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An Insight to Inhibitors
Gas hydrates may form in any location where a free gas, water, the appropriate temperature, pressure and time exists in space, in the atmospheres of the planets, inside the planets and in the technical systems of production, transportation and processing of gases. Hydrates may form and shut the gas flow rate partially or completely in the well bottom zone of a layer; in a well bore in a fountain tubing column, in annular space, in well top pipes or in near well top equipment, in a system of field pipelines and installations, in transport gas pipelines and product pipelines and in underground systems of gas storage. The cost to the petroleum industry to inhibit the formation of gas hydrates is estimated to represent 5% to 8% of the total product plant cost. This paper discusses the various inhibitors, advantages, disadvantages, limitations and estimation.

as hydrates are solid crystalline compounds, which have a structure wherein guest molecules are entrapped in a cage like framework of the host molecules without forming a chemical bond. It is a result of the hydrogen bond that water can form hydrates. The hydrogen bond causes the water molecules to align in regular orientations. The presence of certain compounds causes the aligned molecules to stabilize, and a solid mixture precipitates. The water molecules are referred to as the host molecules, and the other compounds, which stabilize the crystal, are called the guest molecules. The hydrate crystals have complex, three dimensional structures in which the water molecules form a cage and the guest molecules are entrapped in the cages. The stabilization resulting from guest molecule is postulated to be caused by Vander Waals forces, which is the attraction between molecules that is not a result of electrostatic attraction. Another interesting thing about gas hydrates is that no bonding exits between the guest and host molecules. The guest molecules are free to rotate inside the cages built up from the host molecules. This rotation has been measured by spectroscopic means. No hydrate without guest molecules has been found in nature. Thus Clathrates (Inclusion compounds) are stabilized by the weak attractive interactions between guest and water molecules. However, the guest species have some restrictions on its size. This arises from the fact that

there are a limited no. of cage types which encapsulate guest molecule without deviation of the hydrogen bond lengths and angle from ideal ones. All of the cages are not necessarily depend on the temperature and the pressure of the guest compound in equilibrium with clathrate hydrate. To avoid the undesirable formation of gas hydrates in flow lines / risers/pipelines, inhibitor injection is unavoidable.

Chemical Inhibition
There are three types of inhibition. They are Thermodynamic, Kinetic & Anti Agglomerants. Thermodynamic hydrate inhibitors (THI) This inhibitor is added to a two component system (water + gas) which changes the energy of intermolecular interaction and changes thermodynamic equilibrium between molecules of water and gas. Mechanism These chemicals work by altering the chemical potential of the aqueous phase such that the equilibrium dissociation curve is displaced to lower temperature and higher pressure. Electrolytic solutions are used as thermodynamic inhibitors beside alcohols. Actually the chemical potential of water molecules decreases. So, the equilibrium in the reaction of hydrate formation moves to the left.



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Hydrate hydrate Where is chemical potential Water + Gas water + gas The chemical potential of a constituent in a mixture is the increase in the free energy which takes place at constant temperature and pressure when one mole of that constituent is added to the system, keeping the amounts of all other constituents constant i.e. one mole of the constituents is added to such a large quantity of the system that is composition remains almost unchanged. The chemical potential of a constituent in a mixture is its contribution per mole to the total free energy of the system of a constant composition at constant temperature and pressure. It is an intensive property because it refers to one mole of the substance (). Thermodynamic inhibitors (Typically methanol or mono ethylene glycol) are injected into processing lines as a means of hydrate control by breaking hydrogen bonds and by competing for available water molecules. The effective use of inhibitor is possible only when a pipeline operation is thoroughly prepared and controlled. Otherwise the injection of inhibitors will not only be useless, but could also promote plug formation. The risk in using thermodynamic inhibitors includes: Under dosing, particularly due to not knowing water production rates. Inhibitor not going where intended (Operator error or equipment failure). Environmental concerns, particularly with methanol discharge limits. Ensuring remote location supply. Ensuring chemical/ material compatibility; and Safety considerations in handling methanol topsides. Application : Multiphase, gas condensate and crude oil. Advantages: More effective, well understand, predictable and proven track record. Disadvantages : They are added at relatively high concentrations (10-60 wt% in the aqueous phase), Toxic/ hazardous, environmentally harmful and volatile losses to vapor (e.g. Methanol, glycols) Alcohols: Methanol and Ethanol are the hydroxyl group alcohol inhibitors, which when used hydrogen bond with the water molecules. Hydrate inhibition abilities are less for larger alcohols i.e. Methanol > Ethanol > Iso - propanol.

