Guide to the Practical Use of Chemicals in Refineries and Pipelines

Satheesh.

Part I

Pipeline Chemicals

Chapter 1

General Aspects of Pipelines

Abstract

This chapter deals with the issues of the media to be transported: natural gas, crude oil blends, and slurry. Further, the testing and the design of pipelines are reviewed. Maintenance models for petroleum pipelines and methods for the selection of pipeline routes are described. In particular, standards for the measurement density, viscosity, pour point, sulfur content, boiling range distribution, and the carbon number distribution are described.

Keywords

Natural gas; Crude oil blends; Freezing point depressants; Selection of pipeline routes; Standards for pipelines

1.1 History

Pipelines have a long history. In ancient times, pipelines were used for water transport. Examples are still visible in archaeological areas. However, it is clear that these early constructions could not bear high pressures. The advent of gas pipelines occurred between 1820 and 1830 with the distribution of town gas . Nowadays, pipelines are indispensable in the petroleum industry for the transport of various materials, including natural gas, crude oil of various types, and refined products.

The construction and operation of pipelines are described in the literature [1–4], where the additives and chemicals that facilitate the transport of fossil fuel products are discussed.

1.2 Media to Be Transported

1.2.1 Natural Gas

1.2.1.1 Properties of Natural Gas

Natural gas consists mainly of methane, although there are trace amounts of higher hydrocarbons, nitrogen, and even helium. It is typical in the gas transportation and storage industry to try to strip out higher hydrocarbons such as ethane, propane, butane, and unsaturated hydrocarbons from natural gas if the gas is to be transmitted through pipelines.

This leaves mostly methane (with some traces of nitrogen and carbon dioxide) to be transported by the gas pipeline. The materials that are stripped out are then transported or stored separately, often as liquids. A typical composition of natural gas transmitted through pipelines is shown in Table 1.1.

Table 1.1

Composition of the natural gas transmitted from Alberta, Canada, to Ontario, Canada

Source: Morris I, Perry G. High pressure storage and transport of natural gas containing added C2 or C3, or ammonia, hydrogen fluoride or carbon monoxide. US Patent 6 217 626, assigned to JL Energy Transportation Inc. (Calgary, CA); 2001. http://www.freepatentsonline.com/6217626.html.

The compressibility factor z of methane is always less than 1.0 in the normal temperature range (ie, between −40°C and 50°C). Furthermore, the compressibility factor decreases as the pressure rises or the temperature falls; therefore less energy is needed to pump a given volume of methane (measured at standard volume) at any given normal temperature than would be expected at that temperature if the methane behaved like an ideal gas.

This effect is more marked at higher pressures. Similarly, as the pressure is increased at a constant temperature, more methane (measured at standard volume) can be stored in a given volume than would be predicted from the ideal gas equation.

Below 7 MPa, the dominant variable for the compressibility factor in the PV T equation is the molecular weight of the gas. At this pressure, the addition of ethane or propane increases the molecular weight of the gas more rapidly than the compressibility factor z decreases it. Thus there is an advantage to removing ethane, propane, etc., from the gas.

At pressures greater than 7 MPa it is advantageous to add substances such as C2 or C3 hydrocarbon compounds, carbon monoxide, hydrogen fluoride, ammonia, or a mixture of these with natural gas. Ammonia without other additives is useful as an additive for gas storage at pressures down to about 5.5 MPa. Above a lower limit, which varies with the additive being added and the pressure, this results in a smaller Mr × z product, and therefore a decrease in the amount of power needed to compress the mixture for storage and to keep it compressed.

It is also advantageous to add ammonia to natural gas to be transmitted through pipelines at pressures above 5.5 MPa. Depending on the cost, it can also be advantageous to add carbon monoxide. Hydrogen fluoride is also effective, but is prohibitive because of its toxicity and corrosive properties.

One can find the precise amount of each additive that can be added at any pressure for beneficial results by calculating the product of the molecular weight and the compressibility factor z of the resulting mixture, Mr × z, and comparing it with the product of the molecular weight and the compressibility factor z of the original natural gas. If Mr × z is smaller for the mixture than for the natural gas, energy can be saved in pumping and compression [5].

The use of two or more additives has a synergistic effect in many cases, so an even smaller amount of each is needed than would be the case if only one additive were present to produce the compressibility factor z over that of an equivalent standard volume of natural gas at the pressure and temperature involved.

