Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ...

Page 1 of 10

COPYING AND DISTRIBUTING ARE PROHIBITED WITHOUT PERMISSION OF THE PUBLISHER

Prevent methane hydrate formation in natural gas valves

05.01.2013
Massachusetts The discussion here focuses on the thermodynamics involved and on the requirements for a successful natural gas valve application in which the incidences of hydrate formation and icing of the valve are reduced. Keywords: Gas flow across a control valve is considered a classic throttling process that is defined by energy not being added or extracted from the process gas as it traverses the valve. Therefore, total enthalpy is preserved, entropy increases and the process is thermodynamically irreversible. The consequences of this process are that many real gases experience a drop in temperature while following the constant enthalpy line as the pressure drops across the valve. This effect was first described by William Thomson and James Joule, and it now bears their names. The Joule-Thomson effect is leveraged in the production of cryogenic fluids such as liquid oxygen, nitrogen and argon, and it is the principle of operation behind most air conditioners and refrigeration in use today. Natural gas production, storage and transmission usually take place close to ambient conditions, where a small change in temperature can induce the formation of methane clathrates (hydrates). Once formed, methane hydrates can block valves, fittings and pipelines. Newer facilities are using higher transmission pressures, causing the temperature inside the valve to approach or drop below 0C, with the risk of icing on the outside of the valve. The discussion here focuses on the thermodynamics involved and on the requirements for a successful natural gas valve application in which the incidences of hydrate formation and icing of the valve are reduced. Computational fluid dynamics (CFD) studies are also presented showing the Joule-Thomson effect in a real-world valve application. | Glaun, A. , GE Oil & Gas, Avon, Massachusetts; Shahda, J. , GE Oil & Gas, Avon,

What are methane hydrates?

Natural gas/methane hydrates (also known as methane ice) are crystalline water ice-like particles, where methane molecules are trapped inside hydrogen-bonded water molecules. Under the right conditions of pressure and temperature, these form semi-solid particles that tend to agglomerate, building up inside pipelines, valves and other process equipment.

Why worry about methane hydrates in valves?

Hydrate ice particles may clog flow passages in control valves and, in particular, valves with noise attenuation trim (small drilled-hole cages, labyrinth passage stacks, etc.). This sometimes causes a major reduction in the flow across the valve, badly affecting system operation. Severe hydrate formation may even clog large passages of the valve body and pipeline.

How do methane hydrates form?

Hydrates form in natural gas pipelines when the local fluid temperature drops below the hydrate-formation

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 2 of 10

temperature at a specific pressure. This temperature drop can occur when the natural gas flows through a control valve, or when gas travels through transmission pipelines under cold ambient conditions or through any other piece of process equipment where the flow is restricted or accelerated in such an orifice plate. This phenomenon of temperature drop with pressure drop in a real gas is known as the Joule-Thomson effect. Note: Hydrates can form at temperatures well above the freezing point of water (Fig. 1).

Fig. 1. Stability curve showing that methane hydrate is stable at 0.1 MPa (1 bar) if temperatures are low enough, and that it is stable far above the melting point of ice (H2O) if pressures are high enough. Data courtesy of Lawrence Livermore National Laboratory.

Hydrate-formation temperature is difficult to predict and is the subject of many academic papers. Prediction depends on temperature and pressure, water concentration and the composition of the natural gas, where small concentrations of heavy hydrocarbons and other gases such as O2, N2, H2S and CO2 can affect the formation temperature. Software programs are available to help the user predict the formation temperature, but the only way to know for certain is to test a sample of the gas in question.

How is the gas temperature drop calculated?

Flow across a control valve is considered a throttling, constant enthalpy (isenthalpic) process. This implies that the process occurs over a very short period, making it adiabatic (no heat is lost or gained during the process); enthalpy is preserved, and the process is irreversible (i.e., entropy increases and cannot be recovered). For a real gas flowing through a control valve, this process gives a lower downstream temperature. Additional lowering of the downstream temperature may occur due to high downstream velocity of the expanded gas (Eq. 1). For natural gas and reasonable downstream velocities of less than 0.3 Mach number (Ma), the velocity terms in Eq. 1 are two orders of magnitude smaller than the enthalpy and can usually be ignored. (1)

Where: h = Specifc enthalpy V = Fluid velocity

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 3 of 10

1, 2 = Upstream and downstream conditions, respectively.

