure (For Controlled Dissociation . _--__-___--__ _ _ _ _.

Do not reduce the pressure below that required to reduce the hydrate equilibrium temperature below the ice point.D. frequently a non-ideal depressurization must be achieved. there was not an option of using an inhibitor because pipeline topology prevented inhibitor contact with the plug. 6. pressure equalization may be as slow as 3 psi/hour if substantial liquid flows through the plug. While the above method represents an ideal depressurization from only one side. In January 1996 Statoil (Gjertsen et al. ____________________________________________________________________ Case Study 15. Plug permeability and porosity permits pressure communication to determine gas volumes on each side. If hydrates are dissociating (but remain in the line) the pressure will slowly rise to a level equal to the hydrate equilibrium pressure at the ocean bottom temperature. 4.g. 3. 1997) depressured a hydrate plug in a North Sea line which was alternatively used as a black oil producer and a gas injector to maintain reservoir pressure. the pressure should be reduced slightly (e. should be consulted for system start-up.b. 5. and the gas to oil ratio was usually 100-360 scf/ft 3. Maintaining a low ∆P across hydrate plugs will reduce the threat of a projectile by providing both a low driving force and a downstream gas cushion (See Example 15) for any dislodged plug.6 mile pipeline.2. Since there were no connections at the well the plug had to be depressurized 86 .. While the hydrate plugs are porous. 100 psia). Reduce the pressure in stages to a level slightly below the equilibrium pressure.B. with a very low gas to oil ratio. If hydrates have dissociated. Before the hydrate dissociation pressure is reached.2. the line pressure will remain below the hydrate equilibrium pressure. via the access port valves. After each of several pressure reductions wait for the pressure to be equalized across the plug. The line and plug location method is in Case Study 12 in Section III. pausing for equilibration at each stage. It should be noted that liquid permeability through a hydrate plug is about a factor of 1000 lower than that of gas. as indicated in the Statoil Gullfaks case. If the pressure is reduced too substantially. In addition a low ∆P across the plug minimizes JouleThomson cooling at the plug discharge end.000 ft3/day and 16. Since the plug was about mid-way along the 1. an ice plug will result which may be difficult to dissociate. The oil and water production rates were 18. When the plug completely dissociates there will be no ∆P across the section which had contained the plug and Section III. as in the following case study for a plug which had low liquid permeability. Line Depressured from One Side for Hydrate Plug Removal.242 ft3/day respectively. a fairly low value.

from the platform side only. By considering the hydrate formation curve it was determined that the plug equilibrium pressure was 261 psia but that ice would form when the pressure was below 115 psia. Figure 76 shows the depressurization of the line, with the upstream pressure, the platform pressure, and the pressure drop. During dissociation the pressure was decreased in steps, and a slow bleed through was observed from 0-73 hours, from 7390, 95-105 hours, and from 105 through 120 hours. During the time prior to 120 hours, the pressure was above the hydrate equilibrium pressure, and while the upstream pressure decreased steadily, it never decreased to the downstream pressure, indicating that the plug was not very permeable to black oil. A second mechanism was that the light oil ends may have been flashing to maintain a constant pressure upstream. However the increase in downstream pressure occurred much more rapidly as the downstream pressure was lowered, indicating that the plug was porous, even to the black oil. After about 120 hours the line pressure was maintained between 145 -261 psia downstream of the plug. The plug dissociated about 50-60 hours after the downstream pressure had been reduced sufficiently for melting by heat influx from the ocean. This was indicated by a sudden upstream pressure decrease from 1890 psig to 1160 psig, while the downstream pressure increased from 218 psig to 1015 psig during the same period. The pressure was decreased to 145 psig and kept there for over 30 hours to melt the remainder of the hydrates. Restart of the well (see Case Study 18 Section III.D) was accomplished two weeks after the original plug developed. This case is another indication of the long times required to remediate a hydrate plug. ____________________________________________________________________ Case Studies C.25, C.26, and C.27 in Appendix C are an overview of DeepStar Wyoming field studies of hydrate formation and dissociation from one side of the plug. These studies have the best instrumentation of any hydrate studies to date, and provide several exceptions to the concepts in this portion of the handbook. For example, in two of three cases, relatively impermeable plugs were formed, one of which withstood a ∆P of 475 psi and was propelled down the pipeline at a velocity of 270 ft/s. In each DeepStar field trial, depressurization was done gradually in stages from one side of a hydrate plug with prior testing to ensure that an absorbing gas “cushion” existed downstream. Where the hydrate plug existed upstream of an above-ground bend, angle, or valve, the test was aborted and the plug was depressured from both sides due to safety reasons. In depressuring one side of a hydrate plug, it is instructive to simulate the worst-case as a dislodged, frictionless, piston projectile in a pipeline, as in Example 15.

87

Figure 76 - Pressure Change During Depressurization
(From Gjertsen et al, 1997)

3000
Subsea Pressure

2500

Pressure (psig)

2000
Topside Pressure

1500

1000

500

Pressure Difference

0 0 50 100 Time (hours) 150 200 250

____________________________________________________________________ Example 15. Simulation of Hydrate Projectile Upon Depressuring One Side of Plug. Xiao and Shoup of Amoco (1996 a,b,c, 1997) performed a series of simulations of a hydrate projectile in preparation for depressurization from one side of a hydrate plug in a Kerr-McGee, Wyoming 4 inch line. The plug was conservatively modeled as a frictionless piston. Using OLGA® the steady state flow in the line was modeled prior to blockage formation. The model included pipeline topography to obtain steady state liquid volumes trapped at low points in the pipeline. The total mass flow was 92 BOPD and 4.166 MMscf/d. Figure 77 shows pipeline topography and the liquid holdup. At a ground temperature of 34oF, the pipeline was simulated as shut-in for 8 hours, resulting in a simulated plug formation. Hydrate plugs were initially situated at 7,550 ft. from the inlet of a 17,000 ft. pipeline, with upstream pressures of 1150 psig and 575 psig and a constant initial downstream pressure of 50 psig. Transient velocities of two plugs were simulated after formation: (a) a 20 lbm plug which was 5 ft. long, and (b) a 137 lbm plug which was 30 ft. long. Velocity profiles were obtained for each plug, propelled by the initial pressure differentials of 1100 psi and 525 psi., against an initial pressure of 50 psig with a closed valve at the line end.. For an upstream pressures of 1150 psig, the plugs reached a peak velocity 740 ft/s (smaller plug) and 450 ft/s (larger plug). For an upstream pressure of 575 psig, the plugs reached a peak velocity of 550 ft/s (smaller plug) and 340 ft/s (larger plug). The inertial effects of the gas caused rapid acceleration and the final position of the larger plug (700 ft. and 1,700 ft. from the pipe discharge at initial upstream pressures of 1150 psig and 575 psig respectively) was governed by a pressure balance, caused by expansion of the upstream gas and compression of the downstream gas. The simulation indicated that liquid condensate present in the line had very little effect on the plug maximum velocity when condensate was injected far away from the plug initial position. Figure 78 shows the plug velocity as a function of pipe position for the case of 1150 psig upstream pressure with a 137 lbm plug. Plug simulation results were used to plan and execute field plug dissociation tests. The calculated plug velocity was an acceptable match with measured plug velocities in the field with a gamma-ray detector. It should be noted that modeling the plug as a frictionless piston provides conservative results. The modeled plug will be slowed by any friction between plug and the pipe, as well as by blow-by of gas at the wall and through the porous plug. ____________________________________________________________________

88

Figure 77 - Topography and Steady-State Holdup Profile
(From Xiao and Shoup, 1996)

5360 Pipeline 5340 5320 Station Elevation (ft) Holdup

0.14

0.12

0.1

5300 5280 5260 5240
0.04

0.06

5220
0.02

5200 5180 0 2000 4000 6000 8000 10000 12000 14000 16000 Pipeline Distance (ft)
0

18000

Holdup

0.08

Figure 78 - Plug Velocity vs. Plug Location
(From Xiao and Shoup, 1996)
500

4%

Upstream pressure=1 150 psig Downstream pressure = 50 psig 137 Ibm plug

4Oc

350

8 .s H 3 3 0

30a

250

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loo

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0 10500 11500 12500 13500 14500 15500 16500

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a. Plug Dissociation by Heating in a Well. A hydrate plug was experienced in a well feeding a jackup platform in the Norwegian sector in mid-May 1997. Nevertheless standard practice is to inject inhibitor from both the platform and the well side of a plug.III. in an attempt to get the inhibitor next to a plug. However.2. The reader is also referred to Section III. When the ends of a hydrate plug cannot be located. Rule of Thumb 21.3.2. Both ends of a hydrate plug can seal the high pressure resulting from hydrate dissociation with heating. heating may be one of the primary options.a) a substantial gas volume between the plug and injection points (platform or wellhead) hinders contact. Sometimes the increased density of heavy brines can provide a driving force to the hydrate plug face. “Filling the Line/Well with an Inhibitor or Mechanical/Optical Device. Because flowlines have large variations in elevation it is unlikely that an inhibitor will reach a plug without flow. heating is not recommended for subsea dissociation. initially caused by pressurization of the well with water.1. Thermal Methods of Plug Removal. Similarly in a plugged well where the upper plug end is available. causing glycol to be used more than methanol. it is difficult to get an inhibitor such as methanol or ethylene glycol next to the plug without an access port in the plug proximity. as indicated in the below case studies. as discussed on page 68. Density differences act as a driving force to get inhibitor to the face of the plug. Chemical Methods of Plug Removal. While plugs have been proved to be very porous and permeable. particularly in gas systems (see Section III. particularly when the line cannot be depressured to encourage gas flow through the plug.B. Because the limits of a hydrate plug cannot be easily located in a subsea environment. heating is a viable option for topside hydrate plugs on a platform where a thermocamera can be used to determine the plug limits (and where the possibility of multiple plugs has been eliminated). inhibitors must displace other line fluids through density differences to reach plugs which are close to the platform. Without flow.” III. Such a problem is indicated in Case Study 4 of Section I. Heating a plug in a well can be accomplished using a heated wireline broach.C.C. A hydrate plug. When the pipeline is completely blocked. heating is very dangerous because the pressure rises exponentially with temperature.C. _____________________________________________________________________ Case Study 16. formed 89 . Methanol or glycol injection is normally attempted first in a line. and the line can burst as a result. similar to tool the shown in Figure 56.

000 and 29. MEG was re-injected into the well until the pressure rose to 4930 psia. Field personnel first attempted to decrease the pressure in steps to just above the hydrate equilibrium pressure and unsuccessful attempts were made to push MEG through the hydrate plug.C. usually at a platform or floating workover vessel. Even for partial plugs.4. if it is not handled properly. Coiled tubing is 1/2 to 3-1/2” OD tubing of a maximum length between 15. The bend radius at the base of the platform riser presents a limit to coiled tubing penetration. (Sas-Jaworsky et al. because compression usually compounds a plug problem. The plug temperature was approximately 48oF. 90 .. The pressure recovered to 100 psia as an indication that hydrates were dissociating upon pressure reduction. If a number of hydrate particles are present in the line. There were at least six similar pressure reduction and recovery confirmations that hydrates were dissociating in the well. the only way to get gas into the well was by hydrate dissociation via MEG. Mechanical Methods of Plug Removal. so that depressurization had to be used. When the pressure dropped to 4280 psia. This is a particularly precarious condition which can result in a well blow out.below the downhole safety valve in the well. _____________________________________________________________________ III. A total of 0. It was concluded the plug had very low permeability and dissociated very slowly. Five hours after maintaining the pressure at 15 psia. Coiled tubing is the final option for hydrate removal. Questions remained concerning why the plug did not respond to MEG injection. With a higher pressure atop the plug. with a minimum radius of 6-10 ft. The next action was to inject MEG into the well leaving only a small gas volume at the top of the well. the hydrate dissociation was complete and the pressure atop the well rose to 160 psia.. Pigs are not recommended to remove a hydrate plug. pigging could result in a more severe plug.000 ft. hydrate formation at low lying points of the flowline may cause the pig to become stuck. It was determined the keep the pressure at 15 psia on top of the well to provide constant hydrate melting. The tubing is put into the pipeline through a lubricator. The entire hydrate plug melted 12 days after the initial formation. above the plug) maintained pressure above the plug. 1993). each time pressure increases exponentially approached an asymptote of 100 psia. in an effort to get an inhibitor such as glycol to the face of the plug. This concluded the period of “getting to know the plug. indicating that a very small amount of hydrates had dissociated.14 gallons of MEG were re-injected.” At that point the pressure was reduced atop the well to 15 psia and shut-in so that only the additional static head (394 ft.

Coiled tubing must have gas flowby capability in the drive mechanism at the tubing front.D. At that condition. It is not clear that the line 91 .a) illustrates a hydrate plug formation due to an unexpected shut-in when methanol could not be injected. 1.2. Penetration distance is a function of tubing size and pipeline diameter as shown in Table 10.000 . 2. In other case histories coiled tubing has been used successfully. 1997).60 ft. For hydrate applications. On shut-in the line temperature cools very rapidly to that of the ocean floor (40oF for depth greater than 2000 ft. A tractor can be used to pull the coiled tubing through the flowline from the platform side (Figure 80) in lines larger than 4 inch ID at a speed of 5400 ft/hr with penetration distances to 15. This will prevent either pushing the tubing from the plug face or line over-pressure.0 4 or 6 4 or 6 3.5. three new types of coiled tubing are listed from the DeepStar A208-1 report by Mentor Subsea (Davalath. multiple hydrate plugs can form. Case Study 11 (Section III. Table 10. The daily cost of coiled tubing in 1997 is $1 million/d to rent the rig. and (b) depressure the pipeline as soon as possible.2.000 . Coiled tubing can get hydraulic drilling equipment to the plug (Figure 79). gas must be produced from the tubing. Demonstration has yet to be done. For example with the pigdriven coiled tubing shown in Figure 79.B.but a preferred minimum radius of 20 .000 ft. Coiled tubing technology is being developed.75 . 1995) Tubing Size Flowline Size Penetration inch inch ft.8. Penetration Distance of Coiled Tubing (DeepStar A208.000 See Case Study 11 (Section III. 1995): 1. Avoiding Hydrates on Flowline Shut-in or Start-up Shut-in and start-up are primary times when hydrates form.a) for a successful example of hydrate plug removal with coiled tubing and glycol jetting. two actions are recommended: (a) inject a large amount of inhibitor such as methanol or ethylene glycol. Testing is underway in Deepstar Project 3202. 3. The tubing walls are porous to allow air/gas to lubricate the tubing travel for further penetration. Coiled tubing is expensive.2.000 6. A promising coiled tubing being developed is composite coiled tubing.B. requiring special rigs.5 1. III. For a planned shutin. For example coiled tubing was recently used to dissociate a plug at Statoil’s Statfjord field (Urdahl. With the use of coiled tubing it is important to remember that as much as 170 scf of gas evolves from each ft3 of dissociated hydrate.) so that the system is almost always in the hydrate region if the line is not depressured.

Flow /Wiper w/ Integrutirlg Sub Seals Reversing Disks \\ II’ -Drlll Motet- Stationary Rotating Flow Nozzles Cutter Grater Blades Type Cutting Plate .FiQure 79 - Drillin Head for Solids Removal (From Deepstar A-208-1. 1995) /Coiled Tubing SLip Actuating Insulation Nut sups.

(Fluid 1995) Driven Version) API Connection Tractor Section Nornd Force Tractor FOrce \ Flow TrKtion for Force .Figure 80 - Coiled (From Tubing Deepstar Tractor A208-1.

where sufficient water accumulated to form multiple hydrate plugs. dislodged from the line and was propelled by the high-pressure gas trapped inside the line. long. but the plug formation was removed via coiled tubing with glycol jetting. The following study is from DeepStar Report A208-1 (Mentor Subsea. Then the valve at the header side was vented. and when the plug had melted the line was maintained at atmospheric pressure for over one day to eliminate the light components which might form hydrates. 1995.d). and the gas trap between the plugs was estimated to be 160 ft. In this case there were at least two low spots in the line. all parts of the system are particularly susceptible to hydrates.was depressured immediately after shut-in. but it was not depressured for six days. as described in Case Study 15 (Section III. hydrate plugging was prevented by: (1) injecting methanol or glycol during each start-up. page 31). The normal flow in the pipeline was gas with 2% H2S and condensate in the amount of 50 bbl/MMscf. _____________________________________________________________________ On start-up before reaching steady state. The fast-moving hydrate plug blew a hole through a tee near the header within half a second after the valve was opened at the header. The impact of the plug and associated debris caused one fatality and one injury to personnel operating the valve. Pipeline Start-up after Hydrate Formation. Due to a problem at a gas plant a 6 inch 600 ANSI flowline was shut-in at 1000 psi. (2) for planned shutdowns. After several precautions. Multiple Plug Formation after Pressurized Shut-in. while the system is heating with warm fluids from the reservoir. To remove the blockage the wellhead side of the line was depressured by venting over a 15-20 minute period. A typical start-up procedure involves injecting large amounts of inhibitor and using diesel fuel. Follow-up investigations and math modeling showed that 230 . _____________________________________________________________________ Case Study 18. of high pressure gas in a 6 inch line would be sufficient to cause the damage that occurred. During this operation. one of the hydrate plugs partially melted.820 ft. In 1996 a Statoil black oil pipeline plug occurred in the Norwegian sector of the North Sea.C. During this time small hydrate particles which have formed may be compacted by flow (or by pigs) to form a plug.1. the pipeline was depressured within the first 24 hours following shut in. the pipeline was depressured from one side of the plug. 92 . a hydrate inhibitor was injected prior to stopping flow followed by depressurization. Case Study 17 also illustrates the value of line depressuring on shut-in. and (3) for unplanned shutdowns. The plug length was estimated to be 33 ft. _____________________________________________________________________ Case Study 17. In subsequent operations.

