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ral gas pipelines when the local fluid temperature drops below the hydrate-formation 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). 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 , H2 S 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 (is40 35 30 25 Pressure, MPa
drates (also known as methane ice) are crystalline water icelike 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 drilledhole 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.
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.
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200
160
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100 90 80
nt sta Con
line
sure 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. 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
Entropy, kJ/kg
4.1
4.3
4.5
FIG. 2. Temperature drop inside a single-stage trim valve (Line A) and a multi-stage trim valve (Line B).
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enthalpic 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. 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
M tem in. ga p. 5 s 7F Inlet pressure 1,000
1,200
1,200
Heat input, 56 kJ/kg 1 100F 2 3 5 80F 60F 4 810 830 850 Enthalpy, kJ/kg 870 890
Pressure, psi
C 20F onstan t te mp . 0F
Heater max. pressure 2
3 5 4
80F
800
40F
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870
FIG. 6. Minimum inlet temperature when using the existing low-pressure line heaters.
FIG. 7. Heat input at lowest line heater pressure for preventing hydrates at minimum inlet temperature.
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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. 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
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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.
where the temperature can drop below the outlet temperature, although areas are localized and the temperature recovers. 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 pipe-
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lines 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.
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 MS degree in mechanical engineering from Northeastern University in Boston, Massachusetts.
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