Two common methods exist to calculate the temperature drop of natural gas for a given pressure drop across the valve. The first method is to determine the enthalpy at the inlet pressure and temperature and then to determine the outlet temperature at the same enthalpy and outlet pressure. Software programs and web-based calculators can give this data, but the Mollier chart for methane can also be used, assuming an isenthalpic process in the valve from Eq. 1. A Mollier chart, at minimum, displays properties of pressure, temperature, enthalpy and entropy on one diagram, allowing the user to define a state using only two properties and reading off the other properties (Figs. 24). By definition, this is an accurate method of determining the downstream temperature; it is only limited by the accuracy of the Mollier chart and by the users ability to graphically interpolate the chart. Using software may be more precise, but the authors believe that a Mollier chart gives the user a visual sense of how the values are changing and leads to a better understanding of the thermodynamics.

Fig. 2. Temperature drop inside a single-stage trim valve (Line A) and a multi-stage trim valve (Line B).

Fig. 3. Single-stage contoured plug valve (Line A).

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 4 of 10

Fig. 4. Multi-stage, expanding-area trim valve (Line B). After determining the inlet condition on the chart, the user follows the lines of constant enthalpy until the downstream pressure line is reached. The temperature now can be read at this new position. The caveats to this method are that the assumption of constant enthalpy is just thatan assumption. In reality, there is some heat transfer across the valve/pipe boundary, and the process is never precisely a true throttling process. These inefficiencies will result in lower temperatures than the ideal determined above. The second method is a general rule used in the natural gas industry where, for every 100-psi pressure drop, there is a corresponding 7F temperature drop; however, this rule is limited to a maximum valve inlet pressure of 1,000 psi. Using the Mollier chart for methane at room temperature, the accuracy of this rule can be evaluated. It varies from 5.5F/100 psi for inlet pressures of approximately 300 psi, to 6F/100 psi for inlet pressures of approximately 1,000 psi. The rule takes into account inefficiencies and is somewhat conservative. However, for high inlet pressures and small pressure drops, the rule is very conservative. For example, from a drop of 1,000 psi to 800 psi, the temperature drop is 4.5F/100 psi per the Mollier chart. The temperature downstream of the valve is a concern, but the lowest temperature inside the valve trim must also be calculated. In fact, the pressure and temperature at the trim vena contracta (smallest area of flow in the trim) are usually lower than the pressure and temperature downstream of the valve. The lower temperatures inside the valve are due to sudden accelerations of the gas inside the valve trim and typically are thermodynamically isentropic (reversible) in nature. These internal pressure drops can be very large for single-orifice valves and less so for multi-stage control valve trims that drop the pressure over a number of controlled pressure-drop stages; they can be visualized if the reader follows the constant entropy line on the Mollier chart. Fortunately, this vena contracta low temperature is not a permanent change of state, and the temperature due to this effect recovers after the gas passes through the valve trim, leaving only the vena contracta and adjacent areas cold.

How can hydrate formation be avoided?

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 5 of 10

There are several solutions to reduce the incidence of hydrate formation in valves: 1. Appropriate inlet temperature. The natural gas inlet temperature can be chosen so that, when the pressure drops across the valve, the resulting downstream temperature of the natural gas is always above the hydrate-formation temperature. Gas temperatures are normally determined by the gas field, so external heating of the inlet gas prior to entering the valve may be the only option. This is, however, expensive in terms of heating equipment and fuel costs. The required inlet temperature can be determined using the Mollier chart or the 7 F/100 psi rule, by starting at a known safe outlet temperature and then working backward. 2. Inhibitor injection. Inhibitors can be injected upstream of the control valve to prevent the gas from reaching the hydrate-formation temperature, thereby preventing the formation of hydrates. The most common inhibitors are methanol and ethylene glycol; these typically can be recovered from the gas and recirculated. However, inhibitor injection and recovery can be costly. 3. Valve trim design. As noted earlier, even if the valve outlet is above the hydrate-formation temperature, the internal valve trim temperature may not be, and hydrate formation is possible within the valve. If this is the case, then selecting a multi-stage valve that gradually lowers the pressure across the valve trim will help the situation. Note: Trim selection cannot prevent downstream hydrate formation if the downstream temperature is below the hydrate-formation temperature. The Joule-Thomson effect is a state condition from upstream to downstream, and changing the valve trim will not affect this. The red lines in Fig. 2 show the properties of methane as the fluid travels through the control valve from upstream (1) to downstream (2). The long, dashed red line labeled A represents a single-stage control valve where the temperature drops below the hydrate-formation line (blue line), making it possible for hydrates to form inside the trim. The dotted red line labeled B represents a multi-stage control valve where the temperature does not drop below the hydrate-formation line, thus preventing hydrates from forming inside the trim.

Valve icing
Under high pressure-drop conditions, the outlet temperature in the valve may fall below the freezing point of water. This may not cause hydrate formation inside the valve because inhibitors such as monoethylene glycol (MEG) can be used with gas at 10C. Even so, condensation and freezing on the outside of the valve body and pipeline can have serious effects. For example, coastal gas fields on the Saudi Arabian peninsula are notoriously humid and prone to ice buildup. Extremely thick layers of ice can build up, preventing access to the valve body or pipe wall. These layers of ice can add significant weight to the valve and pipeline, with the possibility of structural and/or vibration problems. The valve bonnet may become iced, thus seriously impacting the valve stem packing and raising the potential for leakage.