When the mixture is pumped through a pipeline, however, an additional effect with ammonia emerges. In a pipeline there are pumping stations at intervals along the pipeline. At each pumping station the gas is compressed. As the gas moves toward the next pumping station, it gradually loses pressure and expands. The compression during passage through the compressor station heats the gas.

The gas cools while passing through the pipeline, transferring some of its heat to the surrounding soil through the pipeline wall. Ammonia has the property of being a refrigerant, which absorbs heat as it expands. Thus when a mixture of ammonia and natural gas is compressed and is then subsequently allowed to flow through a gas pipeline, the ammonia cools the mixture as it expands. This is regarded as an additional advantage [6].

1.2.1.2 Transportation Methods for Natural Gas

Natural gas has become a popular energy source worldwide. Natural gas is gaining in importance because of high oil prices. Traditionally, natural gas has been delivered to markets by two main methods [7]: (1) by pipelines and (2) as liquefied natural gas.

Each of these methods is capital intensive. Most advanced technologies include onshore gas-to-liquid floating liquefied natural gas, natural-gas hydrates, adsorbed natural gas, and compressed natural gas.

Alternatives to compressed natural gas technology, the operating differences between liquefied natural gas technology and compressed natural gas technology, and a technical and economic evaluation have been presented [7].

In both liquefied natural gas technology and compressed natural gas technology the gases are stored forms of natural gas. However, the key difference is that compressed natural gas is a gas that is stored at high pressure, while liquefied natural gas is an uncompressed liquid form that is stored at a low temperature.

Thus compressed natural gas requires a much larger volume to store the same mass of natural gas in comparison with liquefied natural gas. The following are used for the transportation of compressed natural gas:

• large wound coils of pipe,

• cargo-containment cylinders,

• tank modules for compressed natural gas,

• composite-reinforced pressure vessels,

• pressure vessels made of fiber-reinforced–plastic.

All these methods are economically comparable. In practice, the methods for the transportation of liquefied natural gas can transport more than twice the amount of gas that could be transported by the methods for the transportation of compressed natural gas. This is because of the increased weight of the storage containers for compressed natural gas, which must be made thicker to withstand the high pressure.

On the other hand, the processing of compressed natural gas is easier than that of liquefied natural gas. The transportation chain for liquefied natural gas starts with gas treatment, liquefaction, and storage before loading of the carriers for liquefied natural gas. This requires a comparatively complicated loading system. Eventually after transport, the liquid is pumped into pipelines of a vaporization system. In the case of compressed natural gas, the transportation chain includes only dehydration and compression at the loading terminal.

It has been concluded that compressed natural gas is very attractive for small reserves. Further, it requires a smaller total investment [7].

1.2.2 Blending of Hydrogen into Natural Gas

Blending hydrogen into an existing natural gas pipeline network has been proposed as a means of increasing the output of renewable energy systems such as large wind farms [8]. If this is implemented with relatively low concentrations, less than 5–15% hydrogen by volume, this strategy of storing and delivering renewable energy to markets appears to be viable without significantly increasing risks associated with use of the gas blend in end-use devices, such as household appliances, overall public safety, or the durability and integrity of the existing natural gas pipeline network.

The impact of hydrogen blends on industrial facilities must be studied in detail. Stationary gas engines will likely require changes to their control systems [9]. Three major risks of adding hydrogen to natural gas are:

1. gas buildup,

2. explosions in enclosures,

3. risk from transmission pipelines.

Compared with natural gas transmission pipeline explosions, there is a consistent tendency for the severity of the risk with hydrogen mixtures to shift spatially, increasing closer to the point of explosion and decreasing further from the point of explosion [10].

1.2.3 Crude Oil Blends

It is has been predicted that after 2014, crude oil production from the Alaska North Slope will decline so much that there will be a need to pump additional liquids through the pipeline to maintain the economical operation of the Trans-Alaska Pipeline System [11].

One of the proposed modes of transportation of the gas-to-liquid products is commingling them with crude oil so that it will from a single phase and then pumping the mixture through the pipeline. This transportation mode changes the properties of the gas-to-liquid product as well as the crude oil.