7. Inhibitor injection and de-pressuring techniques are available for system shut-in and start-up . Joule-Thomson cooling through the plug. from both safety and technical viewpoints. Recommendations and Future Development Areas III. service lines. including radial depressurization. etc. Hydrate plugs are always dissociated. 1. Hourly changes are ineffectual. Heating is not recommended for hydrate plugs without a means for relieving the excess gas pressure when hydrates dissociate. 93 . 3. 11. the hydrate plug will rapidly form an ice plug which may be more difficult to dissociate. Coiled tubing represents the primary mechanical means for dissociating hydrates. knowledge of the precise location and length of a plug would be a vital help in dissociation. 9. Liquid heads removal is a current challenges to flow assurance. _____________________________________________________________________ III. depressurization from one side of a plug has been safely done. more compacted hydrate. but this is seldom effective due to the necessity to get the inhibitor at the face of the plug. 12.1. in an amount which indicated that the pipeline was nearly empty of liquid after the previous depressurization to atmospheric conditions. The lessons of hydrate plug remediation may be summarized succinctly: 1. methanol was injected in the amount of 530 gallons in the 6 inch ID. 8. 10. This implies access points at both plug ends through dual production lines. E. Usually methanol or glycol is injected into plugged flowlines.6 mile line from the platform.Before start-up. 6. Attempts to “blow the plug out of the line” via a high upstream pressure always results in a larger. However. Multiple hydrate plugs should always be assumed and treated as a safety hazard. In some cases. Subsequently the well and the pipeline were put into production without any hydrate problems.E. and the fact that depressurization may cause the plug downstream temperature to decrease below the hydrate equilibrium temperature. but the time scale is usually days to weeks. 5. 2. Some plugs are permeable to gas. In a deepwater line a liquid head on a hydrate plug may be sufficient to prevent depressurization. This concept controls many aspects of hydrate dissociation. 13. The pipeline was then pressurized with diesel from the platform to the sub-sea valve. Many hydrate plugs are porous and transmit pressure easily while acting to obstruct flow.two times of jeopardy in formation of hydrate plugs. A further injection of diesel corresponding to two pipeline volumes was pumped into the pipeline and well. Depressurization from both sides of hydrate plugs is the preferred method of removal. 4. but less so to condensate or black oil. Methods are not well-defined for locating hydrate plugs and determining their length. Deliberate changes and Patience are required. Recommendation Summary for Hydrate Remediation. If the pressure is decreased too much.

1995) based upon case studies represented in the body of this report and in Appendix C. A mathematical model should be refined and verified to include radial dissociation of a hydrate plug.). Recommendations for future work to aid remediation supplements those from DeepStar Report A208-1 (Mentor Subsea.2. 4. and (d) blind flanges and valves at manifold. and reducing line low spots. 3. Investigate the use of various access points along a flowline to allow (1) locating the plug. Consider providing pressure and temperature monitors a various points along the pipeline. 6. 2. 5.E. (c) composite coiled tubing to reduce drag. Eliminate un-necessary restrictions and valves in the system and provide for heating or methanol injection where Joule-Thomson cooling is a problem. (b) dual production lines. Provide for hydrate prevention at these instrument points. and (3) depressuring from each side of the plug. 94 . Consider using a long radius riser (from 20-80 ft. predictive model for hydrate dissociation is not currently available. Recommendations for Future Work. (2) removal of liquid head at each side of a plug.III. eliminating bends and “S” configurations where water might accumulate. Consider installing a heater on the platform to prevent hydrate formation in the choke and/or separator. such s (a) locomotive-type device for pulling coiled tubing. Such options include (a) multiple access points along a pipeline. A proven. (c) wellhead access through service lines with check valves removed or bypassed. Investigate the use of various coiled tubing techniques to enter a long distance subsea line. (b) pigs mounted outside of coiled tubing to assist penetration. 1.

1. The Economics of Hydrate Prevention The Guidelines for Hydrate Prevention Design (Section II. IV. the policy is invariably. prevention.B. for example the cost of a heating system installed around a instrument gas control valve. 7. using such tools as the Consumer Price Index.H) are certain to involve economics which relate to individual cases. Chemical Injection Economics. These economics provided the initial motivation to investigate hydrate prevention via other means. “Why should hydrates be of concern?” the ultimate answer relates to economics.D all imply a direct relationship between safety and cost.the previous three major sections of the handbook. the most-used hydrate inhibitor (Houston. Economics Economics provide the motivation for all engineering action. 1997). In the United States in 1996 the oil and gas production industry used an estimated 400 million pounds of methanol. The Economics of Hydrate Safety While insurance actuaries can set a price on life and limb.” Consideration of the Section I five case studies.” or “If we cannot operate safely.A. a time stamp enables the reader to update the economics. IV.IV. In this section we are concerned with the economics of two principle prevention means: (1) chemical injection and (2) heat management. and remediation . p. With expanding deepwater work the use of methanol is expected to grow 50 .B. safety or the environment) relate directly to economics because such concerns can prevent process operations. plus Case Study 17 in Section III. When we ask. The present section is aimed at providing economics in terms of hydrate safety. we cannot operate. Even concerns of higher value (e.” While safety is related to costs. Lysne (1995.75% over the next five years. Frequently such costs can be minimized in the original process design. In every example provided. IV. because blowout and severe process damage occurred in all cases.g.8) lists three such incidences in which hydrate projectiles erupted from pipelines at elbows and caused the loss of three lives and over $7 million in capital costs. 95 . Shell’s methanol usage in deepwater is forecast at 50 million pounds per year. without expensive retrofits to correct deficiencies. “Safety at all costs. usually an ethical concern for worker well-being dictates safe operation. and companies take welldeserved pride in the number of “accident-free days.

Since methanol recovery is not economical. Methanol had a delivered cost to an offshore Gulf of Mexico platform of $2. and use of steel or stainless steel subsea chemical transmission lines.IV. 1994) shows methanol recovery to be very expensive in Table 3 of Case Study 7 in Section II.D. For example. that both tables are based solely upon methanol only in the free water phase. with the main features: • • • • one surface pump per chemical on the host platform one subsea transmission line per chemical subsea distribution using remotely adjustable. methanol injection is normally considered as an operating cost. It should be noted however. Table 12 gives capital costs for methanol injection systems in 1 well and 20 wells for the Jolliet and Hercules reservoirs. The Deepstar Study CTR 221-1 (Paragon Engineering. pressure compensated flow control valves packaged into control pods.D.2 and II.3.D. The study recommends that there should be one transmission line per chemical and a subsea distribution system.B.a.00 per gallon during the 1996-7 winter.27/lbm during the 1997 summer. making the economics much more favorable. 96 .1. The amounts of chemical injection should be based upon the methods of Section II. 60 mile lines. Such costs fluctuate significantly and are somewhat seasonal. For methanol recovery late in the life of a field. Economics of Methanol and Mono-ethylene Glycol. In that work chemical injection costs (including MeOH) were reported for two Gulf of Mexico cases: (a) the Jolliet reservoir which is naturally gas lifted.G. For ethylene glycol (MEG) a low vapor pressure results in a smaller recovery column.a.1. methanol is significantly dissolved in the vapor and liquid hydrocarbon phases. are provided in Table 11.72/gallon) and ethylene glycol cost were $0. the total installed cost on an existing platform was estimated at $16.11/lbm ($0. Details of annual hydrate chemical costs for 1-well and 20-well cases. recalling the relative advantages and disadvantages of each inhibitor. not just the free water phase (considered in Table 11). As noted in Sections II. typical dockside North Sea methanol costs were $0. frequently methanol losses to the vapor and condensate phases are quite important. and (b) the Hercules reservoir has a heavier crude with low GOR (500 scf/b).7 million ($20 million total installed cost with a new platform) while the annual operating cost is $6 million. One of the most comprehensive documented economic studies of methanol injection was provided by DeepStar I CTR 240 by INTEC Engineering (December 1992).

1 27.6 11.889 0.306 0.157 46. Wells 1 20 Min.964 Jolliet “ “ Jolliet “ “ Hercules “ “ Hercules “ “ 2.2 37.2 0 2.00 Hercules 1 1.8 43.8 27. actuator.540 5.948 36.6 33. and packaging = $6.500 600 43 4.9 34.629 1.00 Hercules 20 2.8 41.700/well.7 0.815 1.400 5.100 1.317 1.263 0 47.400 16.064 Oil bbl/D Gas Mscf/d H2O bbl/D Subcool ∆T( F) o wt% MeOH Cost MeOH gpm k$/yr 35.0 415.026 0. Line ID (in) 0. Statoil provided the below table showing a reduction in condensate price for different methanol concentrations (>30 ppm by wt) in a condensate.20 30.C.0 30.206 0.040 0.367 465 23 2. 97 .1 29.65 60. Methanol loss costs can be substantial when the total fraction of either the vapor or the oil/condensate phase is very large relative to the water phase.3 32.325 1. Transmission Lines (60 miles) Sizing.6 539. Costs and Pumping Skid Costs (From DeepStar I.24 7.700 19.054 15.3 34.2 33. and II.970 911 2.0 Table 12.322 77.Table 11.064 1.9 28.670 3.7 28.3 38.780 Line Cost MM$ 1.051 1.75 54.268 850 2.8 15. CTR 240) Reservoir Jolliet Jolliet No.700 2 17 4 4 124 172 0 666 22 0 4.4 0 14.210 869 376 30 3.D.50 Additional cost of valve.0 37. manifolding.2 30.9 32. Example 7 provides a conservative sample calculation in which 15% of the methanol is lost to the vapor and liquid hydrocarbon.832 0 7.100 1.11 Skid Cost k$ 5.700 22.4 30.412 1.737 1.449 1.821 1. provide a quantitative means of validation of the above Rule-of-Thumb.824 2.03 1. Sections II.79 34. Rule-of-Thumb 22.500 11.7 41.8 31.3 33. life Well yr 1 “ “ 20 “ “ 1 “ “ 20 “ “ 1 5 8 1 5 10 1 5 8 1 5 10 WHP psia 3.948 33.000 12.79 89. Cost of Methanol Usage for Jolliet and Hercules Reservoirs in Gulf of Mexico (from DeepStar I CTR 240) Rsrvr No.325 1.123 2.

B.9 32.9 19. 1997) MeOH conc in Reduction in 1993 Price (comment) C3H8 ppm (wt) 0-30 30-50 50-100 100-200 200-300 >300 0 0-$2/metric ton (MT = 2205 lbm) $2-4/MT (or $0.3 40. o F no hyd 11.2 Max ∆T. Notz (1994) provided one of the best comparisons of operating costs for methanol with kinetic inhibitors in Tables 14 and 15 for a Texaco field in the North Sea.3 0 21.5 28 9.8 KI 1000 lbm active 0 0.128 NA* NA* multi “ “ liquid “ “ gas “ “ 304 287 150 346 295 118 0 17 8.9 0 7.441 0. Notz.9 15 4 72.1.5 8.5 19.25 .$0. Table 14.4 NA* = conditions too severe for kinetic inhibitor (KI) 98 .0 33 2. bbl/d Time in hydrate zone. 0. July 26. Cost Penalties for Methanol in Propane (from Austvik.4 wt% MeOH in H2O 0 16 33 0 20 21 MeOH 1000 lbm 0 20.409 NA* 0.7 31. 1994) Pipeline (in) 16 “ “ 8 “ “ 12 “ “ phase Life yrs of Use 0 7 15 0 7 15 H2O avg.8 33 5. Relative Usage of Methanol and Kinetic Inhibitor in a North Sea Field (P.4 25.b.4 no hyd 17.9 43. hr 0 2.50/ Bbl) $4-6/MT (excludes some crackers) $6-9/MT (excludes most crackers) $9-40/MT (reduced confidence in product) IV. Economics of New Types of Inhibitors.6 30.170 0.Table 13.7 7 10 24.

1997) Chemical Conc/bbl H2O. worse than MeOH).0 $MM Replacing MeOH with KI Whenever Possible KI1.4 9. In one high water production North Sea field. Comparison of Three Types of Inhibitor Costs in the North Sea (M. The incentive for newer kinetic control methods is a substantial capital cost reduction by the elimination of the need for offshore platform equipment.05 0.0 This includes the cost of methanol solvent for the kinetic inhibitor This is the methanol cost in those years when a KI cannot be used because ∆T > 27oF Grainger (1997) compared inhibition costs of methanol. Table 16.4 18. MeOH2 Total MM MM lbm Cost lbm $MM 0.3 5. to capital savings of avoiding regeneration systems) but marginal for retrofits of systems with traditional inhibitors such as monoethylene glycol. 1994) Years When Kinetic Inhibitor is Effective Use Methanol Kinetic Yrs Inhibitor1 MM $MM MM $MM lbm lbm 7-9 6-15 1-4 25.25 0.Table 15. without shipping to the platform.05 0.1 15.5 Line (in) phase 16 8 12 2 multi liquid gas 1 22. (1995) suggested that economics were favorable for new developments (due for example.$7.36 1. and regeneration (Argo and Osborne.7 0. and a small operating cost reduction.7 $6.0 0 17.5 THI 0.9 10.36 1.03 50. BP reckoned the capital costs savings at $50 million for platform costs including methanol injection costs.2 9. and a Threshold Hydrate Inhibitor (THI) which consisted of kinetic inhibitors.wt% Quantity.9 52. lbm Cost/bbl H2O MEG 15 61.03 3. July 26.5 33.9 52. Notz.882 $8-$10 From the above table.8 15.6 7. a corrosion inhibitor. Table 16 represents dock delivery costs.5 .3 0.7 $16-$17 MeOH 15 61.5 15. Comparison of Methanol and Kinetic Inhibitor Cost in North Sea (P.9 4. glycol drying. 1997). August 21. operating cost benefits appear marginal (better than MEG. 99 . Grainger. Bloys et al. glycol. and a solvent.26 Over Entire 15 Year Life of Reservoir Methanol MM lbm 72.

