Journal of Natural Gas Chemistry 16(2007)81–85

Article

A Study on Inhibitors for the Prevention of Hydrate Formation in Gas Transmission Pipeline
Ming Wu1∗ , Shumiao Wang2 , Hongbo Liu3
1. Department of Storage and Architecture Engineering, Liaoning University of Petroleum and Chemical Technology, Fushun 113001, Liaoning, China; 2. R &D Center, Xinao Group, Langfang 065001, Hebei, China; 3. China Petroleum Pipeline Engineering Corporation, Langfang 065000, Hebei, China [Manuscript received August 18, 2006; revised October 27, 2006]

Abstract: Gas Hydrate is usually formed during the transportation and treatment of oil and gas, resulting in the plugging of gas pipeline and equipment. Three thermodynamic calculation formulas are analyzed to deal with this problem. The lowering of the freezing point of the inhibitors ∆T is used to calculate the formation temperature of natural gas hydrates. This is considered to be a good approach because it is not limited by what kind and what concentration of inhibitors one uses. Besides, the rate of lowering of the freezing point could be easily measured. The result of testing methanol and mono-ethylene glycol in a reactor shows that adding 10% inhibitors to the reactor can prevent the hydrates formation. Kinetic inhibitors are favored in the present research. They are divided into two types, polymer and surface-active agents. Their characteristics, mechanisms, and application prospect are separately discussed. Polymer inhibitors exhibit better efficiency. The result of field application of VC-713 inhibiter is also given in this article. In practice, the combination of thermodynamic inhibitors and kinetic inhibitors gives better result. Key words: natural gas hydrate; thermodynamic inhibitor; kinetic inhibitor; polymer; surface-active agents

1. Introduction Gas hydrate is easily formed during the transportation of oil and gas when it contains a certain amount of water, resulting in the damage to the oil and gas industry [1,2]. Since Hammerschmidt [3] discovered in 1934 that gas hydrate would block the gas pipeline, the prevention of hydrate formation has become an important matter. At present, researches on gas hydrate inhibitors have been performed in many countries. During the transportation and processing, especially when the product gases contain saturated water steam and under cold weather conditions, gas hydrate will plug the pipeline, valve, and equipment. The miscible fluid of oil and gas will be transported to certain distance before it is subjected to dehydration and thus, the gas hydrate is easily formed

in the offshore pipeline. Gas hydrate may also be formed during the liquefied separation process under ultralow temperature. Therefore, the investigation on an effective method for preventing and eliminating the formation of gas hydrate has aroused significant interest. In this article, different types of inhibitors, their characteristics, and their effect on hydrate formation are described. The capacity of methanol and mono-ethylene glycol as gas hydrate thermodynamic inhibitors was tested in a reactor. The results show that the addition of 10% inhibitors to the reactor can prevent the formation of hydrate. The field application of VC-713 inhibitor is also given in this article. 2. Thermodynamic inhibitor and calculation formula of natural gas hydrate (NGH)

Corresponding author. E-mail: wuming0413@sohu.com

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Study on the gas hydrate thermodynamic inhibitor has become widespread. The most extensively used thermodynamic inhibitors are methanol, mono-ethylene glycol, diethylene glycol, and some other electrolytes. Inhibitor molecule or ion will compete with the water molecule, changes the thermodynamic equilibrium of water and hydrocarbon molecule (changing the chemical potential of hydration), and prevent the formation of hydrate by moving the phase equilibrium curves to lower temperature and higher pressure. The hydrate will become instable and decomposed and can be easily separated. Some calculation formulas of the gas hydrate inhibitor are as follows: ∆T = K ·x M (100 − x) (1)