Methanol: Methanol is widely used as hydrate inhibitor. It has some disadvantages. Let us consider the LPG pipelines. LPG is made up largely of propane and mixed butanes. The methanol added as an inhibitor, forms propane + methanol and n-butane + methanol azeotropes, because of this methanol will appear in unacceptable levels. Gas contaminated with MeOH is unacceptable in the cryogenic Cold Box part of a LNG plant. MeOH has the freezing point well above the temperature in LNG plant. For this reason the use of MeOH is generally avoided for LNG based gas processing facilities or an additional pre treatment system removing the MeOH from gas is necessary. In pipelines, generally we add corrosion inhibitors. Some corrosion inhibitors are alcohol-based. The methanol added as a hydrate preventer, dissolved the corrosion inhibitor which leads to some unexpected corrosion problems. Under sour conditions the presence of methanol can increase risk of sulfide stress cracking and stress oriented hydrogen induced cracking. Methanol for inhibitor is usually stored on site in tanks that are open to the atmosphere. This allows some air to dissolve in to methanol. Typically, the amount of dissolved oxygen is small, over the long term this could cause problems. (The solubility of oxygen in seawater at 200C is 7.2 ppm as compared to 79 ppm in alcohol.) In sour system, a large amount of methanol has the potential to carry a large amount of dissolved Oxygen. The oxygen can reacts with H2S produces elemental sulphur which increases the risk of under deposit corrosion. In sweet system, oxygen diffuses to the metal surface and increases the corrosion rate. Oxygen introduced into a sour system lead to change in composition and morphology of the iron sulfide layer leading to the formation of FeS scale that is less protective which increases the risk of localized corrosion. Methanol is a volatile substance; we have to pay attention on vapor loss. In practical terms, this means that more inhibitor must be injected than the amount required for mitigating the hydrate formation theoretically. Depending on operating conditions, the solubility loss of methanol into sales gas can be very high, typically 1lb of methanol / MMSCF for every % methanol in water phase. Losses to liquid hydrocarbon are usually less than 1 2 % of hydrocarbon volume. As a general rule, the anti microbial activity of alcohols increases with molecular weight and chain length to about C10, while the methanol is generally considered as poor anti-microbial agent,



Ethanol exerts maximum activity at 60 to 90 Vol.%. The methanol concentration of water discharged (effluent) is limited to 1000 ppm Max.(North Sea). Safety issues (poison, volatility) and inventory management are also main concerns in the handling of the methanol. Methanol is seldom used to dissociate a hydrate plug unless the injection point is vertically above a hydrate plug (as in riser or a well); Methanol is normally used for flow line plugs. Methanol injected in to the gas pipelines can be recovered in gas processing with turbo expander plant. Methanol is fully miscible with water, while the solubility of methanol in hydrocarbons is very small. Therefore, water can be used to extract methanol from the hydrocarbon condensate efficiently. Since water is the solvent, this extraction process is called water wash. More than 96% of methanol injected can be recovered, if good engineering judgment and experience are applied. At 390F and pressure greater than 1000 Psia, the methanol lost to the vapour phase is 1 lbm Methanol / MMSCF for every weight % in the free water phase. Methanol concentration dissolved in condensate is 0.5 weight %. Methanol loss costs can be substantial when the total fraction of either the vapour or the oil / condensate phase is very large relative to the water phase. Glycols: These have more hydrogen bonding opportunity with water through one more hydroxyl group than alcohols. Glycols generally have higher molecular weights, which inhibit volatility; the commonly used glycols are ethylene glycol, tri-ethylene glycol, propylene glycol, and poly-alkylene glycol. Alcohols and glycols, when dissolved in aqueous solution form hydrogen bond with the water molecules and make it difficult for the water molecules to participate in the hydrate formation. The higher the molecular weights of the glycols cause them to remain in the liquid phase so they are more recoverable than methanol. Due to vaporization losses of glycols, Toensend and Ride recommend that ethylene glycol be used where system temperature are lower than 255K and that di-ethylene glycol be used above temperature. It has been learned that minimizing the oxygen level within the closed loop mono-ethylene glycol system is important to avoid transformation of iron carbonate to iron oxide, avoid an increasing corrosion rate and avoid possible degradation of the mono-ethylene glycol. Hence avoiding the oxygen ingress to the system is very important (use Oxygen Scavenger).