For example. Edwards also estimated the operation of an inhibitor recovery unit at 2 hrs/day operator time and maintenance requires 600-700 hr/year at $85/hr. Rule-of-Thumb 24.B. Economics of Insulation.3 BTU/hr-ft 2-oF is required with a flowline pressure of 4000 psia. and the information contained here should be updated by knowledgeable workers. BP currently operates some Southern North Sea pipeline wet.3 BTU/hr-ft2-oF (from DeepStar Report IIA CTR A601-a. Of the two heat management techniques (insulation methods and pipeline heating) only the insulation state-of-the-art is established sufficiently for economics to be available. respectively. and disposal. bundled flow lines are more cost effective.000/ton.G.000 bbl/d. However. As additional costs. deepwater development is causing the cost of such technology to change rapidly. a savings may be realized on the platform itself. BP would like to use unmanned platforms.000 and 50. IV. Heat Management Economics. 100 . a non-jacketed system costs $1. anti-agglomerant economics should include such factors as emulsion breaking.5 -$2.a.B.4.3 BTU/hr-ft2-oF. recovery. 1995) and costs are typically $50-$300/ft for pipes with diameters between 8 inches and 12 inches. IV. Figures 43 and 44 compare the cost of the three above types of insulation for water depths of 6000 ft over 60 miles at oil production rates of 25. If an average U = 0. thereby saving the capital cost of drying the gas on the platform. In order to achieve a desired heat transfer coefficient of 0. but the inhibitor recovery units on some platforms prevents doing so. Technical details and associated economics are provided in Section II. Typical costs of insulation via bundled lines are $1. The minimum overall coefficient achievable with a non-jacketed system is 0. However.5 million per mile.a.2.2. The economics of anti-agglomerants are much less certain than those stated above for kinetic inhibitors. The above Rule-of-Thumb was given by Edwards (1997). The cost of a fixed leg North Sea platform is $77. In addition to capital cost. No documented costs of anti-agglomerants were found.0 million/mile. Rule-of-Thumb 23.

despite large quantities of methanol injection for hydrate prevention.) The final cost of depressurizing the ARCO pipeline was almost 3 million dollars. “At any instant in the North Sea. A dollar today is worth more than a dollar tomorrow due to inflation. Contracts specify delivery and penalties for non-delivery of hydrocarbon. 2. Todd et al.IV.9 million and a FPSO was available for immediate use. 3. Offshore hydrate remediation techniques are very costly if they are not explicitly included into the initial design. Jack-up Rig. reducing the required time to 6-8 weeks. The estimated cost was $1. (1996) report 66 hydrate blockages occurred in one well and production line during winter of 19951996. so that the time value of money is considered. Floating Production and Storage Vessel (FPSO). the question arises about how lost production should be treated .i. 101 . Fields are frequently sold over their lifetime. In this case two solutions were technically available: 1. Austvik of Statoil(1997) indicated the magnitude of the problem by saying. The estimated cost: was $2 million and a delay of approximately eight weeks was needed to locate a suitable rig. production is shut in. From the hydrate group with the largest world-wide remediation experience. Connect a FPSO with a processing plant and flare to the subsea manifold’s fourth flow loop. (The daily cost of coiled tubing was $1 million/d to rent the rig in July.” As one onshore example. 2. Usually deferred production is counted at the end of reservoir life. resulting in production losses of more than $240. The time required for hydrate removal could be twelve weeks. the ARCO Case Study 14 represented a fortunate instance (in April 1996) of having an extra flange available at the manifold for depressurization. but are enormous when considered collectively. as lost or as deferred revenue.e. Other techniques such as the use of coiled tubing were not available at the time. The Economics of Hydrate Remediation When hydrate blockages occur.000. Production losses due to hydrates are site-specific. For example. Flare exiting gas via the rig’s flare stack.C. there is probably a hydrate blockage which requires remediation. 1997. There is consensus that shut-in production should be counted as lost revenue for reasons including the following: 1. When coupled with the fact that all hydrate-blocked lines and wells have to be re-commissioned. and deferred cost means lost revenue during the ownership of a field. Tow a jack-up rig to the site and attach a high pressure riser to the manifold’s subsea tree.

implying that no penalties should be incurred because there was no human error. Nondelivery contract pressures may be eased by considering hydrates as a “Force Majeure” as done in ARCO Case Study 14. 102 . However. the loss of production usually causes time to be the deciding resource during remediation. Typical non-delivery penalty costs are $50.000/day after tax on a gas production unit of 125MM scf/d. During remediation periods.without production losses. the borrowing capacity is typically limited to 5 times the daily capacity. so that gas supplies are purchased from the spot market. Even with such high costs. gas supply is usually met via substitution.

forms when natural gases or oils contain molecules larger than ethane but smaller than pentane. propane. Some initial physical properties. Structure II (sII).1. normal butane. a body-centered cubic structure forms with small natural gas molecules found in situ in deep oceans. in sH a layer of linked 512 cavities provide connections. isobutane. Two recent hydrate conference summaries (Sloan et al.. and sH) shown in Figure A. non-flowing nature. nitrogen. Hydrates normally form in one of three repeating crystal structures shown in Figure A.1.1.Appendix A. Structure I (sI). Since information on structure H is in the fledgling stages. Table A.5 Å) and ethylcyclohexane (9Å) can form hydrates. Hydrate Crystal Structures. carbon dioxide. and since it may not occur commonly in natural systems. most of this appendix concerns sI and sII. sII represents hydrates which commonly occur in hydrocarbon production and processing conditions. Gas clathrates are crystalline compounds which occur when water forms a cage-like structure around smaller guest molecules. Gas Hydrate Structures. A. Hydrate discovery is credited in 1810 to Sir Humphrey Davy. Hydrates concentrate hydrocarbons: 1 ft3 of hydrates may contain 180 scf of gas. The newest hydrate structure H (sH) named for its hexagonal framework. ethane. The crystals structures are given with reference to the water skeleton. to which the reader may wish to turn for a more complete explanation. 1994. Due to their crystalline. sII. and models have been determined for sH and one instance of in situ sH in the Gulf of Mexico has been found. 103 . when water combines with various salts. linking the faces of 512 cavities results in sII. Properties. Gas hydrates of current interest are composed of water and the following eight molecules: methane. composed of a basic "building block" cavity which has twelve faces with five sides per face. Hydrate formation is a possibility where water exists in the vicinity of such molecules at temperatures above and below 32oF. the time they first were observed blocking pipelines. and hydrogen sulfide. By linking the vertices of 512 cavities one obtains sI. Chapters 2 and 3). a diamond lattice within a cubic framework. has cavities large enough to contain molecules the size of common components of naphtha and gasoline.1 provides a hydrate structure summary for the three hydrate unit crystals (sI. hydrates first became of interest to the hydrocarbon industry in 1934. Yet other apolar components between the sizes of argon (3. Monfort 1996) also provide research and applied perspectives of the hydrate community. given the abbreviation 512. as well as in many cases of gas seeps from faults in ocean environments. a careful distinction should be made between these non-stoichiometric clathrate hydrates of gas and other stoichiometric hydrate compounds which occur for example. While they are more commonly called hydrates. and How They Form The following discussion is excerpted from the monograph by Sloan (1998. phase equilibrium data.

Fimre A-l . 1998) Structure Structure IJ I 136 Water Molecules 46 Waler Molecules Structure H 34 Water Molecules .Three Hydrate Unit Crystals and Constituent Cavities (From Sloan.

33 3. a diamond lattice within a cubic framework.1 depicts the five cavities of sI. the lines represent hydrogen bonds with which one chemically-bonded hydrogen connects to an oxygen on a neighbor water molecule.91 4.06 5. Number of oxygens at the periphery of each cavity. Many sH mechanical properties of have not been measured.a.4 14. Variation in distance of oxygen atoms from center of cage.2. Finally structure H hydrates must have a small occupant (like methane. Figure A. Similar formulas for sII and sH are (16[512]•8[51264]•136H2O) and (3[512]•2[435663]•1[51268]•34H2O) respectively. pentagonal. or carbon dioxide) for the 512 and 435663 cages but the molecules in the 51268 cage can be as large as 0. 51264 in sII. nitrogen.713 Not Available 20 20 36 34 1.2. sII.9 Å (e.1 Hydrate Crystal Structure Cavity Description Number of Cavities/Unit Cell Average Cavity Radius.73 5.5 1. This conclusion is true to a first approximation as shown in Table A. Structure I.g. and hexagonal faces (435663). forms when natural gases or oils contain molecules larger than ethane. Å Variation in Radius1. Estimates of structure H cavities from geometric models Inside each cavity resides a maximum of one of the small guest molecules. In addition sH has a cavity with square. 104 .1 a oxygen atom is located at the vertex of each angle in the cavities. a body-centered cubic structure. 3.95 4. four.2.1 Geometry of Cages in Three Hydrate Crystal Structures in Figure A. or eight hexagonal faces: (denoted as 51262 in sI. A. As may be calculated via Table A. and sH.4 20 24 46 II Small Large 512 51264 16 8 3. typified by the eight guests associated with 46 water molecules in sI (2[512]•6[51262]•46H2O). ethylcyclohexane). consequently sI hydrates are found in situ in deep oceans with biogenic gases containing mostly methane. forms with natural gases containing molecules smaller than propane. In Figure A. and hydrogen sulfide. Structure II.Spaces between the 512 cavities are larger cavities which contain twelve pentagonal faces and either two. Mechanical Properties of Hydrates. Table A. Properties Derive from Crystal Structures. A. or 51268 in sH). all three known hydrates have the amazing property of being approximately 85% (mol) water and 15% gas. % Coordination Number2 Number of Waters/Unit Cell I Small Large 512 51262 2 6 3. with the exception of thermal conductivity and thermal expansivity. if all the cages of each structure are filled. The fact that the water content is so high suggests that the mechanical properties of the three hydrate structures should be similar to those of ice. 2. sII represents hydrates from most natural gas systems gases. Structure H has not been commonly determined in natural gas systems to date.1. carbon dioxide. indicating two guests in the 512 and 6 guests in the 51262 cavities of sI.91 4.73 20 28 136 H Small Medium Large 512 435663 51268 3 2 1 3 3 3.

95 77x10-6 14est 3. For example.4est ~0. Molecule sizes which are close to the hatched lines separating cavity sizes exhibit the most non-stoichiometry.Table A. H2O molecules Lattice Parameters at 273K Dielectric Constant at 273 K Far infrared spectrum H2O Diffusion Correl Time. the concept of "a ball fitting within a ball" is a key to understanding many hydrate properties. Other molecules such as CH4 and N2 are small enough to enter both cavities (512+51262 in sI or 512+51264 in sII) when hydrate is formed of single components.23 Pm3n Fd3m 46 136 12. or i-C4H10 fits the 51264 of sII). 4.49±. 220 58.6 2. they will cause sII to form.88 56x10-6 12 3.9 is necessary for stability of a simple hydrate.5Å molecules will not stabilize sI and above 7. Below 3. Figure A.g.b.33 NA NA NA 52x10-6 14est 3. methane will distribute in both cavities of sII and ethane will enter only the 51264 cavity of sII. Guest: Cavity Size Ratio: a Basis for Property Understanding. The sizes of stabilizing guest molecules range between 3. C2H6 fits in the 51262 of sI.9 1. given by the 105 .36 94 Peak at 229 cm-1.51±.2est ~0. 2.5 Å molecules will not stabilize sII.8 3.1 9.5 0.2 may be used to illustrate five points regarding the guest:cavity size ratio for hydrates formed of a single guest component in sI or sII. Table A.6 0. (µsec) H2O Diffusion Activ. due to their inability to fit securely within the cavity. Therm. The hydrate cavity occupied is a function of the size ratio of the guest molecule within the cavity.3 shows the size ratio of several common gas molecules within each of the four cavities of sI and sII.33 5. because propane and i-butane are present in many natural gases.5 Å.3 0. Some molecules are too large to fit the smaller cavities of each structure (e.2 Comparison of Properties of Ice and sI and sII Hydrates Property Spectroscopic Crystallographic Unit Cell Space Group No.02 8. Note that a size ratio (guest molecule: cavity) of approximately 0. 1. To a first approximation. The largest molecules of a gas mixture usually determines the structure formed. 3. Energy(kJ/m) Mechanical Property Isothermal Young’s modulus at 268 K (109 Pa) Poisson’s Ratio Bulk Modulus (272 K) Shear Modulus (272 K) VelocityRatio(Comp/Shear):272K Thermodynamic Property Linear.02 A. In such cases.4 1.2.8 2. Expn: 200K (K-1) AdiabBulkCompress:273K(10-11Pa) Speed Long Sound:273K(km/sec) Transport Thermal Condctivity:263K(W/m-K) Ice Structure I Structure II P63/mmc 4 a =4.33 8. 5.3 ~58 58 Peak at 229 cm-1 with others 240 25 50 50 8.52 c =7.0 17.5 and 7.

1998) .Relative Sizes of Hydrate Guest and Host Cavities (From Sloan.Figure A-2 .

1 F indicates the cavity occupied by the simple hydrate former As seen in Table A. As the temperature is reduced (or as the pressure is increased) hydrates form from gas and liquid water at the line.2. because CH4 lends slightly higher stability to the 51262 cavity in sI than the 51264 cavity in sII.769 0. with a preference for sI. as any amount of propane is added to methane the structure changes (sI sII) to a hydrate with much wider stability conditions.855F 0.898F 1. so that to the left of the line the hydrate will exist with the excess phase (gas).02 1.5 7.07 Molecule N2 CH4 H2S CO2 C2H6 C3H8 i-C4H10 n-C4H10 Cavity Type=> Guest Dmtr (Å) 4.28 6.3 Ratios of Guest: Cavity Diameters for Natural Gas Hydrate Formers (Molecular Diameter) / (Cavity Diameter) Structure I Structure II 512 51262 512 51264 0.3.3 also illustrates the dramatic effect of gas composition on hydrate stability. so three phases (liquid water + hydrates + gas) will be in equilibrium. On the other hand. All of the conditions given in Figure A. When the ratio is significantly less than 0.21 0.3 are for temperatures above 32oF and pressures along the lines vary exponentially with temperature.07 1.700 0. so that gases of pure propane form sII hydrates from free water.3.00 1.655 0. hydrate stability at the three-phase (LW-H-V) condition is always much more sensitive to temperature than to pressure.c.23 1. when as little as 1% propane is in the gas phase.817F 0. Note that a 50% decrease in pressure is needed to form sII hydrates. Phase Equilibrium Properties.25 1.744F 0.39 0. A.939F 1.58 5.08 1. ethane as a single gas forms in the 51262 cavity in sI.29 1.12 5. the molecule will not fit within the cavity and the structure will not form.834F 0.826 0.804 0.976 F 1.27 1.superscript “F”.616F 0. Table A.10 1.782F 0. because ethane is too large for the small 512 cavities in either structure and too small to give much stability to the large 51264 cavity in sII.36 4. for methane+propane mixtures.3 pressure is plotted against temperature with gas composition as a parameter.687 0. In Figure A.9 the molecule cannot lend significant stability to the cavity. Put explicitly.943F 0.41 0. With further reduction of temperature (or increase in pressure) the fluid phase which is not in excess (water in pipeline environments) will be exhausted. Similarly propane is too large to fit any cavity except the 51264 cavity in sII. a gas of that composition will exist in equilibrium with liquid water. Æ 106 . methane's size is sufficient to lend stability to the 512 cavity in either sI or sII.5 6. At conditions to the right of the line.11 1. Figure A. Consider a gas of any given composition (marked 0 through 100% propane) on a line in Figure A.1 4.912 1.868 0. When the size ratio exceeds unity.

Three-Phase (Lw-H-V) Equilibria of Methane+Propane Mixtures (From Sloan.Figure A-3 . 1998) of .- .

to i-C4H10. and (c) the transport of components to the growing solid-liquid interface. although their guest:cavity size ratios differ (0.3. wherein C3H8 occupies most of the 51264 cavities. All three kinetic components are under study. In a conceptual picture. As one illustration. The answer to the questions.000 BTU/(lbmol gas) is valid for most natural gas hydrates. (b) growth of the solid crystal.976). As a second illustration. 1/T) in previous paragraphs.e.500 and 57. We don’t know how hydrates form. but an acceptable model for any has yet to be found. A. enthalpy change) required to dissociate hydrates to a vapor and aqueous liquid.5.943 and 0. Chapter 5). A. For further detailed discussion the reader is referred to Sloan (1998. When natural gases dissolve in water there is conclusive evidence that water molecules organize themselves to maximize hydrogen bonding around each apolar molecule.3.200 BTU/(lbmol gas) because they both occupy 51264 cavities. A. The heat of dissociation (∆Hd) may be considered to be the heat (rigorously. With the model. with values given at temperatures just above the ice point.1.Any discussion of hydrate dissociation would be incomplete without indicating that hydrates provide the most industrially useful instance of statistical thermodynamics prediction of phase equilibria. one may predict the threephase pressure or temperature of hydrate formation. The kinetics of hydrate formation are clearly divided into three parts: (a) nucleation of a critical crystal radius. by knowing the gas composition.2. For sI and sII. using the Clausius-Clapeyron relation [∆Hd = -zR d(ln P)/d(1/T)]. but also the cavity occupied within a wide range of component sizes. while CH4 occupies a small number of 51264 and many 512. by the following steps: 1. similar slopes of lines in Figure A. Heat of Dissociation. Figure A. Formation Kinetics Relate to Hydrate Crystal Structures. to a fair engineering approximation (±10%) ∆Hd depends mostly on crystal hydrogen bonds. the kinetics) of hydrate formation are controversial topics at the forefront of current research. but we can make some educated guesses about kinetics. Enthalpies of dissociation may be determined via the univariant slopes of phase equilibrium lines (ln P vs. ∆Hd = 34. "What are hydrates?" and “Under what condition do hydrates form?” in the previous sections is much more certain than answers to "How do hydrates form?". to n-C4H10. The resulting liquid clusters resemble the solid hydrate cavities of 107 .000 BTU/(lbmol gas) over wide ranges of composition.a. Conceptual Picture of Hydrate Growth. The mechanism and rate (i.d.4 shows similar line slopes (and thus ∆Hd values) for binary mixtures of methane when the large guest is changed from C3H8. The van der Waals and Platteeuw model which forms the basis for HYDOFF was formulated after the determination of sI and sII structures shown in Figure A. Since natural gases almost always contain such components.3 show that mixtures of CH4 + C3H8 have a value of ∆Hd = 34. this laboratory proposed that clusters at the water-gas interface may grow to achieve a critical radius as shown schematically in Figure A. simple hydrates of C3H8 or iC4H10 have similar ∆Hd of 55.

4p .Figure A-4 . 47 (OF) 55 67 7 1 0 l- 1 0 ‘- TEMPERATURE (1000/K) . .3$.Three-Phase (Lw-H-V) Equilibria of Methane+ (Propane and Tvo Butanes) (From Sloan. TEMPERATURE . .27 . 1998) .