hydrate; ∆T gives the lowering of hydrate formation temperature, denoted by K. It should be pointed out that for deriving equation (2), the following two assumptions are made: (1) the component of inhibitor will not dissociate and generate hydrate itself; (2) R, n, and ∆H are constant. Further refinement may be necessary. From the above two formulas, it can be seen that the inhibitors with smaller molecular weight are more effective to lower the hydrate formation temperature. Methanol and ammonia are considered to be the desirable organic reagent and mineral substance, respectively. Now much research is focused on the study of new inhibitors. Glycol is not poisonous, its boiling point is much higher than methanol, and evaporation loss is negligible. Glycol is suitable for the station where plenty of natural gas be treated. From this study, it is concluded that the thermodynamic inhibitor is effective only when its content is less than up to 6% of the gas to be treated. Besides the above-mentioned organic inhibitors, inorganic acid solution (dilute electrolyte solution), including those of sodium chloride, calcium chloride, rough niter, and lithium chloride, can also be used. As far as effectiveness, nonpoisonous nature and low cost are concerned, calcium chloride is the best choice. Sodium chloride is also frequently used. But the corrosivity of its dilute electrolyte solution restricts its applications under many conditions. According to the thermodynamic derivation, it is concluded that the theoretical formula for calculating the lowering of hydrate formation temperature ∆T from the lowering of inhibitor freezing point ∆T is given by ∆T = nλ λ T0 T0
2

In Equation (1), ∆T represents the temperature lowering for the formation of hydrate, K is a constant specific to each inhibitor, M is the molecular weight of the inhibitor; x is the mass concentration of the inhibitor. Hammerschmidt [4] gives the empirical formula (1) for the calculation of lowering of gas hydrate temperature, and the K values for some of the inhibitors are listed in Table 1.
Table 1. The K values of some gas hydrate inhibitors Inhibitor Methanol, ethanol, cymene, ammonia Sodium chloride Glycol, propyl Sulphonal K values 1228 1220 2195 2425

It should be pointed out that Equation (1) does not consider the content of inhibitor in the saturated gas phase, and it is just enough to lower the saturation steam pressure. This equation is not applicable for the inhibitors that are not tested. Pieroen gives a formula for the calculation of lowering of gas hydrate formation temperature and X3 (Pieroen equation): ∆T =
2 nRT0 X3 ∆H

∆T

(3)

(2)

Where T0 represents the freezing point of pure water, K; λ represents the solidification heat of pure water, K/kg; λ represents the solidification heat of inhibitor, K/kg; T0 gives the freezing point of inhibitor, K. Among the formulas above, Equation (1) is an empirical formula and is not suitable for untested inhibitors. Equation (2) is a theoretical formula, which is confined only to dilute nonelectrolyte inhibitor solution. Equation (3) is applicable for all inhibitors regardless of its types and concentrations. In addition, using this equation, the lowering of freezing point can be easily measured and therefore, it is widely used.

Where X3 represents the mole fraction of dilute nonelectrolyte solution; T0 represents the hydrate formation temperature without inhibitors denoted by K; ∆H means the heat of formation of one mole hydrate with n mole water at T0 , denoted by J/mol; R is the gas constant and its value is taken as 1.987/(mol·K); n represents the number of water molecules in the

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3. Kinetic inhibitor The addition of certain quantity of kinetic inhibitors limit or delay the growth of gas hydrate and thus prevent the formation of hydrate [5]. The added concentration of this kind of inhibitor is low. These inhibitors prevent the agglomeration of hydrate crystal grain and plugging by decreasing the rate of formation of hydrate. This is accomplished by the addition of small quantity of chemical adjunct, which reduces the nucleation rate of hydrate as well as delays and even prevents the formation of critical nucleus and thus interferes the first growth direction and directional stability of hydrate crystal to prevent the formation of hydrate. This method has two advantages: only small quality of inhibitor is required and has high efficiency. It has become the hot point of present research [6]. On the basis of the different mechanism of molecular reaction, Kinetic inhibitor can be divided into three: Hydrate Growth Delay inhibitor, Hydrate Agglomeration Inhibitor, and Dual-Purpose Inhibitor. Hydrate Growth Delay inhibitor will delay the growth rate of hydrate nucleus and prevent their rapid growth, and when the hydrate is stagnated in the fluid, it leads to their deposition. Hydrate Agglomeration Inhibitor restricts the assembling tendency of the hydrate crystal and leads to suspension of the hydrate in fluid and then flow out with the fluid without blocking. The content of the Kinetic inhibitor used is generally from 0.01% to 0.5% with its molecular weight ranging from several thousands to millions. Its cost comparing with the thermodynamic inhibitor is more than 50%. It significantly decreases the stocking volume and pour volume. Its use and maintenance are very convenient. Kinetic inhibitor generally contains polymer and surface-active agents, and only small amount of this inhibitor is required for preventing the formation of hydrate. Emulsification between the water phase and the oil phase will occur to prevent the agglomeration of the hydrate crystal before the formation of the hydrate. The advantage of this inhibitor is that its performance is not influenced by temperature [7]. The characteristic of this type of polymer molecule chain is that it contains many water-soluble genes and has long fatty carbon chain. The polymer monomers are usually PVP, (N, N -2 dimethylamine) ethyl methacrylate, PVCap, N -acyl polyolefine imine, polyisopropyl methyl orange, N, N -alkyl acrylamide,