Toensend and Ride suggest that some other factors should be considered for the use of glycol injection system. The presence of salt is serious obstacle due to fouling and corrosion. The PH of the solutions should be controlled at 7 to avoid corrosion. The glycol atomization. (at low temperature) Glycol-water solution will freeze, if they are too dilute or too concentrated Nelson indicates that at 233 K the viscosity of 80 wt% of methanol was only three times that of water at ambient conditions. While the viscosity of ethylene glycol was 480 times that value for the same condition. In order to ensure flow through valves. Heat exchangers we have to maintain the viscosity between 100-150 centipoise. Dew point reductions of 35-40 0C without gas stripping and 50-60 0C with it are obtainable. At contactor temperature above 60 0C, Tetra Ethylene Glycol should be considered. At 390F and pressure greater than 1000 Psia, the maximum amount of MEG lost to the gas is 0.02 lbm/mmscf. The mole fraction of MEG in a liquid hydrocarbon at 390F is 0.03% of water phase mole fraction of MEG. The concentration of inhibiting MEG in the water phase can be determined from methanol concentration with a simple correlation of inhibitors. Wt.% MEG = -1.209+2.34(wt.% MeOH)0.052(wt.% MeOH) 2+0.0008(Wt% MeOH) 3 . MEG injection is used when the required MeOH injection rate exceeds 30 gal / hr for onshore gas lines. The following formula was used to calculate the amount of MEG required to inhibit the hydrate in Sakhalin - 2. MEG Rate (m3/hr) = 1 + 4.2 * 10-3* Gas Rate (Ksm3/ hr) + 2.4 * 10 -3 * Condensate rate (M3/hr). Advantages: Low capital & operating costs, reliable, Recoverable (Regeneration & Reclamation), very flexible and low weight. Disadvantages: Heat required, may foam with Oil/ Condensate and limited dew point reduction.

Low Dose Hydrate Inhibitors (LDHI): Kinetic Inhibitors

Kinetic inhibitors does not shift the hydrate equilib-



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rium conditions; rather, they decrease the rate at which hydrate form, preventing plugs for a period longer than the free water residence time in a gas line. They bond with the hydrate surface, delaying crystal growth for a period of time that is longer than the residence time of free water in the system. Kinetic inhibitors are added at low concentrations (less than 1 wt% in the aqueous phase). Mechanism 1. It adsorbs on the surface of hydrate micro crystals and dispersed droplets of water in the flow of a fluid. It sharply change the diffusivesorptional exchange at the inhibitor water interface; Which decrease the rate of micro crystals growth, their coagulation, sedimentation and adhesive parameters, thus preventing the formation of large gas hydrate plugs in wells/ pipelines. 2. Thus kinetic inhibitors do not prevents the hydrate formation, but shifts the time and space the formation of large hydrate plugs. 3. It must be very soluble in water, not hydrolyze to insoluble compounds, and adsorb well on a polar surface of hydrate micro crystals forming and external surface preventing the association of hydrate crystals. Fatty acids, mixture of fatty alcohols and amines etc can be used as kinetic inhibitors.e.g., Poly-N-Vinyl Amides, Poly-N-Vinyl-N-Methyllaptamide and PolyN-Vinylpyrolidone (PVP) The one of the paper by Fu et al. describes the successful application of the copolymer of vinylmethylacetamide and vinylcaprolactam to four field locations. In all cases the KHI provided a workable and cost-effective alternative to traditional inhibitors. However, all systems were gas based and none of the cases were representative of black oil systems. NOTZ et al. report on successful field trials of poly vinyl pyrolidone (PVP) in gas wells and pipelines in Wyoming. They support that PVP was used as a replacement for methanol giving beneficial reductions in chemical costs and improved hydrate control. Applications: Multiphase, gas and condensate Advantages: Low cost, Low volumes (21 wt %), environment friendly, non toxic and tested in gas systems, Performance Not influenced by temperature. Disadvantages : Limited sub-cooling (<100C) i.e.,