Labile Clusters Upon dissolu&n of gas in water.Schematic Model of Hydrate Cluster Growth (From Sloan. faces. Primary Nuclealion and Growth When the size of cluster agglomerates nacbes a critical value. 1998) + Gas A.Figure A-5 . . but no gas molecules dissolved in wafer 6.C. D. Initial Condlflon Pressure and temperature in hydrate’ forming region. Agglomeration Labile clusters agglomerate by sharing. thus increasing disorder. growth begins. labile ctusters form immediately. .

After attaining the critical radius [D]. once about 100ºF is passed. These fluid clusters are envisioned to join other clusters as the beginning of the hydrate crystallization process. No satisfactory kinetic model currently exists for formation or dissociation. The cages may either dissipate or grow to hydrate unit cells or agglomerations of unit cells [C]. surface formation. to stable nuclei [D] which can grow to large species. At point [B]. and stable hydrate crystals are dissociated. when the system is heated. The reader should note that the above is a largely unproven hypothesis. no residual structure remains to promote hydrate formation. the cages are termed “labile” . the crystals grow rapidly in a period sometimes called catastrophic growth. The hydrate dissociation models derived from solid moving-boundary differential equations do not account for the porous. thus forming metastable nuclei. whose only justification is to serve as a mental picture for qualitative predictions and future corrections. kinetic characterization of hydrates is very ill-determined. and therefore is only approachable by very approximate models. there are still labile microscopic species in the water that range in size from multiple hydrate unit cells [C] to metastable nuclei [B]. However.2. 3. Once the hydrate dissociation point is reached and passed. Most hydrate nucleation models assume homogeneous nucleation and typically cannot fit more than 80% of the data generated in the laboratory of the modeller. Since these metastable unit cells at [C] are of subcritical size. Figure A. and occlusion nature of hydrates on a macroscopic scale. it is driven to the left in Figure A. Due to the unsatisfactory state of hydrate kinetics knowledge. these species causes a decrease in induction or metastability time of a successive run. through metastable species [B] and [C]. In both kinetics and thermodynamics the hydrate phase is almost never measured. One has only to turn to the recent review of hydrate kinetics by Englezos (1995) or to the author’s monograph (1998) to determine the following unsettling facts which act as a state-of-the-art summary: • Hydrate nucleation is both heterogeneous and stochastic. These residual structures are present up to a certain level of thermal energy above dissociation. this area is the subject of intensive research at the present. hydrogen-bonded liquid water and gas are present in the system. Water clusters around gas molecules to form both large and small clusters [B] similar to the hydrate cages of sI and sII.they are relatively long-lived but unstable. either in the liquid or the vapor side. At the beginning of the process (point A). 108 • • • • . The above cluster model conceptual picture is most likely to occur at the interface.1. the results from one laboratory are not transferable to another laboratory or field situation. At temperatures below that upper boundary. 5. because the “building blocks” of crystals remain in the liquid. 4. In our conceptual picture. Hydrate growth kinetics are apparatus-dependent. The metastable nuclei are in quasi-equilibrium with the liquid-like cages until the nuclei reach a critical radius. The figure depicts the progress of molecular species from water [A]. In contrast to well-determined thermodynamic properties. Figure A. they may either grow or shrink in a stochastic process.5 indicates an autocatalytic reaction mechanism hypothesized for hydrate formation based upon limited experimental evidence.5.

before proceeding. Executive Summary Program Specifications This program has been developed to run in IBM-PC compatible computers having DOS as operating system. HYDCALC.5 in. If there is a safety consideration or an important process decision to be made based upon the program’s predictions. the author should not and cannot be held totally accountable for the use of the predictions which the program provide. an executable file to prediction hydrate formation conditions.B.DAT.1.DAT is present.DAT is an optional file.EXE an executable file to determine the isenthalpic (∆H=0) and isentropic (∆S=0) gas expansion conditions. User’s Guide for HYDOFF and XPAND Programs A Word of Caution While it is hoped that the programs accompanying this book will be of use in estimating the limiting conditions of hydrate formation.EXE.DAT). Section B. Use of this program is specified in Section II.1. 2. HYDOFF B. disk provided with this handbook contains four files: 1.Appendix B.EXE. FEED.XLS. HYDOFF. Appendix B provides common examples using HYDOFF and XPAND which may then be modified by the engineer for his/her own purposes.2 details the use of XPAND. a file to be used as external input of the feed components and composition for HYDOFF. while Section B.1 considers the use of HYDOFF (and FEED. FEED.5 in disk or copied to the hard-drive and then executed. 3.a. It is recommended to make a backup copy of the 109 . B. Running the Program The program can be executed directly from the 3. and 4. a shortcut estimation spreadsheet to calculate methanol or monoethylene glycol amounts. the user is cautioned to obtain a second opinion from someone knowledgeable in hydrate phase equilibria. Contents of the Disk The 3. it should be noted that HYDOFF will run regardless whether the file FEED. The program is executable without any additional hardware or software requirements. XPAND.

1.and four-phase conditions (I-H-V. The program has the central purpose of providing information about hydrate phase equilibria with and without thermodynamic inhibitors. The units and feed composition can be changed at any point during the execution of the program without actually exiting. the version accompanying this handbook has been abbreviated for rapid use. Specifications for a Problem Before any calculation is performed by the program.b. components present in the feed. virus). However.program in case problems occur (e.g. simply type HYDOFF and follow the instructions given by the program. such as: units that he/she prefers to operate in.DAT file which can be read by the program.. The program provides pressure predictions of structure I and II hydrates at a given temperature with and without thermodynamic inhibitors (methanol. It should be noted that at no point in the program is the user asked to enter an initial guess for the calculations (for pressure predictions). The program has its own 110 . salt (NaCl). to which the reader is referred for a full explanation. LW-H-V-LHC). or mixtures thereof) at three. The method used by the program for hydrate phase equilibria is based on the van der Waals and Platteeuw model. Note: When specifying components directly in the program (i. feed composition. LW-H-V. concentration of thermodynamic inhibitor(s) in the free aqueous phase. not using FEED. temperature. Program Overview The essence of the program is same as the program accompanying the monograph by Sloan (1998). B. It should be noted that the FEED. the user is asked to input some basic information. as described by Sloan (1997.EXE. The program has a MAIN MENU that directs the user to the desired type of calculation. The feed components and composition can be directly input in the program or specified in the FEED.DAT for feed input) components can be separated by a space or comma or <ENTER (or) RETURN>. and if applicable. Once a particular calculation is chosen.DAT file must be present in the same directory as HYDOFF. At the DOS prompt.c.e. type and amount of thermodynamic inhibitor(s). Chapter 5) and the hydrocarbon fluid phases are modeled with the Soave-Redlich-Kwong equation of state with parameters obtained from experimental measurements. B.1. the user is asked to enter the temperature.

(1951)) Gas Composition: Component Methane Ethane Propane i-Butane n-Butane Nitrogen n-Pentane n-Hexane Pressure prediction @ T = 51. R.d.1.35 °F Mole % 73. The maximum number of components is limited to 17 (seventeen). 3.20 0. the user does not have to specify the equilibrium phases for any calculation. et al. and hydrate).29 6.00 111 . feed.1.90 0. 4.e.55 15. 3. Some Important Notes The program is structured to prompt the user whenever incorrect or improper information is input.Temperature and Pressure predictions for Hugoton Gas (experimental data by Kobayashi. B. Equilibrium pressure.70 3. The weight percentage of methanol as inhibitor is limited to 50 wt%. Hydrate equilibrium crystal structure (sI or sII). 1. Also. Following is a list of limitations and guidelines of which the user should be aware. The total amount of methanol is assumed to be in the aqueous phase. B. Example 1 . fluid hydrocarbon. 2. Phase components and compositions (i. Different outputs will be shown for each calculation type. What to Expect for an Answer The standard output for hydrate phase equilibria calculations will display: Equilibrium phases (I-H-V. 4. The equilibrium phases are given as output of the predictions.internal initial guess. 1.36 0. Possible partitioning of methanol into other phases (condensate or gas) is neglected. 5. Examples to follow will better illustrate how the program is structured and the format of the output. LW-H-V or LW-H-V-LHC).00 0. 2.e.. The freezing point depression for systems containing both methanol and salt is determined by additive contributions of methanol and salt in solution. Fractional occupancy of cages by hydrate formers in each type of hydrate cavity.

DAT (No=1 Yes=2)? 1 How many COMPONENTS (excluding Water) are present? 8 sII HYDRATE FORMERS 1. Hydrogen Sulfide 112 . FEED. Carbon Dioxide NON-HYDRATE FORMERS 9. namely. Ethane 5.EXE file. i-Butane 7. Is the FEED COMPONENTS and COMPOSITION saved under FEED. Decane 12. Hexane 15. Toluene 3. 1997 COPYRIGHT : Professor E. Press RETURN to continue . Dendy Sloan Center for Hydrate Research Department of Chemical and Petroleum-Refining Engineering Colorado School of Mines..DAT. CO 80401 PHONE:(303) 273-3723 FAX:(303) 273-3730 This program has been designed to provide phase equilibria of hydrates in a manner consistent with available experimental data. please make sure the information is entered correctly into FEED. Octane 10. AVAILABLE UNITS ARE AS FOLLOWS : (1) (2) TEMPERATURE Fahrenheit Kelvin PRESSURE psia kPa Please select the desired set of Units : 1 The program has been designed to allow the user to input the feed components and composition directly in the program or through an external file.DAT If the user wishes to read the feed components and composition from FEED. Golden. Nitrogen 2. n-Pentane 13. Nonane 11. Your comments and feedback are welcome for future improvement of the program. n-Butane 8.HYDRATE PREDICTION PROGRAM: HYDOFF (ACCOMPANYING THE OFFSHORE HYDRATE HANDBOOK) Release Date : July 3rd. Methane 4.DAT is in the same directory as the executable HYDOFF. i-Pentane 14. Propane 6.DAT (user has to CHANGE the COMPOSITIONS ONLY) and FEED. Heptane 16..

7329 : 0.0390 : 0.0000 THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE (1) (2) (3) (4) (5) (6) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 1 Enter the required Temperature (in 51.0055 : 0.1500 : 0.0020 : 0.35 F Equilibrium PRESSURE : Experimental pressure 365.Which Components are present? Please list Hydrate formers first 1 2 3 4 5 7 9 11 Enter the MOLE FRACTIONS of each Component : Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Methane Ethane Propane i-Butane n-Butane Nitrogen Pentane Hexane : 0.1 psia 399. . .0036 : 0. Equilibrium Hydrate : STRUCTURE II Composition of Phases at Equilibrium 113 .35 F) PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH MAIN Program for Equilibrium Hydrate Predictions Display CURRENT Feed Composition Change FEED Composition Change Program UNITS DISCARD all Data and begin NEW Problem Exit HYDOFF Program Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF THREE-PHASE (Lw-H-V) EQUILIBRIUM CONDITION Temperature : 51.92 psia Press RETURN to Continue .0670 : 0.

0000 .0000 .Program terminated.0390 .0739 .0000 HYDRATE .7329 .0000 .0390 .0408 .0036 .Methane Ethane Propane i-Butane n-Butane Nitrogen n-Pentane n-Hexane FEED .0055 .0000 Press RETURN to Continue .0444 .0000 VAPOR .0055 .0377 .0063 .0670 . Fractional Occupancy of Cages Methane Ethane Propane i-Butane n-Butane Nitrogen n-Pentane n-Hexane SMALL .0000 Do you wish to do another calculation at the SAME composition? (No=1 Yes=2) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 7 THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE (1) (2) (3) (4) (5) (6) MAIN Program for Equilibrium Hydrate Predictions Display CURRENT Feed Composition Change FEED Composition Change Program UNITS DISCARD all Data and begin NEW Problem Exit HYDOFF Program PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF 6 End of run : HYDOFF Stop .3076 .5777 .0000 LARGE .7329 .0000 .7602 .0020 .1008 .0000 .1500 .0155 .0000 .0461 .0670 .0011 .6916 .1500 . . .0020 .0036 .0000 .0299 . 114 .

Your comments and feedback are welcome for future improvement of the program. Carbon Dioxide NON-HYDRATE FORMERS 3.Example 2 . Ethane 5..DAT If the user wishes to read the feed components and composition from FEED.. i-Butane 7. namely. 1997 COPYRIGHT : Professor E.DAT. (1983)) HYDRATE PREDICTION PROGRAM: HYDOFF (ACCOMPANYING THE OFFSHORE HYDRATE HANDBOOK) Release Date : July 3rd.DAT (No=1 Yes=2)? 1 How many COMPONENTS (excluding Water) are present? 7 sII HYDRATE FORMERS 1. Methane 4.. Propane 6. Press RETURN to continue . Dendy Sloan Center for Hydrate Research Department of Chemical and Petroleum-Refining Engineering Colorado School of Mines.-J. Hydrogen Sulfide 115 . Nitrogen 2.DAT (user has to CHANGE the COMPOSITIONS ONLY) and FEED. please make sure the information is entered correctly into FEED. AVAILABLE UNITS ARE AS FOLLOWS : (1) (2) TEMPERATURE Fahrenheit Kelvin PRESSURE psia kPa Please select the desired set of Units : 1 The program has been designed to allow the user to input the feed components and composition directly in the program or through an external file. and Robinson. D. H.DAT is in the same directory as the executable HYDOFF. CO 80401 PHONE:(303) 273-3723 FAX:(303) 273-3730 This program has been designed to provide phase equilibria of hydrates in a manner consistent with available experimental data.B.Pressure prediction with methanol (experimental data by Ng. Is the FEED COMPONENTS and COMPOSITION saved under FEED. FEED.EXE file. Golden. n-Butane 8.

Nonane 11. i-Pentane 14. Toluene Which Components are present? Please list Hydrate formers first 1 2 3 5 7 8 9 Enter the MOLE FRACTIONS of each Component : Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Mole Fraction of Methane Ethane Propane n-Butane Nitrogen Carbon Dioxide Pentane : 0. n-Pentane 13.03 F Equilibrium PRESSURE : Experimental pressure 800. Heptane 16.01 psia 116 .9.1419 : 0.03 F) PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH MAIN Program for Equilibrium Hydrate Predictions Display CURRENT Feed Composition Change FEED Composition Change Program UNITS DISCARD all Data and begin NEW Problem Exit HYDOFF Program Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF Enter the WEIGHT PERCENT of Methanol (up to 50wt%) 10 FOUR-PHASE (Lw-H-V-Lhc) EQUILIBRIUM CONDITION WITH INHIBITOR(S) Inhibitor :10.7160 : 0.0079 : 0.0079 THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE (1) (2) (3) (4) (5) (6) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 2 Enter the required Temperature (in 47. Octane 10.00 wt% Methanol Temperature : 47.6 psia 773. Hexane 15.0596 : 0.0473 : 0.0194 : 0. Decane 12.

0473 .1419 .0473 .0079 HYDRATE .Press RETURN to Continue .00 wt% Methanol Temperature : 33.0000 .0079 LIQUID .0390 .0000 Press RETURN to Continue .0358 .7630 .0405 .0000 .1419 .0194 .7064 .0000 .0079 .0596 .2615 .2 psia 117 . .0473 .0596 .71 F Equilibrium PRESSURE : Experimental pressure 691.0194 .1036 .71 F) PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF Enter the WEIGHT PERCENT of Methanol (up to 50wt%) 20 FOUR-PHASE (Lw-H-V-Lhc) EQUILIBRIUM CONDITION WITH INHIBITOR(S) Inhibitor :20.0079 . .0194 .0679 . Equilibrium Hydrate : STRUCTURE II Composition of Phases at Equilibrium Methane Ethane Propane n-Butane Nitrogen Carbon Dioxide n-Pentane FEED .6033 .0079 . .0647 .0596 .0221 . Fractional Occupancy of Cages Methane Ethane Propane n-Butane Nitrogen Carbon Dioxide n-Pentane SMALL .0000 LARGE .0000 Do you wish to do another calculation at the SAME composition? (No=1 Yes=2) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 2 Enter the required Temperature (in 33.0011 .1419 .0132 .8 psia 566.7160 .1094 .7160 .7159 .0167 .0079 VAPOR . .

0642 .7159 .0473 .2772 .7159 .0000 .0317 .1419 .0000 LARGE .0194 .5931 .0079 .0139 . .0000 Press RETURN to Continue .0000 . .7618 .0473 .0596 .0000 Do you wish to do another calculation at the SAME composition? (No=1 Yes=2) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 7 THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE (1) (2) (3) (4) (5) (6) MAIN Program for Equilibrium Hydrate Predictions Display CURRENT Feed Composition Change FEED Composition Change Program UNITS DISCARD all Data and begin NEW Problem Exit HYDOFF Program PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF 6 End of run : HYDOFF Stop .0079 LIQUID .0000 .0596 .0367 .Press RETURN to Continue . .0194 .0786 .7487 .0079 .0079 . .0709 . 118 .Program terminated. Fractional Occupancy of Cages Methane Ethane Propane n-Butane Nitrogen Carbon Dioxide n-Pentane SMALL .0194 .0150 .0596 .0473 .7160 .0079 VAPOR .0079 HYDRATE .0991 .0375 .1419 .0199 . Equilibrium Hydrate : STRUCTURE II Composition of Phases at Equilibrium Methane Ethane Propane n-Butane Nitrogen Carbon Dioxide n-Pentane FEED .0007 .1419 .