A real-world problem
A natural gas producer was flowing gas through a control valve with the following winter conditions:
z z

Upstream: 975 psia, at 57F Downstream: 180 psia, with icing on the valve and pipe.

The icing was unacceptable to the plant operator, and the only line heaters available were rated at 350 psia and could not be used to heat the inlet gas. For the purposes of this example, the natural gas is assumed to be methane. An isenthalpic analysis showed that the downstream temperature reaches 14F (Fig. 5, points 12). Using a gas industry general rule, the downstream temperature could reach 1.3F (Fig. 5, points 13). The end user required that the downstream temperature be no less than 40F to prevent icing and hydrate formation.

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 6 of 10

Fig. 5. Heating required at inlet pressure to keep outlet temperature above 40F. Solution 1: Heat gas at the valve inlet. A common solution to this type of icing problem is to use pipeline heaters just upstream of the valve. The fuel for the heaters is usually the flowing natural gas itself. However, this solution is costly in terms of lost gas and the expense of high-pressure heaters. Referring to Fig. 5 and using the 40F minimum outlet temperature requirement (dashed blue line), point 4 can be located and the temperature can be back-calculated to maintain 40F at the outlet of the valve. The gas inlet temperature should be above 95F (point 6) to avoid falling below 40F at the outlet. Using an isenthalpic analysis, the inlet temperature should be above 84F (point 5) to avoid falling below 40F at the outlet. The difference between points 5 and 6 is quite substantial, and, as discussed earlier, the authors believe that, for high pressures, the 7F/100-psi rule is overly conservative. The isenthalpic analysis is ideal for this measurement; the true value lies somewhere in between. Note: The addition of hydrate inhibitors might lower the end users specification of 40F minimum temperature at the outlet of the valve. In this case, point 4 would move to a lower value to the left and the analysis would be repeated, thereby lowering the minimum required inlet temperature to prevent hydrate formation. The rate of energy input required to heat the gas can be read directly from Fig. 5 by subtracting the enthalpy at point 6 from the enthalpy at point 1. If this value is multiplied by the mass flowrate in kg/s, then the answer is the rate of energy input in kJ/s or kW. As mentioned before, this analysis is independent of the type of trim in the valve. If the analysis shows that the temperature at the outlet is low enough to form hydrates, then changing to a multi-turn or multi-stage trim will not alter the conditions at the outlet. A multi-stage valve will, however, limit very low temperatures inside the valve trim. Solution 2: Use available low-pressure heaters. The first option considered was to save the customer from having to buy new equipment by using the existing, 350 psia-rated line heaters (Fig. 6). This method required staging the pressure drop by placing another valve in the line. The first pressure drop occurred from 975 psia to the heater maximum pressure of 350 psia, and then down to the outlet pressure of 180 psia.

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 7 of 10

Fig. 6. Minimum inlet temperature when using the existing low-pressure line heaters. In the methodology of this solution, the outlet drop should not fall below 40F, which allows point 4 to be located. An isenthalpic analysis is used to back up to the heater pressure of 350 psia, which gives points 3 and 5, respectively. Point 2 is located on the 40F minimum line, and an isenthalpic analysis is used to back up to the inlet pressure of 975 psia, giving points 1 and 6, respectively. The heat input is calculated from points 25. The addition of heat at 350F reduces the minimum inlet temperature to 84F from 95F, with no heat addition. Note: As with solution 1, the addition of hydrate inhibitors might lower the end users specification of 40F minimum at the outlet of the valve. In this case, point 4 would move to a lower value and the analysis would be repeated, thereby lowering the minimum required inlet temperature to prevent hydrate formation. Solution 3: Apply new low-pressure heaters. If the answers from the first two solutions are inadequate, the next step is to examine the lowest-pressure-rated line heaters that can be used and still operate year-round at the minimum inlet temperature of 57F. This requires a slightly different methodology than that used previously. Referring to Fig. 7 and starting at the minimum inlet temperature at point 1, the pressure must then be determined for when 40F is reached. This gives point 6, which is at 732 psia. Knowing that the endpoint is point 4, one can work backwards, using isenthalpic analysis, to arrive at point 5. The enthalpy difference between points 5 and 6 is the resulting heat input required. Comparing the result of solution 3 to solution 1, a small reduction in heat input is required. Note that the heat input found when using the general rule is identical to that found when using the isenthalpic analysis.

Fig. 7. Heat input at lowest line heater pressure for preventing hydrates at minimum inlet temperature.