2-propyl-2-imidazoline, acrylate, N -methyl N -ethyl acetamine, etc. The mechanism of their operation is via the formation or adsorption of eutectic crystals to prevent the growth of hydration nucleus so that the hydration particles are scattered and do not gather, thus the hydrate formation is prevented. Many hydrate dynamic inhibitors have been developed, and among them, PVP, PVCap, VC-713, and P (VP/VC), which are composed of PVP and PVCap in the ratio 1:1. PVP, are considered as the first generation kinetic inhibitors. In 1972, Yukiev first introduced the idea thatsurface-active agents can be assembled as hydrate defence agents. Recently, French Petroleum Institute (I.F.P.) has listed surface-active agents in a series of patents, and proved that nonionic amphiprotic compound could restrict the formation of gas hydrate in the gas pipe. Some of them are amide compounds. The most efficient surface-active reagents are hydroxy carboxylic acid amide, (in which the carboxyl group with 3–36 atoms are better, 8–20 best), alkoxy dihydroxy carboxylic acid amide (or polyalkoxy dihydroxy amide), and N, N -dihydroxy carboxylic acid amide. The common surface-active agents used in industry for this purpose are SDS, SAS, DLS, and decyl benzene amine. They all contain weak electronegative oxygen atoms. At present, the polymer inhibitor gives better results and is applied more extensively. The most important function of Kinetic inhibitor is the effective prevention of hydrate formation. Any fault associated with the pouring system and the well not closed regularly or the insufficient use of inhibitor will cause hydrate blocking, and under these conditions, Kinetic inhibitor cannot be applied. The hydrate blocking can be prevented by the addition of methanol or by adopting the pressure drop method [8]. Therefore, in actual application a combination of kinetic inhibitor and thermodynamic inhibitor are used to solve the hydrate-plugging problem. We have tested the influence of different concentrations of thermodynamic inhibitor on the hydrate formation temperature. Here we take methanol and glycol as examples. We also take VC-713 as the sample of kinetic inhibitor and test its effect on the spot. 4. Experimental 4.1. Sample analysis 4.1.1. Experimental equipment

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Figure 1 shows the experimental equipment. It is composed of six parts. They are high-pressure sapphire cell, churn-dasher, constant temperature air bath, pressure increase system, temperature and pressure test system, and data collection system.

Figure 2. Hydrate formation in the reactor after adding dif ferent content of methanol (1) field pipeline, (2) 0% methanol solution, (3) 10% methanol solution, (4) 20% methanol solution

Figure 1. Schematic diagram of the experimental apparatus for hydrate formation 1–Inlet valve, 2–Air bath, 3–Sapphire cell, 4–Magnetic stirrer, 5–U magnet, 6–Floating piston, 7–O-ring, 8–Pressure gauge DS–Driving system, DPT–Differential pressure transducer, TT–Temperature transmitter, DAS–Data acquisition system, PDP–Positive displacement pump, MC-Methane cylinder

4.1.2. Experimental results According to the mole composition data of the natural gas transported in a ground pipeline, we simulate the field condition in our laboratory as presented in Table 2. The environment temperature is 6 . After the addition of the inhibitor, hydrate formation in the reactor is shown in Figures 2 and 3.
Table 2. Mole composition data of natural gas transported in the reactor Component of natural gas CH4 CO2 C2 H6 C3 H8 H2 O Composition (mol%) 85 2.5 11 1 0.5

Figure 3. Hydrate formation in the reactor after adding dif ferent content of glycol (1) field pipeline, (2) 0% glycol solution, (3) 10% glycol solution, (4) 20% glycol solution