DAT. P. Press RETURN to continue .Example 3 . namely. please make sure the information is entered correctly into FEED.DAT (No=1 Yes=2)? 1 How many COMPONENTS (excluding Water) are present? 2 sII HYDRATE FORMERS 1.DAT is in the same directory as the executable HYDOFF. 1997 COPYRIGHT : Professor E. FEED. Ethane 5. et al. Methane 4.DAT If the user wishes to read the feed components and composition from FEED. Nitrogen 2. Hydrogen Sulfide 119 . CO 80401 PHONE:(303) 273-3723 FAX:(303) 273-3730 This program has been designed to provide phase equilibria of hydrates in a manner consistent with available experimental data..D. Dendy Sloan Center for Hydrate Research Department of Chemical and Petroleum-Refining Engineering Colorado School of Mines..Temperature and Pressure predictions with salt(s) (experimental data by Dholabhai.DAT (user has to CHANGE the COMPOSITIONS ONLY) and FEED. Your comments and feedback are welcome for future improvement of the program. Propane 6. i-Butane 7.EXE file. Is the FEED COMPONENTS and COMPOSITION saved under FEED.. Golden. n-Butane 8. Carbon Dioxide NON-HYDRATE FORMERS 3. AVAILABLE UNITS ARE AS FOLLOWS : (1) (2) TEMPERATURE Fahrenheit Kelvin PRESSURE psia kPa Please select the desired set of Units : 1 The program has been designed to allow the user to input the feed components and composition directly in the program or through an external file. (1994)) HYDRATE PREDICTION PROGRAM: HYDOFF (ACCOMPANYING THE OFFSHORE HYDRATE HANDBOOK) Release Date : July 3rd.

Heptane 16. Equilibrium Hydrate : STRUCTURE I Composition of Phases at Equilibrium Methane Carbon Dioxide FEED . n-Pentane 13.1530 HYDRATE .01 F) PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH MAIN Program for Equilibrium Hydrate Predictions Display CURRENT Feed Composition Change FEED Composition Change Program UNITS DISCARD all Data and begin NEW Problem Exit HYDOFF Program Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF THREE-PHASE (Lw-H-V) EQUILIBRIUM CONDITION Temperature : 40.7222 . Nonane 11.1530 THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE (1) (2) (3) (4) (5) (6) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 1 Enter the required Temperature (in 40. .8470 .8470 .2778 Press RETURN to Continue . i-Pentane 14.9. Decane 12.75 psia Press RETURN to Continue . Toluene Which Components are present? Please list Hydrate formers first 1 8 Enter the MOLE FRACTIONS of each Component : Mole Fraction of Mole Fraction of Methane Carbon Dioxide : 0.01 F Equilibrium PRESSURE : Experimental pressure 494.1530 VAPOR . . Hexane 15. . 120 .6 psia 496.8470 : 0. . Octane 10.

02 THREE-PHASE (Lw-H-V) EQUILIBRIUM CONDITION Inhibitor : 5.1034 LARGE .02 wt% NaCl Temperature : 47.4 psia F) PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF 980.6610 .3191 Do you wish to do another calculation at the SAME composition? (No=1 Yes=2) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 5 Enter the MOLE FRACTIONS of each Component : Mole Fraction of Mole Fraction of Methane Carbon Dioxide : 0.823 : 0.03 psia 121 .7737 .177 PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 3 Enter the required Temperature (in 47.Fractional Occupancy of Cages Methane Carbon Dioxide SMALL .93 F Equilibrium PRESSURE : Experimental pressure 1012.93 Enter the WEIGHT PERCENT of Salt 5.

.1770 VAPOR .8230 .Program terminated.8230 . .6566 .3305 Do you wish to do another calculation at the SAME composition? (No=1 Yes=2) 1 PLEASE CHOOSE ONE OF THE FOLLOWING OPTIONS (1) (2) (3) (4) (5) (6) (7) (8) 7 THE FOLLOWING OPTIONS ARE CURRENTLY AVAILABLE (1) (2) (3) (4) (5) (6) MAIN Program for Equilibrium Hydrate Predictions Display CURRENT Feed Composition Change FEED Composition Change Program UNITS DISCARD all Data and begin NEW Problem Exit HYDOFF Program PRESSURE Pressure Pressure Pressure PREDICTION prediction prediction prediction at at at at a given given T given T given T TEMPERATURE with Methanol with Salt (NaCl) with Salt+MeOH Change FEED Composition Change UNITS Return to MAIN Menu Quit HYDOFF 6 End of run : HYDOFF Stop .1136 LARGE . Equilibrium Hydrate : STRUCTURE I Composition of Phases at Equilibrium Methane Carbon Dioxide FEED .Press RETURN to Continue . . . 122 .1770 HYDRATE .8028 .2850 Press RETURN to Continue . Fractional Occupancy of Cages Methane Carbon Dioxide SMALL .7150 .

2) Copy the file XPAND. Select the components which are present in the natural gas by entering the number corresponding to each component and pressing <Enter (or) Return>. ethane. Note: The composition of the gas has to be entered on a mole fraction basis and not on a mole % basis. b) the upstream temperature (oR) before the gas expansion. 3) A screen appears requesting input of the mole fraction of each component specified in the previous screen.2. To run XPAND. After copying. Program Overview This program is used to calculate Joule . and i-pentane.Thomson cooling of a gas with expansion across a restriction.2. B.EXE and DOSXMSF.2. such as a control valve. The program will not accurately calculate expansions for gases containing nitrogen. 2) A menu will be displayed listing six different gas components. or hydrogen sulfide. 3) Obtain/copy the file DOSXMSF. propane. n-butane. i-butane. The value entered must be between 1-6. XPAND B. to access the program on your computer. do the following: 1) Locate the directory which contains XPAND. 4) A prompt appears requesting you to enter the following a) the upstream pressure (psia) before the gas expansion.a.EXE 2) Type “XPAND” The program will run and with the initial display “Enter the number of components”. Execute the program through the following steps: 1) Enter the number of components in the expanding gas. After entering each value. Please note that this program can only calculate gas expansions which contain methane. you must be in MSDOS or a Windows MS-DOS prompt.EXE from the disk to the hard drive.EXE to the same hard drive directory.b.B. carbon dioxide. press <Enter (or) Return>. and 123 . Running the Program The file is located in the floppy which has been attached to this handbook. Continue to do this until all the components in the gas are entered. To install XPAND: 1) Insert the disk into the drive.

2. 2= C2H6. Section II. Example 1 . obtained using HYDOFF. Consequently. Press <Enter (or) Return> after each entry. These steps were used to calculate the final temperature of a gas expanded from 1500 psia. 100 oF to 300 psia. Once this is done.40 1. 5= n-C4H10.34 0. B.F. 5) A prompt appears requesting input of a first guess (oR) of the downstream temperature T2. guesses for T2 should be input until the ∆H is within ±0. 3= C3H8 4= i-C4H10.c) the downstream pressure (psia). repeat this process with the same upstream temperature pressure. This guess is the decreased temperature after expansion. but with several intermediate downstream pressures.70 5.30 1. at the correct T2 the ∆H across the expansion should be negligible (zero).14 Enter the number of Components: 6 Which components are present? 1= CH4. For Joule-Thomson cooling.Step-by-step calculation of the gas expansion found in Example 12. 6= i-C5H12 Component 1: 1 Component 2: 2 124 . because the expansion curves are not linear in pressure and temperature. Once T2 is entered. However.c. record the XPAND initial and final conditions. Output from the Program This method may be used to get the final temperature upon expansion of a gas from an upstream temperature and pressure to a downstream pressure. Plot the ∆H=0 expansion pressure-temperature line to determine an intersection with the hydrate formation line. Gas Composition: Component Methane Ethane Propane i-Butane n-Butane i-Pentane Mole % 92.3.40 0. a table appears listing the initial conditions and the ∆H across the expansion. before pressing enter to leave the program.500 BTU/lbmol.

enter another guess for outlet temperature in degrees Rankine.000 R 1st delta H = 891.501 BTU/lbmol-R .234 BTU/lbmol Ideal gas delta H = -376.179 BTU/lbmol-R 2. Methane: 0.336287E-01 9.053 Propane: 0.000 psia P2 = 300. Input your guess for T2(R) (Enter “0” to exit the program).602 BTU/lbmol 1st delta S = Ideal gas delta S = 2nd delta S = Total delta S = .700 R T2 = 520.7 Enter P2 (psia): 300 Input your guess for T2 (R) (Enter “0” to exit the program).219 BTU/lbmol Total delta H = 313.377816E-01 2nd Guess 125 .059 BTU/lbmol-R 2.Component 3 Component 4 Component 5 Component 6 3: 4: 5: 6: Enter the mol fraction of each component.014 n-Butane: 0.000 psia 1st Guess T1 = 559.414 BTU/lbmol 2nd delta H = 201.0014 Enter P1 (psia): 1500 Enter T1 (R): 559.620 BTU/lbmol-R If the above values are unsatisfactory.336287E-01 9. 500 8.461145E-01 P1 = 1500.927 Ethane: 0. 520 8.014 i-Butane: 0.0034 i-Pentane: 0.

7 oR resulted in a XPAND calculation of ∆H = .000 psia 3rd Guess T1 = 559.324399E-01 P1 = 1500.P1 = 1500.234 BTU/lbmol Ideal gas delta H = -562.336287E-01 9. 100 oF to 300 psia will cause a gas temperature reduction to 29 oF (488. This value of Total delta H is sufficiently close to zero indicating an isenthalpic expansion process.784 BTU/lbmol 1st delta S = Ideal gas delta S = 2nd delta S = Total delta S = .078 BTU/lbmol-R 2. enter another guess for outlet temperature in degrees Rankine.700 R T2 = 488. 488.136 BTU/lbmol-R .179 BTU/lbmol-R 1.364 BTU/lbmol for the 6 component gas mixture.0. The intersection point of the P-T expansion line (obtained from several XPAND calculations) with the hydrate formation line (obtained from HYDOFF) will differ from the intersection point obtained by just using a straight line drawn between 126 .179 BTU/lbmol-R 2.000 psia P2 = 300.7 oR).000 psia T1 = 559.070 BTU/lbmol-R 2.245 BTU/lbmol-R If the above values are unsatisfactory.000 R 1st delta H = 891. Several such calculations at intermediate downstream pressures should be done.926 BTU/lbmol-R .000 psia P2 = 300. 0 The 3rd guess of T2 = 488.7 8.689 BTU/lbmol Total delta H = -.909 BTU/lbmol 2nd delta H = 225. This result indicates that a pressure drop from 1500 psia. Input your guess for T2(R) (Enter “0” to exit the program). Input your guess for T2(R) (Enter “0” to exit the program).102 BTU/lbmol 2nd delta H = 216. because the expansion P-T line is non-linear.700 R 1st delta H = 891.700 R T2 = 500.348 BTU/lbmol Total delta H = 112.234 BTU/lbmol Ideal gas delta H = -665.364 BTU/lbmol 1st delta S = Ideal gas delta S = 2nd delta S = Total delta S = .027 BTU/lbmol-R If the above values are unsatisfactory. enter another guess for outlet temperature in degrees Rankine.

29 oF) and the hydrate formation line 127 . and 300 psia. 100 oF.the two end points for the P-T expansion (1500 psia.

The API oil gravity was 49. When additional wells were brought onstream. Over the first few weeks of production. The high pressure gas exposed to the cold water in the flexible line formed a complete hydrate blockage over a period of 14 hours. The blockage was located by venting the gas above the plug and filling the void with liquid. Flowing conditions prior to the blockage were 12 MMSCFD of gas. The blockage length was suggested to be 8 to 10 ft long. The volume of liquid and pressure was recorded. the gas dehydrators were shut down. The volume of fluid required to fill the line corresponded to approximately 200 ft of pipeline. When the wet gas and condensate entered the cold export line (65oF). To save operating costs. the wells did not produce significant quantities of water. causing the line pressure to increase to 1800 psi before production was stopped.Additional Case Studies of Hydrate Blockage and Remediation Case Study C. The line was successfully pigged with the product gas and condensate the next day. This incident resulted in three days of production downtime at an operating cost of $40. 5500 BOPD condensate. The export line carried gas and condensate over a distance of 52 miles. CTR 208A-1 by Mentor Subsea (1996) denoted by “*” 128 . 1 Studies from DeepStar II. water was being accumulated in this low spot. water condensed and accumulated at the bottom of the catenary loop in the flexible line at 200 ft below the surface. A flexible line was installed between the floating production platform to the top of a rigid riser.Appendix C . The gas gravity was 0.A. there was some residual water-base completion fluid being produced. suggesting that the blockage was located near the surface. To prevent hydrate formation three changes were made to the pipeline operations: -methanol was injected -gas was continuously dehydrated and -the line was cleaned periodically with foam pigs. The prospect was located at Greens Canyon Block 29 in the Gulf of Mexico in 1527 ft of water.1*1 Placid experienced a hydrate plugging problem in an export pipeline.000. The export line was depressurized on both sides and the gas dissociated from the hydrates was vented. The pipeline inlet conditions were 70oF and 1050 psi. located 200 ft below the water line.68. The flexible pipe was 12 inch ID and 16 inch OD with a working pressure rating of 2160 psi. Since the line was not being pigged.

Future operations considered the use of hydrate inhibitors in the winter months.826 inch with a working pressure limit of 1800 psi. First. Since surface access is usually available to the blocked location. a blockage occurred. which was well below the hydrate formation temperature at 360 psig.Case Study C. the line was heated using the heating tape. The line ID is 3. the pressure on both sides of the plug was reduced. In the winter as the gas is throttled through the distribution valve. To prevent this problem. 2200-ft long gas flowline plugged with hydrates during the winter. The gas pressure is approximately 1100 psi. A combination of depressurization. The ground surface temperature was -20°F. typically. the Joule-Thomson cooling across the valve drop causes hydrate formation (see Section II. The flowing conditions were 120°F and 360 psig at the wellhead.2* Chevron had a 4 inch OD. methanol can be injected to clear the blockage in the line. Then. The heat input was lowered to conserve electrical energy consumption. However. The flowline material is carbon steel A333. the pressure on both sides of the plug was equalized so that the plug would not move like a projectile. chemical. there was no mechanism to monitor the fluid temperature throughout the line to insure that hydrates would not form as the heat input was reduced. and thermal techniques was used to remove the plug. This was effective in dissociating the hydrate plug. typically. One solution recently being tested is to vary the gas flow rate to keep the valves and gas distribution lines warm enough to keep them above the hydrate formation temperature. Before this blockage occurred.3* In Chevron's platform operations in the Gulf of Mexico. Currently Chevron is installing pumps to inject a kinetic inhibitor or alternative cost-effective chemicals. The problem is usually not severe. Then. Methanol was injected upstream of the hydrate plug.E). 129 . There were several lessons learned from this experience. The line is not equipped for pigging. This flowline is in the Whitney Canyon field located in the Carter Creek area of Wyoming. The flowline is wrapped with heating tape and insulation to keep the line warm enough to prevent freezing or hydrate formation. A corrosion inhibitor was used to prevent corrosion. hydrates form in the gas-lift distribution valves on the platform. The gas is generally not dehydrated. Production was shut down for one day for this remedial operation. Case Study C. methanol is injected. there were no hydrate inhibitors used.

there was no methanol or other chemicals injected at the wellhead or at the processing unit. One meter is 4 inch ID with a 2 1/4 inch orifice plate and another meter is 3 inch ID with a 2 1/8 inch ID orifice plate. Water production rate was 10 bbls/day. rated to a working pressure limit of 1000 psi. In fact. Hydrates formed in an uninsulated 4 inch Schedule 80 (4 inch ID. Based on this experience. The line was insulated with a polymer coating which is sufficient to keep the gas above the hydrate formation temperature under flowing conditions. production was shut down for about eight to ten hours. The blockage occurred during an extended 130 . Flowing wellhead conditions were 105°F and 5750 psi. The well was flowing 200 bbl/day of oil (API 57) and 7.4* Chevron reported a hydrate problem in their Carter Knox field in South Central Oklahoma. This caused hydrates to form at the second meter. It took four hours to completely remove the hydrate accumulation. After choking the well stream to 620 psi at the production unit. Although there was no free water. This was an early indicator of the hydrate formation and it was detected before a complete blockage occurred. 4 ½ inch OD) sales gas line.Case Study C. Before hydrates formed. The condensed water contributed to forming the hydrate plug. Furthermore. the gas cools rapidly due to the cold environment. Case Study C. The production unit was pre-heated to 190°F prior to start-up. the gas was saturated with water vapor at the pipeline inlet pressure and temperature. In one incident. Two flow meters were installed about 120 ft downstream from the production unit on the sales line. a complete blockage formed in a 6 inch. Additional pressure drop occurred under flowing conditions at the second meter. the hydrate accumulation near the meter caused an erroneous flow reading that deviated from the first meter. the line was depressurized and a pump injected methanol into the line. In the winter when the ambient temperature is in the upper 40's. the temperature drops to approximately 62°F at the pipeline inlet. It took several hours for the hydrates to form. Ambient temperature is approximately 3 to 5°C (37 to 41°F). The operator is currently considering changing the 3 inch ID flow meter to a 4 inch ID flow meter to eliminate the restriction in the sales line. The production unit is designed to remove liquids from the well stream but the gas is saturated with water vapor and there is always some liquid carryover into the vapor phase.5 MMscf/d of gas.5* Chevron reported several incidents of hydrate blockages in onshore gas gathering lines in Canada. 15 mile pipeline. The pipe was X42. methanol is currently injected at the rate of 10 gallons/day whenever ambient temperature drops below 50°F. To remove the hydrate plug. The condensate content was approximately 20 bbls/MMscf.

shut-in period over a 300-ft section underneath a road crossing. Previously, hot taps had located a blockage in the same location. While hot tapping was an option, in this case, it was considered too risky. Furthermore, hydrates do not typically form in these 6 inch lines if depressurized within the first 24 hours. To remove the blockage, two methods were used simultaneously. First, the line was depressurized on both sides of the plug. Then, a welding rig applied electrical current directly to the 300-ft section of the steel pipe. The line was heated to 20 to 25 °C (68 to 77°F) using the welding rig. This approach was effective in melting the hydrate plug. The remedial operation took two days to complete.