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 8 of 10

At this point, it becomes a question for the end user of economics and complexity. Solution 1 appears to be less complex, since it requires only one control valve; however, a large pressure drop across one valve results in a severe service application with low internal valve trim temperatures, possibly requiring an expensive multi-turn or multi-stage valve. High-rated pressure-line heaters also must be purchased, and significant heat must be added to the upstream gas. Solution 2 does not appear to be useful since an additional valve would need to be added to the line to accommodate the pressure drop from 350 psia to the outlet pressure of 180 psia, and the system would not be able to run unless the ambient (inlet) temperature reached 84F. However, there are some geographical locations where this might not be such a burden. Solution 3 requires the complexity of an additional valve, but the pressure drop is broken up into two reasonable steps, resulting in two less severe applications and warmer internal valve trim temperatures. Lower-rated pressure-line heaters would need to be purchased, and significant heat would need to be added to the upstream gas.

Numerical analysis for valve trim temperature

CFD can be used to model the flow through the trim of the valve. An accurate CFD analysis to capture JouleThomson effects is only possible if advanced real gas formulations are used. A real gas model takes into account non-ideal compressibility effects, whereas an ideal gas CFD analysis will only predict localized drops in temperature resulting from increases in velocity and reductions in local pressure due to the acceleration of the fluid as it negotiates turns in the valve trim. The proprietary CFD program used in this case has a real gas model that uses the Redlich-Kwong formulation to predict the fluid properties, taking into account the non-ideal compressibility of the working fluid. The program predicted 54F at the outlet of the trim, which compares favorably to an isenthalpic analysis using a Mollier chart, which predicts 54.5F. Fig. 8 shows a representative 22-turn trim (pictured is a half-symmetry model of one flow channel) with an inlet pressure of 975 psia and an outlet pressure of 180 psia. The results show the even, gradual, staged pressure drop through the valve trim. This style of trim serves two main purposes: One is to lower the outlet jet Ma, producing a quiet valve, and the other is to reduce the temperature drop inside the valve trim to minimize hydrate formation and icing.

Fig. 8. CFD pressure plot of a representative 22-turn, multi-stage valve trim. Fig. 9 shows the temperature results. The plot clearly shows the Joule-Thomson effect of a permanent temperature drop from inlet to outlet. It also shows areas inside the valve trim where the temperature can drop

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing | ... Page 9 of 10

below the outlet temperature, although areas are localized and the temperature recovers.

Fig. 9. CFD temperature plot of a representative 22-turn, multi-stage valve trim. A real gas solver formulation allows for the solving of Joule-Thomson effects.

Even accepted global standards for valve sizing, such as IEC 60534-2-1, do not take this real gas effect into account and base the sizing exclusively on upstream temperature, assuming an ideal gas where interstage and downstream temperature equals the upstream temperature. (Note: IEC 60534-2-1 does warn that compressibility of real gases should be taken into account if an accurate upstream density is to be calculated.) IEC control valve noise prediction standard 60543-8-3 explicitly states in its scope statement that ideal gas laws are assumed, and it uses the upstream temperature to determine downstream density, velocity and Ma. For this specific problem, the downstream velocity can be under-predicted by 8%.

Takeaway
Hydrate formation and icing in natural gas pipelines and valves can be greatly reduced or even prevented entirely if a detailed study of the thermodynamics of the system is undertaken. An intimate knowledge of the process gas is essential so that properties, such as hydrate-formation temperature, can be accurately determined. Also, using real gas analysis, internal valve trim temperatures can be calculated, leading to a better understanding of the type of valve trim required to inhibit hydrate formation. HP The authors

Asher Glaun is a senior engineer and technologist for Masoneilan Control Valves at GE Oil & Gas. He has worked in the control valve industry for over 12 years. Prior to his work with GE Oil & Gas, Mr. Glaun was employed for 11 years at Bird Machine Co. in the design of high-speed centrifuges. His work at GE involves leading new technology development specializing in fluid dynamics, CFD, structural analysis/FEA and valve acoustics. Mr. Glaun graduated with a BSc degree in mechanical engineering from the University of Cape Town, South Africa, and he obtained an MS degree in mechanical engineering from Northeastern University in Boston, Massachusetts.

Joseph Shahda is a senior applications engineer for Masoneilan Control Valves at GE Oil & Gas. He has over 16 years of experience in the control valve industry, with a focus on applications engineering and delivering control valves solutions to customers worldwide. Mr. Shahda holds an

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013

Prevent methane hydrate formation in natural gas valves | Hydrocarbon Processing |... Page 10 of 10

MS degree in mechanical engineering from Northeastern University in Boston, Massachusetts.

http://www.hydrocarbonprocessing.com/Article/3198949/Prevent-methane-hydrate-form... 5/8/2013