Where curve (1) indicates the temperature and pressure of the field pipeline; % indicates the percentage of glycol addition. After adding the inhibitor, under the same pressure, the hydrate formation temperature clearly drops. The more the inhibitor content, the higher the temperature drop. At the same temperature, the hydrate formation pressure obviously ascends with the inhibitor content. After adding the inhibitor, its uncharged cluster produces some type of interaction force with the water molecule and destroys the liquid water molecule grid generated by the hydrogen bond. Thus, the water molecule needs to surmount this interaction for the formation of grid. So the gas hydrate needs some extra energy to change the conditions of hydrate formation temperature and pressure from the

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actual operating condition. From the figures, it can be seen that by the addition of 10% methanol or glycol, the hydrate generation curve and temperature pressure curve of the ground pipeline do not intersect, and the formation of hydrate in the reactor can be efficiently prevented. The traditional thermodynamic inhibitor has the disadvantages that large quantity of inhibitor is required for the prevention of hydrate formation. It also requires huge storage and injection equipment and causes environmental pollution. Its use is inconvenient and is not economical. Therefore, much interest is paid on the development of kinetic inhibitors instead of the traditional thermodynamic inhibitor. 4.2. Kinetic inhibitor experiment on-the-spot A field test was performed by the addition of VC713 inhibitor to a sea well mouth in Beihai. This well produces 0.566×106 m3 of natural gas, 1.59 m3 of congealed oil, and 0.64 m3 of water per day. The produced fluid is transported to a platform, where it is separated, compressed, and dehydrated through a 9.4 km long and 0.2 m diameter pipeline. VC-713 is a terpolymer, when added with a solution of concentration of less than 2%, and when infused with a viscosity lower than 45 MPa·s, its concentration in the water phase of pipeline is approximately between 0.25% and 0.5%. There are four steps for field measurements. First step is the determination of the operating conditions of the pipeline. Second step analyzes the formation of hydrates. The highest degree of supercooling is measured in the third step, and the forth step evaluate the effect of low concentration on the formation of hydrates. The formation rate of hydrate can be judged by detecting the decrease in flow and by the increase in pressure. Fluid temperature and pressure of the terminal point are used to estimate supercooling of the fluid in the pipeline. Under the field test condition of adding 0.5% VC713 inhibitor (see Table 3) it is concluded: The difference between the flat temperature and the melting point at the cooling curve during the course of crystallization is defined as supercooling. It was found from the experiment that VC-713 inhibitor did not reduce the effort of clearing away hydrate of

methanol under the condition of hydrate formation. VC-713 is more economical than methanol.
Table 3. Hydrate generation conditions after adding 0.5% VC-713 inhibitor Number of days 3–4 4 3 8 Supercooling ( 4 2 1 12 ) Hydrate generation not formed not formed not formed formed

5. Conclusions Two types of inhibitors are described in this article, they are thermodynamic inhibitors and kinetic inhibitors. Three thermodynamic calculation formulas were analyzed, and the lowering of freezing point by the addition of inhibitors is used for the calculation of the formation temperature of the natural gas hydrates. From the results of testing methanol and mono-ethylene glycol as the inhibitors in a pipeline it is concluded that using 10% inhibitors for the pipeline could restrict the hydrate formation. Kinetic inhibitors were also studied. They are divided into polymers and surface-active agents. The result of applying VC-713 in the field showed that polymer inhibitors had better efficiency and good application prospect. In practice, it is better to use the thermodynamic inhibitors together with the kinetic inhibitors. References
[1] Long J. The 73th Annual GPA Convention, New Orleans. LA. 1994 [2] Sloan E D. Gas Research Institute Topical Report. GRI-91/0302, 1992, 6 [3] Hammerschmidt E G. Ind Eng Chem, 1934, 26(8): 851 [4] Makogon Y F. Hydrates of Natural Gas. Wang M Sh trans. Beijing: Petroleum Industry Press, 1987. 10 [5] Xu Y J, Yang X X, Ding J, Ye G X. Natural Gas Industry, 2004, 24(12): 135 [6] Wu D J, Hu Y F, Yang J T. Natural Gas Industry, 2000, 20(6): 95 [7] Zhao Y, Ding J. Natural Gas Industry, 2004, 24(12): 132 [8] Chen G L. Natural Gas Industry, 2004, 24(8): 89