Case Study C.6* LASMO experienced a wax and hydrate combination in its Staffa field in the UK sector of the North Sea in 1993. A single, uninsulated, 8 inch flowline was installed between two satellite wells and a minimum processing platform facility (Ninian Southern Platform), located 6.3 miles away. Furthermore, there was no capability of round-trip pigging the line because a single line was used. The seabed terrain near the tree was uneven and the flowline passed over another flowline about 1.2 to 1.9 miles from the tree. Production conditions were 6000 BOPD with a GOR of 1600 scf/bbl, 0.5 to 1% water cut. The produced fluid consisted of a high GOR, high API gravity crude with some water. Fluids were produced from the reservoir by a pressure decline mechanism. The average cloud point temperature of the crude oil was 79°F. The wax content in the crude oil was 5%. The flowing wellhead conditions were 942 to 1595 psia and 122 to 194°F. Due to the very high heat losses to the sea through the uninsulated line, the unseparated multi-phase stream cooled to the seabed temperature within 1.2 to 1.9 miles from the tree. The fluid arrived at the platform at a temperature of 44°F, which was well below the wax cloud point temperature. Without thorough documentation, it is believed that hydrate formation (due to erratic methanol injection) might have served as a nucleation point to cause wax precipitation in this line. In any case, wax deposited in the flowline within a period of several days after production was started. Even though certain paraffin inhibitors were used, they were not completely effective. Periodically, the flowline was soaked with chemical solvents without much success. Sometimes, pressure was applied to force the plug, but this actually exacerbated the problem by accumulating the paraffin into a ball. Thermochemical, heat generating chemicals were considered, but were rejected because they were considered relatively new technology.

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As a contingency plan, LASMO developed an inductive heating coil to be deployed using an ROV to heat the flowline and melt the wax inside the line. Although this technique was developed, it was never implemented in the field. Two problems with this technique were that a significant amount of power and time were required to heat the flowline and its contents. Furthermore, even after melting the wax and flowing it, it could cool and re-deposit before arriving at the platform. Approximately 1.2 miles of the pipeline, filled with a wax blockage, was cut out and replaced. Even after replacing the blocked section of the line, the line became plugged with wax a second time. Injection of chemical inhibitors, methanol or solvent soaking did not work. In 1995 due to multiple problems with hydrates and wax, LASMO abandoned the field. Repeated attempts to clear the blockages with chemical such as methanol have failed and the operated decided that it was not economical, considering the amount of reserves remaining, to replace another section of pipe as was done in 1993.

Case Study C.7* Texaco experienced a hydrate plug in a 12-3/4 inch gas export line at a platform, located in Garden Banks 189. The water depth is 725 ft. The line connects to a larger gas transportation line located on the seafloor. In this case, the gas was not dehydrated sufficiently before pumping the gas into the export line. As a result, the water vapor condensed and settled out in an U-bend at the bottom of the riser. The condensed water collecting at the low spot formed hydrates. In this case, hydrates formed very rapidly and formed a near-complete blockage before it was detected. The line injection pressure rose very rapidly. To remove the hydrate plug, the gas was vented from the platform end and methanol was lubricated down the riser. The line had a check valve downstream of the riser to prevent gas from backflowing to the platform. After injecting some methanol, the hydrates completely melted and the line was cleared. A total of twenty to thirty 55-gallon drums of methanol was used for the entire operation. Production of 8000 bbls of liquid/day and 70 MMscf/d from the platform was shut down for two to three days during this remedial operation.

Case Study C.8* Texaco reported a hydrate restriction in another gas export line from a platform at Greens Canyon Block No. 6 in 600 ft. of water. In this case, hydrates slowly accumulated in a 10-3/4 inch line over a period of several days. While production was not shut down, two actions was taken to remove the restriction: (1)

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the gas dehydrator was turned on to remove water vapor from the gas stream and (2) methanol was injected into the gas export line.

Case Study C.9* Texaco also reported a gas hydrate blockage in an instrument isolation valve block in their Strathespay field in the North Sea. However, there have been no reports of hydrate blockage in the flowline because the line is adequately insulated. This field is located in 442 ft of water. The valve block has a 1/4 inch ID port leading to a pressure transducer. Since the fluid is static in this section of the line, the produced gas had water vapor that condensed and formed hydrates. The valve block and pressure port is uninsulated and exposed to very cold seawater (4°C). The hydrate blockage resulted in erroneous pressure transducer readings. To remove this blockage, the line was purged with methanol. Periodically, the line is now purged with methanol to prevent this problem. This workover operation, however, is undesirable and increases operating cost. One design flaw with this system is that the transducer line (1/4 inch ID) is situated above the valve block. Even if this line is periodically filled with methanol, the fluid will drain out and into the flowline. This will allow the wet gas to enter the transducer line and plug it with hydrates. One design option is to change the orientation of the valve block so that the transducer line is connected to the bottomside of the valve block instead of the top side. With this configuration, the line can be filled with an oil-based gelled fluid, mixed with methanol, glycol or an oil-based fluid between the flowline and the transducer sensor. Otherwise, it may fill with water, causing hydrate formation. In deepwater systems where transducers may be changed as part of a larger system, isolation valves may not be necessary.

Case Study C.10* Elf Norge has reported hydrate formation in their North East Frigg subsea flowline. The 16 inch flowline transported gas condensate from a subsea template with six wells, located 11.1 miles from the Frigg platform. During some period, only one well was flowing at a rate of 35 MMscf/d. At this low gas flow rate, most of the water and condensate settled out and accumulated in the pipeline. After a few days, the gas flow rate was increased by starting three other wells. After the gas flow rate increased to 70 MMscf/d, the pressure and liquid level in the inlet gas-liquid separator became unstable. The wells were shut down. The separator was found filled with hydrates. Samples taken from the separator contained large, solid blocks of hydrates, which took about one day to melt.

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Analysis of the liquid samples showed that the methanol content was 11-wt%, which was well below the 26-wt% required to avoid hydrate formation. However, Elf reported that the flowline did not plug with hydrates although it experienced subcooling up to 6°C. Hydrates were found just downstream of the choke on the platform. Due to Joule-Thomson cooling (see Section II.E) the gas/water mixture experienced the lowest temperature downstream of the choke. Before re-starting production, the separator was depressurized and circulated with steam to remove the hydrates. About 9000 gal of methanol were injected into the pipeline inlet, the outlet and upstream of the pipeline outlet choke. An additional 21,000 gal of methanol was injected during the first two days of restart, when the gas flow rate was gradually re-established. The liquid outlet valve of the inlet separator was severely eroded during the hydrate formation period. This might have been due to a combination of metallic particles, scale, or hydrate crystals flowing at high velocities through the valve. The valve had to be replaced. Another reason for forming hydrates downstream of the choke was the lack of an upstream heater. In many subsea completions, a heater is installed upstream of the separator and choke to prevent hydrates or wax formation and to improve the separation efficiency.

Case Study C.11* The following information was provided by Marathon on gas hydrate formation observed in a gas export pipeline from their Ewing Bank 873 platform in the Gulf of Mexico: "Hydrate formation occurs in the gas export line from the Ewing Bank 873 platform The line leaves the platform and contains a 900-ft deep loop before joining a subsea "T" connection. The line is 8 inch nominal size. The water depth ranges from 775-ft at the EW 873 platform to a maximum of 950-ft then 470-ft at the subsea connection. Seafloor temperature is estimated to be 55°F. Hydrate formation is inferred from pressure buildup in the line, and the fact that methanol can be successfully used to remediate. Methanol is pumped continuously for inhibition at approximately 140 gal/day for 32 Mmscf/d. The pressure drop in the line is a function of flow rate. It is normally in the range of 50 to 100 psi, depending on flow rate. It can be modeled accurately. If it increases much beyond the normal level (say an additional 30 psi), then a slug of methanol is periodically pumped. The hydrate restriction appears to be between the EW873 platform and the low point. Pigging has not been attempted, for a variety of reasons, but primarily due to high risk for minimal benefit. Methanol is cheap and low risk. The routine technique of depressurizing the line is not used at EW 873 because shutting-in production would be required."

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Case Study C.12* Phillips reported gas hydrate plugging problems in their Cod pipeline in the North Sea. The pipeline is 47 mile, 16 inch (ID=15.124 inch) carbon steel, designed to transport gas and gas condensate from the Cod platform to the Ekofisk center. The liquid is a light hydrocarbon with a specific gravity of 0.66. The current Cod production is approximately 35 MMSCFD and 1700 BPD of condensate. Gas hydrates completely plugged the Cod pipeline several times. In March 1978 hydrates formed and a pig became stuck in the hydrate accumulation. The hydrates were removed by depressurizing the line. The line was backflowed in an attempt to remove the pig. The backflow attempt was unsuccessful. While the pigs remained in the line, the restriction did not prevent the gas flow. A slug of 1700 gallons of methanol was pumped to try to dissolve all the hydrates in the line. During the re-start, methanol was continuously injected into the pipeline. On the Cod platform, even though the gas stream was dried adequately, the liquid condensate stream was not dried properly. Therefore, the wet condensate stream mixed with the high-pressure gas to form hydrates in the pipeline. Since 1981 the operating pressure has declined so that the pipeline is now operating outside the hydrate-formation conditions.

Case Study C.13* Texaco performed field tests in several of their Wyoming wells to evaluate the use of PVP, a kinetic inhibitor (see Section II.F.2.b). The kinetic inhibitor can be used at very low concentrations, ranging from 1/2 to 1 wt% instead of using 10 to 50 wt% of methanol to achieve the required level of hydrate inhibition. Prior to the field tests, these Wyoming wells and flowlines were experiencing hydrate plugging problems in the wells and the surface flowlines at methanol injection rates of 30 gallons/day. Flowing wellhead conditions were up to 2000 psi and 52 to 56 oF. Gas production ranged from 0.8 to 1.4 MM scf/d. Freshwater production rate ranged from 2 to 40 bbls/d. Methanol was replaced with a 4% polyvinylpyrrolidone (PVP) solution. The 4% PVP solution consisted of 4-wt% PVP, 16-wt% water and 80-wt% methanol. The PVP solution was pumped at a rate of 2 to 21 gallons/day, representing an aqueous phase concentration of less than 0.05 wt%. At these concentrations, the kinetic inhibitor was effective in preventing hydrates. This represents a cost savings in the order of 50% compared to using 100% methanol.

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Statoil lowered the flowing temperature by reducing the flow rate and entered the hydrate region. Re-start after shut-in using four approaches: a.14* Similar to Case Study 13. fields. 2. a kinetic gas hydrate inhibitor. re-start at high flow rate. Condensate content is 16wt% and water content is 2wt%. A comprehensive summary is listed in the references by Austvik et al. 1997.1 to 0. Texaco has completed extensive testing of kinetic gas hydrate inhibitors in onshore U. Texaco conducted another series of field tests in East Texas to evaluate PVP. 136 . Nineteen hydrate formation and dissociation experiments were conducted using the 6 inch test/service line. The gas flow rate ranged from 1 to 24 MM scf/d. re-start with 5-wt% methanol injection. Continuous flow . Cool pressurized line. Two. tests were conducted on 4 inch to 6 inch flowlines that were one to eight miles long. Texaco is continuing to experiment with alternative chemicals for optimizing costs and for application in offshore flowlines. located 7. Similar to the Wyoming field tests. c.Case Study C.1 miles away from the subsea manifold. Many of their fields are currently using kinetic inhibitors to reduce methanol consumption costs. The experiments were done in 1994 using a 6 inch test/service subsea line in their Tommeliten Gamma field. Pressurize line from template side. re-start at high flow rate. Cool pressurized line.8 to 40 bbls/day. The manifold gathers the flow from six subsea wells. 9 inch production lines and one 6 inch test/service line are installed to carry the flow from a subsea production manifold. in three types of experiments as follows: 1. Pressurize line from platform side. Water flow ranged from 0. Continuous flow without methanol injection. re-start without methanol injection. hydrates formed rapidly when the methanol rate was greatly reduced. b.. Following depressurization subsequent hydrate plugging was prevented by injecting the kinetic inhibitor at concentrations in the range 0.5 wt% of the aqueous phase.15 Statoil conducted 19 controlled field experiments of gas hydrate blockage formation and dissociation.Production rate was reduced and methanol injection is stopped. The line is connected to the Edda platform. d.S. 1995. Combined Case Study C. In this field. 3.

Statoil also used two gamma densitometers to detect the arrival of slugs and hydrate lumps on the platform. 4. Statoil also concluded that the results and recommendations developed from these field experiments cannot be directly applied to other fields with different conditions and fluid compositions. (3) at the choke. If the gas released from hydrate dissociation is not properly vented. 7. 3. In some cases.B. Statoil measured pressure and temperature at the following places: (1) at the manifold. 5. valves and bends. hydrate chunks flowed to the platform and plugged the topside piping.1 summarizes the observations in these field tests and operations used to form and remove hydrate blockages.b) for a plug less permeable to a Statoil black oil. (2) at the top of the riser upstream of the heater. Hydrate plugs were porous and permeable. hen the plug was subjected to a differential pressure.During these experiments. Laboratory tests performed with 10 to 20-wt% methanol also found similar results (reported by Yousif et al. 2. Combinations of depressurization and methanol injection were effective to remove all plugs. Methanol can be injected at the manifold end or at the platform end. heating the pipe from the outside can be risky. the trapped gas may potentially over-pressure the line. However. and (4) in the separator. the dissociation rate will be reduced. Table C. Gas flow through the plug causes Joule-Thomson cooling leading to additional hydrates or ice. Following are general conclusions reported by Statoil on these field experiments: 1.2. the gas from the manifold side flowed through the plug. 1996). If additional hydrates or ice form in pore spaces within the hydrate plug. 137 . This was indicated by a gradual drop in pressure at the manifold when the gas was being vented from the platform side. Field tests were done at 5-wt% methanol.. Underinhibition of methanol increases rate of hydrate formation and risk of plugging. Hydrates formed easily and rapidly after fluid conditions entered the hydrate region. Methods to remove hydrates in the topside piping include injecting methanol and/or spraying warm water on the outside surface. A thermocamera was used to detect the temperature profile of the topside lines and to detect ice/hydrate formation. See Case Study 12 (Section III. 6.

The hydrate plug dissociated slowly. Additionally. Several blocking events occurred topside before a blockage occurred somewhere between the template and riser.16. it is believed that the MeOH never reached the plug. and liquid present in the pipeline.5 miles away from the platform. Plug 1 was kept under the equilibrium temperature until it was dissociated. it was determined that the plug was approximately 2.17. taking nine days before it was removed. small buckling in the pipeline. Due to the fact that MeOH had to travel five miles. The hydrate plug was removed through one-sided depressurization. The equilibrium pressure for the hydrate plugs was approximately 200 psi at the ambient temperature. the pipeline was depressurized to dissociate the hydrate plug. (26 hours after start-up).Case Studies C.1 shows the measured pressure difference across the two plugs in Case Studies C. allowing hydrates to form at the temperatures of 60oF. 3400 gallons of methanol were injected into the wellhead to assist in dissociation. One-sided depressurization of the pipeline removed the plug after seven days. Case Study C. Upon blockage. The plug location was estimated from evaluating the rate of pressure change on both plug sides. It was thought that this practice had little effect on increasing the rate of dissociation. Figure C. When the production reached a rate of 12 MMscf/d. After several partial blocking events.17 This case study summarizes two blocking events in the above Statoil field study on hydrate formation in the Tommeliten Field of the North Sea. methanol injection was stopped. The figure highlights the change of permeability of the plug as a function of time. Case Study C. a complete hydrate plug formed approximately 2. 138 .16 and C. After observing pressure changes on both sides of the plug. The total blockage time was 25 days. The production line was maintained for 40 hours without any hydrate blockage of the line. Figure C.2 shows the pressure in the riser during the hydrate removal process. the horizontal nature of the pipeline. Methanol was injected continuously into the line throughout the start-up process to prevent hydrate formation. Plug 2 was temporarily kept above the equilibrium point to limit the cooling effects caused by Joule-Thomson cooling. These curves have been generated removing large pressure fluctuations that occurred while reducing the pressure. The experiment originated as a depressurized line that was brought into production.16 and C. The riser temperature was 16oF below the hydrate formation region. The uninhibited line was shut-in at full well pressure and cooled to ambient sea temperature. The line was then started and began producing at a rate of 12MM scf/d without any methanol present.17 as a function of time.5 miles from the platform.