typically only guaranteed for less than 10 0C, time dependency, it may interact with other chemical inhibitors (corrosion inhibitors), testing programs are required prior to implementation, there are no established models for predicting the effectiveness and limited experiences in oil systems.

These are surface active chemicals (surfactants) which do not attempt to prevent hydrate crystals from forming but rather prevent them from agglomerating to form hydrate plugs. Mechanism The antiagglomerant works by emulsifying hydrates in the hydrocarbon liquid. Hydrates are carried as a Non Agglomerated slurry, without viscosity increase up to 50 % water cut. Thus they do not display the same pressure temperature limitations as kinetic hydrate inhibitors. However, antiagglomerants known to date only work in systems with a continuous hydrocarbon liquid phase and then effectiveness is dependent on the type of oil/ condensate, the salinity of the formation water and the water cut. In addition, the operation of the pipeline can also important since dispersions of small hydrate crystals will be favored by higher velocities where as at low flow rates crystals may settle out and agglomerate that the oil hydrates density difference is sufficient. This is analogous to the behavior of water oil dispersions in wet crude oil pipelines. The antiagglomerants provide protection up to 40:60 water oil ratios. Application : Multiphase, gas condensate and crude oil. Advantages: Low volumes (21 wt %), environment friendly, non toxic and It does not have the sub cooling limitations. Disadvantages :There is uncertainty about the effectiveness of antiagglomerants compared to kinetic hydrate inhibitors and it is postulated that agglomeration may still proceed. One major limitation of antiagglomerants compared to kinetic hydrate inhibitors and thermodynamic hydrate inhibitors is that they are limited to lower water cuts due to the requirement for a continuous hydrocarbon liquid phase, Limited experience, No predictive models, System specific. NH3: Ammonia is more than twice as effective as methanol on a weight basis, NH3 seldom used due to the



reaction of NH3 with CO2 in the gas to form solid plugs of ammonium carbonate, bi carbonate, and carbonate which are more difficult to remove than hydrate plugs. The handling of ammonia is safety consideration. At extreme conditions, NH3 can be used as inhibitor. Salts: Commonly used salts are Nacl, Kcl, CaCl 2 and Sodium salts in the solution and interact with the dipoles of water molecules and cause clustering. This clustering also causes a decrease in the solubility of potential hydrate guest molecules in the water. These combine to require substantially more sub cooling to cause hydrates to form.

Drilling Fluid Inhibition

The desirable characteristics of hydrate inhibitor for drilling fluids are as follows. The lowest density possible with maximum hydrate suppression. The drilling fluids play a vital role in the hydrate suppression. The desirable properties of the drilling fluids are: The relative density of the drilling fluid must have an appropriate change range. The drilling fluid can supply a definite pressure to counteract the stratums and prevent hydrates around the borehole from decomposing to keep the borehole well stable. For practical situation of hydrate sediment, its optimum density should be in the range of 1.05 1.2, according to the safe density window of drilling fluid. The drilling fluid should be able to effectively inhibit shale hydration and gas hydrate aggregation in the drilling pipe and blowout preventer. The drilling fluid should have good rheological properties and stability at low temperatures. The drilling fluid should prevent calcium- and magnesium ion pollution. Normally, the concentration of calcium and magnesium ions in the ocean is about 0.40 g/kg and 1.28 g/kg respectively. Though these percentages are less, they can greatly influence the performance of the drilling fluid. The drilling fluid must have sufficient lubrication and low filtration. While drilling in gas hydrate bearing formations, it is suggested that the drilling fluid have a high circulation speed to inhibit gas hydrate decomposition and reformation. Because the heat produced by aiguilles cutting stratums can be rapidly dissipated by the drilling fluid, the drilling fluid can be renovated rapidly. This