Pressure Difference Across Plugs (From Berge. 1996) 1600 1400 Pressure Difference (psi) 1200 1000 800 600 Plug 2 (Case Study 17) Plug 1 (Case Study 16) 400 200 0 0 50 100 150 Time (hours) 200 250 300 .Figure C-1 .

1996) 400 350 300 Pressure (psi) 250 Plug 1 (Case Study 16) 200 150 100 Plug 2 (Case Study 17) 50 0 0 50 100 150 Time (hours) 200 250 300 .Riser Pressure vs.Figure C-2 . Time (From Berge.

the pipeline became completely blocked with hydrates approximately 30 miles from the offshore platform. the line had not been pigged for three months and during that time offshore process upsets were thought to allow free water into the line. After pigging.19 Amoco reported hydrate plug formation in a 70 mile export pipeline located in the North Sea. When blockages occur in the pipeline. they emphasized that the pressure must be maintained above 87-145 psig. The concentration of water in the gas phase is usually low enough to prevent free water formation. High pressure drops began to form in the pipeline. Early symptoms of hydrate formation are increases in differential pressure and reductions in gas production. Hydrate plugs usually form in subsea interfield pipelines and in the bottom of incoming risers. the usual time needed to carry out this remediation is 4-14 days. Two possible tools for pipeline remediation were methanol injection and depressurization of the pipeline. Methanol could not be used as a remediation method because of the plug’s distant location. but the pig became stuck in the line and had to be removed through flow reversal. causing ice formation. requiring pigging.18 Occidental Oil and Gas Company reported hydrate blockages forming in a gas and associated condensate transport line located in the North Sea. the gas is dehydrated and then compressed from 350 psig to 1300 psig.Case Study C. the equilibrium temperature moves well below 32oF. The export pipeline operates at 4930 psig with a wellhead temperature of 86oF. Depressurization was 139 . Depressurization can be avoided by adding large volumes of methanol until dissociation occurs. If the pressure drops below these values. Secondly. Occidental also emphasized the importance of minimizing the differential pressures across the plug to prevent hydrate projectiles. which cools down to the ambient sea temperature of 35oF at the outlet. To combat this. methanol is injected maintaining 25 wt% in the free water phase. The cold temperatures place the pipeline within hydrate formation conditions for the gas. Hydrate slush appeared with the pig on the offshore platform. Ice cannot be dissociated through depressurization and consequently takes more time to remove than hydrate plugs. However. The first method consists of methanol injection and depressurization of the pipeline from both sides. two methods are used to remediate plugs. the usual time needed to remove blockages through this method is 1/2-1 days. Hydrates form when insufficient amounts of methanol are injected into the pipeline. A late symptom of hydrate plugs is complete blockage of flow. Under normal operating conditions. consequently two-sided depressurization became the only viable means of dissociating the hydrate plug. The amount of gas used to displace the pig was utilized to estimate the plugs location. Case Study C.

After eight weeks. The total economic loss due to the hydrate was 31. a hydrate plug formed in the manifold. Overall. dissociating the plug in twelve hours. the hydrate plug was in the manifold for sixty days. gas flowed into the well from the formation. Depressurization was carried out on both sides of the plug.carried out over a two week period. Overall. Consequently.5 million due to remediation expenses and loss of sales. The manifold was initially loaded with water. Case Study C. the gas influx was stopped by perforating the casing. and was not drained and loaded with ethanol prior to production start-up. and was done in slow steps to prevent any high pressure buildups due to multiple plugs. The hydrate remediation process lasted eight weeks and cost $500. Depressurization of the manifold was then used to dissociate the plug. but the hydrate plug was still present after 2 days. First. production was maintained through a test production line. first with undersized pigs and then full-sized. The line was restarted by slowly sweeping the pipeline with dry gas. ethanol was injected into the manifold to begin dissociation. Two methods were attempted to dissociate the pipeline. During depressurization. blocking valves in a production line. building up to high gas rates. all production from the wells flowing into the manifold had to be shut down. Start-up of the pipeline was carried out by filling the manifold with ethanol and then resuming production. No problems were witnessed during start-up. channeling through the primary cement column at 7. Case Study C.150 ft of water off the California coast. the plug shut-down production for three months and cost $5.21 Barker and Gomez (1989) describe an Exxon experience with a hydrate in a well located in 1. Some dissociation did occur (indicated by pressure increases). 140 . as is normal practice. and the migrating gas entered the freshwater mud at the subsea wellhead. but production was maintained throughout that time via a test production line.20 Petrobras reported a hydrate blockage in a subsea manifold.750 ft. While drilling.000 to carry out. However. the plug was completely dissociated and full production could resume. with a result of severing the drillstring and stripping it up through the BOP’s until the severed drillstring end was above the gas sand. located around 2000 ft water depth. Due to difficulties with the wellhead hanger packoff.500 bbl oil and the wages of two engineers(1 week) and two technicians (3 days). The line was consistently pigged.

Gas flowed into the well and plugged the choke and kill lines. Testing of BOP’s at the surface indicated that the failure was not caused by mechanical failure from the BOP’s which were then free of hydrates.100 ft of water in the Gulf of Mexico. After four days of warm drilling mud circulation. The well was secured and the BOP’s were pulled. The well was shut-in at the surface. Wireline tools were blocked by a bridge inside the tubing string and further pulling caused separation. After cementing operations which secured the well bore. Subsequently the lubricator was found to be full of hydrates. Hydrates and trapped gas were found in the chokeline and the kill line of the bottom eight riser joints. with a ocean bottom temperatuere of 40oF. 141 . of water located offshore South America. After coiled tubing was run inside the drillstring. After all ram-type BOP’s were opened. the drillstring was backed off at 5. resulting in a recovery of hydrates. Subsequent operations were hampered by the inability to use either line. the BOP’s were recovered.100 psi. which exposed the tubing to high pressure gas and cold 45oF water.2 lbm/gal mud down the drillstring and into the formation at surface pressures up to 3. The drillstring was perforated about 400 ft above the annular gas/liquid contact. Production was gas and condensate at several hundred barrels per day with a water cut of about six percent.A through drillstring perforating gun was then run to shoot the 7 in. Case Study 23 Davalath and Barker (1993) described a hydrate problem in 595 ft. Under these conditions the tubing fluid was about 29oF below the hydrate formation temperature.22 A second Exxon drilling instance was reportedby Barker and Gomez (1989) in 3. The gas influx was killed by pumping a 14. casing just above the gas snad. Three sets of successively shallower performations were required to remove the gas completely in the annulus. both the chokeline and the kill ine were found plugged. possibly because of hydrates in the ram-block recesses. A 15 hour production test was followed by a 25 hour shut-in period to collect reservoir pressure buildup data. The well was completed with a 7 inch casing and 3. Case Study C. the lower-middle ram-type BOP’s could not be completely opened or closed. which led to the formation of hydrates.000 ft. and recovered. and a cement plug was set in the casing. At the conclusions of the kill operation.5 inch tubing. hot mud was circulated and gas was allowed to migrate into the coiled-tubing/drillstring annulus before being circulated out of the well.

plugs.7852 ft downstream with P. Direct contact with the hot glycol removed the hydrate plug but more than 13 days were lost because of this incident. (2) 3.395 ft downstream with P. During plug and abandonment operations. and dual gamma-ray sensors to monitor plug velocity. (It was difficult to discern the differences between water. the operator found ice-like solids inside the tubing bore of the tree at the seafloor and in the annulus bore. 17. As indicated in the Hydrate Plug Remediation portion (II) of this handbook. sensing. and condensate) and. Elevation varied over 250 ft. 27 Three controlled hydrate field tests were completed on Devon Energy-Kerr McGee 900 psia gas condensate line in the Powder River Basin of Converse County.5” flow orifice. Case Studies 25. length. and density.Attempts were made to melt hydrates by (1) pouring glycol into the top of the tubing.T. back-P control valve. rather than blowing it from the tubing. blowdown capability. During normal production methanol was injected at the subsea tree.T sensors. and pig launcher. 26. (3) increasing the pressure up to 7.381 ft long from wellhead to separator-receiver (SRU-10) and pig receiver.T sensing. (3) 5. At the end of the 142 . The pipeline had the following instruments at five sites: (1) the wellhead (Werner-Bolley) with P. Normally in winter. The object of the tests was to show that one-sided depressurization can be safely performed in the field.483 ft with P. methanol injection. The above attempts were unsuccessful and the authors noted that the pressure increase caused a more stable hydrate. The test line was 4 inch. (4) 6.T sensors and blowdown. the standard onshore dissociation procedure is (a) to balance the pressure on both sides and (b) to reduce the balanced pressure to move outside of the hydrate region. Case Study 24 Davalath and Barker (1993) also reported hydrate formation during well abandonment in the Gulf of Mexico. Wyoming from 1/27/97 to 2/20/97. A coiled tubing string was stripped inside the tubing and 175oF glycol was circulated to the hydrate plug at 311 ft. (2) using heated mud and seawater. The solid hydrate plugs were dissolved by circulating heated CaBr2 brine through a coiled tubing string run inside the tubing.624 ft downstream with P. and mostly buried to a depth of 5 ft with a ground temperature of 34oF. 1. (5) 11. After stopping production the flow lines and tree piping were filled with seawater and corrosion inhibitor from the surface to the seafloor.000 psi at the surface to break the hydrate plug. the flowline is continually treated with MeOH and pigged daily to prevent hydrate problems.T sensors.

The other. However.900 Newtons.300 and 9. before eroding further down the pipeline.800 Newtons. less permeable blockage. the pressures at the four sites. about double that of more porous blockages. One relatively impermeable blockage was formed in the cold portion of the line between Sites 4 and 5. Test 2 was aborted because hydrates formed upstream of site 2 (undesirable form a safety standpoint because site 2 is above ground with 2 ball valves and 2 45o bends. The following steps were used to conduct a test: • Data collection initiated • Methanol injection stopped at the wellhead • Methanol injection begun at site 4 • Pig launched at site 1 and received at SRU-10 • Blockage formation monitored • Line isolated after blockage formation • Blockage dissociation by blowdown at sites 2. then lodged to form another. These plugs were longer (ca. or SRU-10. Case Study 25 (Test 1) had 2 blockages.line was a Separator-Receiver Unit (SRU-10) which contained a pig receiver and blowdown. 90 and 175 ft) than those of Test 3. Hydrates were dissociated by reducing balancing the pressures on either side. more permeable blockage was formed in the warm portion of the line. The differential pressure ranged from 271 to 475 psi.9%.3 ft/s in the pipeline.300 and 26. Average superficial gas velocity was 6. The liquid in the water/condensate plugs was between 4. which dislodged and passed site 4 with a speed of 270 ft/s. Case Study 27 (Test 4) had a blockage which formed on the downstream side of site 4 and then was moved upstream of site 4. Case Study 26 (Test 3) resulted in a short (25 ft) blockage with low permeability. Each time the plug was driven past site 4. On the next page is a table summarizing the characteristics of the plugs: 143 . Temperatures were not analyzed because the RTD was an external measurement. via line depressurization at site 2. and the gamma ray measurements proved invaluable in analyzing hydrate formation and dissociation. without blockages.5 and 4. Both were cleared by blowdown at site 4. the orifice measurement. The average steady state liquid holdup at Site 4 is 3.9%. The differential pressure across the blockages ranged between 112 and 174 psi.4. corresponding to a total load between 6. corresponding to a total load between 15.

300. Mass/ Load (g/s/n) Max plug Velocity.00150.Test Dates Block Time.13 2 2/1-5/97 62 NA Aborted NA NA NA NA NA 3 2/6-8/97 37 25 390 NA 2960 0.14 4 2/19-20/97 143 90. 30.07 9857 0.00038 65 2.29 144 . 70 475 1.0067 NA 0. hrs Plug Length. psi Max Gas Sprfcl Velocity cm/s Max Load. ft Max ∆P.00029 270 2. ft/s Shr Strss N/cm2 1 1/27-31/97 85 NA 174 12. n Leakage.15 26908 0.

Rules-of-Thumb Summary A summary is presented for all of Rules of Thumb in the handbook.3. where possible the accuracy of the Rule-of-Thumb is provided in the appropriate Section.b) At 39oF and pressures greater than 1000 psia. Rule-of-Thumb 5: (Section II.3. lbm/MMscf Rule-of-Thumb 3: (Section II.Appendix D. Virtually all offshore gas processes cool upon expansion. psia 500 1000 1500 2000 15. Rule of Thumb 1: (Section II. together with the Section from which they were extracted. and exceptions can always be found. the maximum amount of MEG lost to the gas is 0.03% of the mole fraction of MEG in the water phase. Rule-of-Thumb 4: (Section II.5 wt %.a) For long pipelines approaching the ocean bottom temperature of 39oF.B.B.5 Water Content. (Section II. the maximum amount of methanol lost to the vapor phase is 1 lbm MeOH/MMscf for every weight % MeOH in the free water phase. since only a 145 . these Rules-of-Thumb are based upon experience and they are intended as guides for the engineer for further action. As indicated at the outset.B. above 6000 psia the temperature will increase upon expansion.B.3. Rule-of-Thumb 2: (Section II. or that further consideration of hydrates was unnecessary.b) At 39oF and pressures greater than 1000 psia. using a Rule-of-Thumb the engineer might determine that a more accurate calculation was needed for inhibitor injection amounts.0 9.A) At 39oF. hydrates will form in a natural gas system if free water is available and the pressure is greater than 166 psig.B.c) The mole fraction of MEG in a liquid hydrocarbon at 39oF and pressures greater than 1000 psia is 0.3.0 7.c) The concentration of methanol dissolved in condensate is 0.3. the lowest water content of the outlet gas is given by the below table: Pipe Pressure.002 lbm/MMscf.E) Natural gases cool upon expansion from pressures below 6000 psia.0 5. Rule-of-Thumb 7. For example. Rule-of-Thumb 6: (Section II. Rules-of-Thumb are not intended to be “Absolute Truths”.

146 . Rule-of-Thumb 10. etc. In gas/condensate or gas/oil systems.2. Rule-of-Thumb 15: (Section III.b) VC-713. shutin. loss of inhibitor injection. Section II. it is always better to take a large pressure drop at a process condition where the inlet temperature is high.g. to prevent hydrate formation in unusual circumstances.a) Use of anti-agglomerants requires a substantial oil/condensate phase. Rule-of-Thumb 14: (Section III) Hydrate blockages occur due to abnormal operating conditions such as well tests with water. (Section II. startup.2. Rule-of-Thumb 8.b) Monoethylene gylcol injection is used when the required methanol injection rate exceeds 30 gal/hr.F. e.1) In gas-water systems hydrates can form on the pipe wall. PVCap. The maximum water to oil ratio (volume basis) for the use of an anti-agglomerant is 40:60 on a volume basis. Rule-of-Thumb 12. and co-polymers of PVCap can be used to inhibit flow lines at subcooling less than 15oF. Rule-of-Thumb 9.3) Where drying is not a possibility.F.few reservoirs and no current pipelines or process conditions are above 6000 psia. Rule-of-Thumb 11.b) PVP may be used to inhibit pipelines with subcooling less than 10oF for flow lines with short gas residence times (less than 20 minutes).F.E.2. hydrates usually form as particles which agglomerate to larger masses in the bulk streams. with water phase residence times up to 30 days.3) It is always better to expand a dry gas.F. changes in upstream pressure due to throughput changes. dehydrator malfunction. (Section II. Rule-of-Thumb 13: (Section II. In all recorded instances hydrate plugs were successfully removed and the system returned to service.A.1.E. (Section II. (Section II.

a) A lack of hydrate blockages does not indicate a lack of hydrates. Rule-of-Thumb 17.b) The cost of a fixed leg North Sea platforms is $77.A. (Section IV. (Section III. (Section III.Rule-of-Thumb 16: (Section III.1. 147 . Rule-of-Thumb 22. inhibitor is usually lubricated into the line from the platform in an attempt to determine the plug distance from the platform. in an oil with a natural surfactant present) and can be detected in pigging returns.000/ton.1. for safety reasons. or months.g.3) Because the limits of a hydrate plug cannot be easily located in a subsea environment.1) Agglomeration of individual hydrate particles causes an open hydrate mass which has a high porosity (often > 50%) and is permeable to gas flow (permeability to length ratio of 8. weeks. a shut-in will cause the entire line to rapidly cool into the hydrate region.7 . Rule of Thumb 20. Regardless of the method(s) used to dissociate the hydrates. Hydrate particles anneal to lower permeability at longer times.B.B. (Section IV. Such an open hydrate mass has the unusual property of transmitting pressure while being a substantial liquid flow impediment.a) When a hydrate blockage is experienced. Rule-of-Thumb 23.B.2. it should always be assumed that multiple plugs exist both from a safety and a technical standpoint.B. the time required for hydrate dissociation is usually days. While one plug may cause the initial flow blockage. Rule-of-Thumb 18: (Section III. Attempts to “blow the plug out of the line” by increasing the upstream pressure will result in more hydrate formation and perhaps rupture due to overpressure Rule of Thumb 19.a) Methanol loss costs can be substantial when the total fraction of either the vapor or the oil/condensate phase is very large relative to the water phase.1. both confidence and patience are required to observe the result over a long period of time. Rule of Thumb 21.11 × 10-15 m).C. Frequently hydrates form but flow (e. heating is not recommended for subsea dissociation. and low lying points of water accumulation will rapidly convert to hydrate at water-gas interfaces. (Section III.C) When dissociating a hydrate plug. After a deliberate dissociation action is taken.

Typical costs of insulation via bundled lines are $1.Rule-of-Thumb 24. (Section IV.5 million per mile.3 BTU/hr-ft2-oF. a non-jacketed system costs $1.0 million/mile.2) In order to achieve a desired heat transfer coefficient of 0. 148 .5 -$2.B.

Remediation and Economics at Statoil Reseach Center.. Gjertsen. T.. E.. A. p.D.K. paper OTC 8541.P. L. Texas (18-21 February 1997) Argo. C.Urdahl.” Proc. R. 533.. J. July 13 . BHRA Group Conf. Hustvedt. Thomas. Gas Processors Asosication Conference.B. Osborne.. Proc. 27th Ann OTC.A. Trondheim. SPE Int. Sugier.. (Monfort.. Personal Communication Estimation of Capital and Operating Cost Associated with Threshold Hydrate Inhibitors.. L.... 1997. Norway. A. Lysne.. Prevention.).” J. E. “Formation and Removal of Hydrate Plugs. R. Houston. on Natural Gas Hydrates. 2-6 June (1996) Bloys. Lacey.” Proc. 7th Inter. T. Symp. D. C.. Blain. C. L. Austvik.” in Proc. C. eds New York Academy of Sciences.. p 94. Tech. E.. June 7-9. Lynch. C. 297 (March 1989) Behar. “Tommeliten Gamma Field Hydrate Experiments. U. O.. B..” 1st Internat Conf.. “Plugging Control of Production Facilities by Hydrates. on Multiphase Production.. 41.715. “Formation of Hydrates During Deepwater Drilling Operations. J. E. July 18. Field Trial at Tommeliten. E. D. I..H. Proc. Meland. Personal Communication Regarding Safety. Happel. Gomez.G. M.... Vol. Hnatow.G. Cannes. C. San Antonio.” Oil & Gas Journal. on Natural Gas Hydrates.D. Gjertsen. Lysne. (1995) Austvik... TX.References Aarseth. L.15. on Oilfield Chemistry. (1995) 149 . “Commercial Deployment of Low Dosage Hydrate Inhibitors in a Southern North Sea 69 Kilometer Wet-Gas Subsea Pipeline. Houston. B. Toulouse. Delion. Conf. Austvik... Wichert. (March 1997) Baillie. F. Hustvedt. 37 (April 1987) Barker... May 5-8. “Chart Gives Hydrate Formation Temperature for Natural Gas. T. Priestley. Petrol..W. J.-S. Sloan. 2nd Intnl.. M. Texas. Houston. BP Sunbury Research Centre. P. Ser. Conf. Berge. (1994) Berge..” SPE 37255.. “Use of Electrical Power in Control of Wax and Hydrates. 1997. “The Importance of Porosity and Permeability of Hydrate Plugs in Pipes.K. Publication 14. Texas May 1-4. Argo..” OTC 7772. 1997. Osborne. “Laboratory Testing and Field Trial of a New Kinetic Hydrate Inhibitor..B. ed.” Proc 1997 Offshore Technology Conference.

”Deepstar Insulation Requirement for Pipeline Bundles. “Evaluation of the Impact of Methanol Recycle/Recovery Facilities on Offshore Production Systems. 157 pages and a appendix. “Methods to Clear Blocked Flowlines. (January 1996) 150 .. Houston. S. “A Series of Enthalpy-Entropy Charts for Natural Gases. Stewart. T.” Trans AIME.” Mentor Subsea (J.. W. Conf..G. & Facil.. Sortland. A. Dean. Inc.O. 22 pages and references. 1996) Davalath. T. 34 pages and 3 appendices. (June 1994) DeepStar II CTR 230-1. U.” Paragon Engineering. J. of Society Petroleum Engineering.Brown. 4 Sections and 3 Appendices. p 250 (Nov. Gas Hydrates and Their Relation to the Operation of Natural-Gas Pipe Lines ..” Intec Engineering. S.. 160. Barkley. 68th Annual Tech. 3-6 October 1993.M. S. E.. 10 pages (January 1994) Chevron Canada Resources. 216 pages. (December 1992) DeepStar I CTR 240-1 “Chemical Injection System Study. DeepStar I CTR 230-1 “Control Systems. Davalath.” Proc.L. Edwards.. 1946. Bureau of Mines Monograph 8. (December 1992) DeepStar II CTR 221-1. “Hydrate Handling Guidelines: Safety and Loss Control Manual. Texas.S. (December 1994) DeepStar II CTR 223-1. authors) CAPP Guideline for the Prevention and Safe Handling of Hydrates. Inc. 27 pages (July 23. G. Jr.” SPE Prod. “Operational Experience with Hydrate Formation in Liquid Hydrocarbon Lines. Frost.and Texaco Exploration Producting Technologty Department (R..M. Tutorial and Review (August 1994) DeepStar IIA CTR A208-1. Barker.G. “Hydrate Inhibitor Design for Deepwater Completions. Kashou. SPE 26532. King.. J. 65 (1945) Canadian Association of Petroleum Producers (R. Osborne.” Texaco Central Engineering and Purchasing Department . Duncum. A. author)..N.R. C. Mohr Research & Engineering.W. J.” Intec Engineering. “Pipeline/Flowline Pigging Strategies” H. Sharples. Deaton. CTR 640-1. (June 1994) DeepStar II..” Chevron Internal Report.” Paragon Engineering Services. authors). 4 Sections and 1 Appendix. “Trials of Threshold Hydrate Inhibitors in the Ravenspurn to Cleeton Line. 1992) Corrigan.. 101 pp.W.

(June 18-20.. (December 1995) DeepStar IIA CTR A212-1.R. “Insulated Flowline Options Identification Study..16 pages and 2 appendices.DeepStar IIA CTR A209-1. 23 pages and 5 appendices. Davalath. October 1997. Urdahl. Brown. M.. and Southwest Reserch Institute. A. (T. Duus. “Deepwater Gulf of Mexico Insulated Pipe-in-Pipe Study. Personal Communication Regarding the Use and Economics of Threshold Hydrate Inhibitors. Kuhl. (February 1996) DeepStar IIA CTR A900-3.A. Revised 10th Edition. (December 1995) DeepStar IIA CTR A601-d. “GC-184 Paraffin/Hydrate Inhibition Study .” Proc. T. Netherlands (June 11. (December 1995) DeepStar IIA CTR A601-c. pg 289. Oklahoma 74145 Gjertsen. Yousif.Phase Two.. author) 36 pages.” IIT Research Institute. S.. author).D.p. Offshore Division.H.H. “Kinetics of Gas Hydrate Formation and Kinetic Inhibiton in Offshore Oil and Gas Operations. 1997) Englezos. “Deepwater gulf of Mexico Integrated Towed Flowline Bundle Design Study. Inc. Sloan. G. 6526 East 60th Street. 1997) Grainger.” INTEC Engineering Company. P. 151 . “Paraffin and Hydrate Detection Systems...” Snamprogetti. 9 Sections and 2 appendices. Austvik.R. BHR Group 1997 Multiphase ‘97 Conference. (July 17. Conf. Final Report. Gas Processors Suppliers Association.” Conoco. 1997) Hatton .J. (August 1995) DeepStar IIA CTR A601-b. 1995) GPSA Engineering Data Book.A. O.. BP Dimlington Terminal . 220 pages and 5 annexes.. R.” written personal communication to E. Cannes. Offshore & Polar Eng. Barajas. . SwRI Project 04-8217. Inc.” Paragon Engineering Services. “Removal of a Gas Hydrate Plug From a Subsea Multiphase Pipeline in the North Sea. 103 pages. Prepared for DeepStar 3204 Subcommittee. the Hague.” Proc. Tulsa. U.. “Non-Jacketed Insulation Coating. France.J. Brown author) (June 1992) Edwards. L.. Westport Technology Center International (M. Hydrate Plug Decomposition Test Program. “Hydrate Formation Tests Requirements for Multiphase Oil Systems... (April 1996) DeepStar IIA CTR A601-a.M. (September 3.K. “TR Oil Services Perspectives on the Use of Alternate Hydrate Inhibitors.” Mentor Subsea (J.” Kvaerner . C.S. A. 5th Int.

” GPA Research Report RR-66. France 2-6 June. Report. 13th Symposium on Thermophysical Properties. Carbon Dioxide. R. R.715. Colorado Kent. Pennwell Publishing. eds. Kobayashi. Proc. and Hydrogen Sulfide. D.. Elenbaas. and Dissociation in Pipeline Design and Operation.. (1981) Makogon. Weinaug. Majeed... (1994) Loh.N. Erbar.R. J. H. M.. 1997 Katz. (1959). “Industrial Experience in Evaluation of Hydrate Formation. New York. M.Houston. D. Vary.I..” Mobil Internal Report.” Proc. Sloan. “Orwell Field Pipeline Blockage Report.E.m Stange. 23 pages. 96 (1983) Lynch.S.D. “Equilibrium Phase Composition and Hydrating Conditions in Systems Containing Methanol. D. 482 pages (1997) Manning.. ed.” Oil & Gas Journal. Maddox. J. Conf. McGraw-Hill Book Co..F. F.. E.P. D. University of Trondheim (1995) Makogon. Hydrates of Hydrocarbons.. 237 pages.. Gas Processors Association.” 1st Internat. J. Y. R. D. F. New York Academy of Sciences.. Norwegian Institute of Technology. E. Vol... Handbook of Natural Gas Engineering. J. C.. 1996 Ng.K.. p 75. 81(20). M. D. Oifield Processing of Petroleum: Volume One: Natural Gas. J..” ARCO British Ltd. Hnatow. Light Hydrocarbons.Ing. Inhibition. November 1996 Lysne. Foucaud. 160: 140 (1945) Katz. “Prediction of Conditions for Hydrate Formation in Natural Gases. Boulder. Tulsa (1991) Monfort. An Experimental Study of Hydate Plug Dissocation by Pressure Reduction.H.S.. “New Hydrate Formation Data Reveal Differences. Pennwell Publishing. Cornell. Selim.. and Thompson. 802 pp.. p... Conf.P. “Hydrates in Natural Gas Lines. A. Happel..F.B. P. Kelkar... on Natural Gas Hydrates.” Trans.D.F. S. Secretariat. on Natural Gas Hydrates. (April 1983) 152 . J. 18 Chemin de la Loge.N. R. AIME..-J. (joint with Canadian Gas Processors Association) Tulsa. 1997.H. Hydrates of Natural Gas. July 31.. Personal Communication: Survey of USA Methanol Usage. Pennwell Publishing.June 1996. Coolen.. F..E. Thesis. Robinson.C.“Hydrate Dissociation Rates in Pipelines. Y. 7 pages (1992) Lingelem. Poettmann... 2nd Intnl.. June 22-27. Sloan E. M. Inc.:L. 31078 Toulouse Cedex..L..A. April .

Clathrate Hydrates of Natural Gases. R. 1994 Notz.. OK (1958) Robinson.. CO2. (April 1987) Nielsen. P. H.D. Technol... July 26. E. “Vapour-Liquid and Vapour-Liquid-Liquid Equilibria for H2S..K.K. Robinson. “The Influence of High Concentrations of Methanol on Hydrate Formation and the Distribution of Glycol in Liquid-Liquid Mixtures.” Proc. 715. D.-J. Ng. Chevron Production Technology Co.K.” GPA Research Report RR-149. Houston...B.. and a Gas Condensate in Aqueous Methanol or Ethylene Glycol Solutions.. Proc. New York. D. p 425. (First) International Conference on Natural Gas Hydrates. Gas Conditioning Conference. Hnatow. C. C. ‘The Study of Separation of Nitrogen from Methane by Hydrate Formation Using a Novel Apparatus. C.” World Oil.” GPA RR-106. 27th Ann OTC . H..-J. (Second Edition) 704pp (1998) Sloan.-J. M.. 1997) Sloan.D..A. 256 (November 1996) Polderman.E. R. 26 (1986) Sas-Jaworsky. “Discussion of the Paper. Gas Processors Association. J.’ J.-J. B. Gas Research Institute.. "The Glycols as Hydrate Point Depressants in Natural Gas Systems. Chicago (1995) Ng.’” 1st Internat Conf. (June 1993) Shuler. Happel...J. P. 64th Ann.. eds.” OTC 7777. OK (1983) Notz... P. II.. Gas Processors Association. on Natural Gas Hydrates.. Houston (March 1985) Sloan. Personal Communication of HYDCALC program (June 10.Ng... Texaco Technical Memorandum (TM 94-0145) on Relative Inhibitor Costs. Todd.L. R. “The Application of Kinetic Inhibitors to Gas Hydrate Problems..G.B.-J. Chen. J. S. Can.715. Vol. Blount. Gas Processors Association. “Use of Methanol for Hydrate Control in Expander Plants. J.B.. Petrol.. Tulsa..D. Marcel Dekker. “Hydrate Formation and Inhibition in Gas or Gas Condensate Streams. L. Annals of New York Academy of Sciences. Jr. Norman. Bucklin.D... “The Colorado School of Mines Hydrate Program. Sloan. (1994) Notz. P.. E.. Inc. Bumbgartner. Happel. Tailby.. Hnatow. “Coiled Tubing. GPA Convention. Gas Conditioning Conference. Tulsa. Chen.D. 1994 153 .W. pg 55. M. eds New York Academy of Sciences..” Proc. 25(4)." Proc.Operations and Services.J.B. Schaneman. Texas May 1-4 (1995) and SPE Prod & Facil.D. E... A. Norman. Selected Light Hydrocarbons. H.

L.Steady-State Results. Busby..J.. ed..S. San Antonio. 2-6 June (1996) Yousif.” J... J. Majeed. S. Hydrate Control in Natural Gas Systems. Xiao.. L. OK 73070. Remediation.J.S. (a handbook for operating personnel).. Norman.M. Todd. Reid and Assoc. “OLGA Simulation . 16 Sections (1996) Todd. Amoco Letter to G. G. 68th Annual GPA Convention.. on Natural Gas Hydrates. 8. Li. Lysne. (September 23. Sloan. Hatton. Trondheim.D. Shoup. Hatton.. P. “Flow Pattern Maps for the Kerr McGee 4 Inch Pipeline.O. J. Shoup. Southwest Research Institute. and Molec.” in Proc.”November 6. G. 71.S. Overa. S. Biox 1188. F. Shoup. Xiao. Recog.. J. and Economics at Statoil Reseach Center. Personal Communication. M. Southwest Research Institute.. Amoco Letter to G. “The Effects of Low Concentration Methanol Solutions on Hydrate Formation.Stange. E. D. E.M.. M.J. A. 2nd Intnl. Hatton. B.L. Shoup.Gas Freezing and Hydrates. 1997. Norway. J. “OLGA Simulation . T. Inclus. Austvik. Hourcade. Personal Communication on Safety.Plug Movement Results.” Proc. Reid. June 18. O.. p. Xiao.. “Depressurization of Natural Gas Hyrates in Berea Sandstone Cores. Yousif. Phenom. 1996b.. 1996a.. 1997. Xiao. 1978) Urdahl. Hall..H. J.J.” September 16... L... Experimentations and Modeling of the Multiphase Equilibrium and Inhibition of Hydrates.. July 14. J.P. Southwest Research Institute. Texas (March 1989) Texaco (J. Conf. M. 1996c.. G. 291. Prevention. E.). G. (Monfort.Plug Movement Results: Efect of Injecting Condensate on Plug Movement. “OLGA Simulation ..P. Toulouse. D. Barbin. K. (1990) 154 .. Amoco Letter to G. Berge.” September 23. Selim. Southwest Research Institute. Amoco Letter to G.. 1997 Townsend.” February 5. Peterson) Reliability Engineering . Hatton.

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