process is helpful for cooling the drilling fluid by cold water around drill pipe in deep seas, which can help control of the hydrates around the borehole and wellbore stability. Compatibility with most common drilling fluid components Compatibility with most salts to balance hydrate suppression and fluid density EXXON (1988) used salt at saturation limit range of 150-170 mg/lit to prevent hydrate formation. SHELL used 20 wt % Nacl & partially hydrolyzed poly acryl amide muds for drilling depths between 2000-7500 feets (Gulf of Mexico). HALF proposed, 14 lbm/gal mud is to be used to protect against hydrate formation in 7500 ft is environmentally safe and nonflammable. In addition 20 wt % Nacl & 30 wt % glycol will protect against hydrate formation up to 5000ft. In a recent survey of drilling literature, the most common deepwater drilling fluids are 20 to 30 wt.% NaCl / PHPA (Partially Hydrolyzed Polyacrylamide) systems that have been used successfully at depths up to 7500 ft. High KCl (<24 wt.%) drilling fluids are the second most frequently used. While KCl gives very strong shale stability, it is a much weaker hydrate inhibitor than NaCl. The PHPA NaCl system can function effectively with limited amount of KCl (3 wt%) or without KCl at all. Such particular formulation with 20wt% NaCl for hydrate inhibition, the 10 lb/gal fluid could provide hydrate inhibition depths up to 1650ft (Most common in GOM). There is experience with 18 CaCl 2 drilling fluids in the field at concentration of <32wt.%, these drilling fluids provide fairly strong shale inhibition and are capable of excellent hydrate inhibition but are difficult to formulate as good drilling fluid because of the interaction of Calcium ions (Ca2+ ) with clay and water soluble polymers. A 50% solution of Potassium Formate (KCOOH) has a freezing point of around -600C and has high density. This is the reason behind the use of KCOOH (as additives) in drilling fluids. Regeneration and recovery is also simple in principle. It can be used as an inhibitor also. Glycerol and Poly glycerol have acceptable physical and environmental properties, but their high density prevents their use in the low density formulas required by deep water formation-fracture gradients. Sodium Chloride (NaCl) is the cheapest and most effective additive for thermodynamic hydrate inhi-



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bition in water based muds. Often top hole sections must be drilled with mud weights in the 9 to 10 lb/gal range, thus limiting the amount of salt (NaCl) that can be added to the drilling fluid to provide hydrate inhibition. Traditionally, high levels of glycol, at times in excess of 20 wt% are used to provide acceptable levels of hydrate inhibition. At high concentrations, calcium chloride is also very effective hydrate inhibitor, but environmental and numerous technical constraints limit the use of calcium chloride in water based mud. The hydrate formation in fresh water based mud depends on the concentration of salt. Only salt will behave as antifreeze for hydrate formation among the other contents of fresh water based mud. Most effective salts in terms of affectivity and degree of sub cooling are CaCl 2 , NaBr and NaCl. Howard indicated how to calculate the effect of salts on the hydrate formation temperature by freezing point depression data for the salts. Teq,s= Teq- 0.8 * Tfreezing Where, Teq,s= Hydrate Equilibrium Temperature in brine 0C Teq= Hydrate Equilibrium Temperature in brine 0C Tfreezing = Freezing point depression by brine 0C By using the above equation it is possible to estimate the salt concentration in drilling fluids. A performance report Nigeria: Glydrill Promotes Trouble free Drilling includes information about deepwater well offshore Nigeria was successfully completed by using a Potassium Chloride, Glydrill MC system. They used 4 to 5% Glydrill MC to achieve chemical well bore stability. The KCl+Glydrill MC fluid provided a cost effective system for drilling all hole sections. Another performance report Denmark: Glydrill System Successfully Drills 7,827 ft Section contain information about how the drilling fluid performed exceptionally throughout the well, giving high levels of lubricity and well bore stability. The system, utilizing a high potassium content, was designed to stabilize the long section of reactive and lubricity. Also this system had lower fluid costs by completely recycling which affected in reducing overall fluid costs. Also it was environmentally acceptable. The Glydrill water base system was approved for discharge, thus reducing overall mud

costs by eliminating the expense of slurrification and injection equipment. This system did not affect on cementing operation and also the cement contamination did not affect the performance of the system. The contamination of Glydrill MC and Glids HD provided low coefficient of friction resulting in minimum torque and drag throughout the system. The addition of Glydrill MC and 1.5% Glide HS provided well bore stability. Glydrill MC polyglycol of M-I L.L.C is a medium cloud point (the temperature, where polyglycol additives change from being soluble which is at lower temperature to being insoluble at higher temperature) additive designed for medium to high salinity poly glycol system. The physical appearance is straw yellow to opaque, brown liquid. It has 1.012 specific gravity and solubility in water is variable. Cloud point of this liquid is above 150 0 F in situation of 3% of Glydrill MC Poly glycol and 10% concentration by volume of NaCl. Anti aggloraments, dispersant additives or kinetic additives are added with thermo-dynamic inhibitors to prevent/ slow hydrate formation. A few methods are available to predict the hydrate formation in the drilling fluids such as Mud activity method, Drilling fluid composition method & Resistivity and Density method. Selection of method is based on the past experience. Evaluation of Inhibitors The relative inhibition power (RIP) is defined as, RIP = (End point with inhibitor End point without inhibitor)/ (End point without inhibitor) Inhibitor Estimation Step 1: Calculate hydrate formation conditions. (Use gas gravity chart or empirical equations or simulation) Step 2: Calculate the weight percent MeOH /MEG required in the free water phase. (use Hammerschmidt Eq.) Step 3: Calculate the mass of condensed water. (In the absence of water analysis, use water formation curves) Step 4: Calculate mass of produced water flowing into the line. Step 5: Find the total mass of water. (Add Condensed & Produced water) Step 6: Calculate MeOH / MEG in total water phase.



Step 7: Calculate MeOH / MEG lost in gas phase. Step 8: Calculate MeOH / MEG lost in condensate. Step 9: Find total MeOH / MEG required (Total water / gas / condensate phases) Step10: Add design margin.



There is no single guideline to select inhibitor which inhibits hydrate formation. The selection is based on the GOR, Water cut, operating conditions, environmental conditions, physical & chemical properties of the inhibitor, interaction with other injection chemicals such as corrosion inhibitor, stability, solubility, environmental regulations, availability, safety & cost. However this paper briefs about various inhibitors and its applicability & limitation. This paper also outlined the estimation procedures. Kinetic & Anti - Agglomerants should be used based on the previous experience and proven track record. While using the salts as inhibitors, solubility (precipitate formation) & scale formation problems has to addressed additionally. 12.





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This publication thanks Mr. B.Chandragupthan, Senior Engineer (Process Technology), Saipem India Projects Ltd for providing this article. Mr. Chandragupthan holds a Bachelor of Technology (Chemical Engineering) from University of Madras and a Master of Technology (Refining and Petrochemical Engineering) from University of Petroleum and Energy Studies, Dehradun, India. Hehas previously worked as a Deputy Manager (Process Dept.) with PL Engineering Ltd., Gurgaon, India. He has more than six years experience in Plant Design, Operations and Maintenance. He has published / presented more than twenty papers on Gas Hydrates, Flow Assurance and Energy Economy.