The physical and chemical properties of the gas-to-liquid product and its blends with crude oil from the Alaska North Slope have been assessed. From the data, the optimum blend ratio to minimize the transportation costs economics has been evaluated. It has been demonstrated that the flow behavior of the gas liquid blends is very temperature sensitive.

The viscosity and the density of the blends were found to decrease with increasing amounts of gas liquid and with increasing temperature. The rheograms for the specific crude oil are shown in Fig. 1.1. The flow behavior is Newtonian at temperatures above 20°C and changes to Bingham below 20°C.

Figure 1.1 Rheograms for crude oil at various temperatures. Source: Abhijeet IA, Chukwu GA, Khataniar S, Patil SL, Dandekar AY. Rheology of gas-to-liquid products: Alaska north slope (ANS) crude oil and their blends for transportation through the trans-Alaska pipeline system (TAPS). SPE Proj Facilit Construct 2006; 1(4):118. http://dx.doi.org/10.2118/100375-PA.

The optimum gas-to-liquid ratio in the blend is obtained from the average pressure drop per mile under the specific conditions of transport. This is shown in Fig. 1.2.

Figure 1.2 Pressure drop versus gas-to-liquid ratio. Source: Abhijeet IA, Chukwu GA, Khataniar S, Patil SL, Dandekar AY. Rheology of gas-to-liquid products: Alaska north slope (ANS) crude oil and their blends for transportation through the trans-Alaska pipeline system TAPS. SPE Proj Facilit Construct 2006; 1(4):118. http://dx.doi.org/10.2118/100375-PA.

The optimum amount of gas to liquid in the blend is governed by various factors, such as flow behavior parameters of the fluid, pipeline characteristics, elevation changes, and operation temperature. The optimum gas-to-liquid blend to crude oil blend ratio was found to be 1:2.5 [11].

1.2.4 Heavy Crude Oils

Heavy crude oils constitute a significant portion of the known global petroleum reserves [12]. Vast deposits of heavy crude oils are located in Colombia, Venezuela, Mexico, and Canada. Heavy crude oils are highly viscous or solid at ambient temperature, and have an American Petroleum Institute (API) gravity of 20 or less. Heavy crude oils include the high molecular weight hydrocarbons referred to as tars, petroleum tars, or tar sands, such as the deposit known as the Athabasca Tar Sands in Alberta, Canada.

The production of heavy crude oil and bitumen is very costly. This arises because of the extremely low mobility caused by high viscosity [13].

In addition of being more viscous than conventional crude oils, some heavy crude oils are rich in asphaltenes, metals, and resins. Some heavy crude oils contain high levels of sulfur, nitrogen, nickel, and vanadium [14]. Further, they are rich in the condensed polyaromatic compounds which react readily to form coke. The presence of these types of compounds may result in various problems in the recovery, transportation, treatment, and refining of these oil types [12].

On the other hand, the transportation of heavy and extra heavy crude oils from the well head to the refinery is becoming important because their production is currently rising all over the world. Such oils are characterized by an API gravity of less than 20 and high viscosity. The issues of transportation of heavy and extra heavy crude oil by pipelines have been reviewed [15].

Various methods have been developed to transport heavy oils through pipelines. The commonest method is to blend the heavy crude oil with a light hydrocarbon to decrease the overall viscosity. Different technologies for reduction of the viscosity have been reviewed as have the advantages and disadvantages [14]. The methods for facilitating the transport of heavy crude oils are summarized in Table 1.2.

Table 1.2

Easier transport of heavy crude oils

Source: Hart A. A review of technologies for transporting heavy crude oil and bitumen via pipelines. J Petrol Explorat Product Tech 2013;4(3):32736. http://dx.doi.org/10.1007/s13202-013-0086-6.

The catalytic upgrading process in situ was specifically developed for the recovery and upgrading of heavy oil and bitumen [16]. The effects of the reaction gas media used in the upgrading process were investigated, in particular the effects of hydrogen, methane, nitrogen, and a blended gas mixture. The viscosity reduction and the conversion of hydrocarbons into lower boiling fractions follows the same trend as the API gravity.

The most relevant parameters in pipeline transportation of heavy crude oil are velocity, viscosity, temperature, density, and pour point [17]. Heavy crude can be transported on trunk systems in a variety of modes, including segregation, blending, and batching.

Segregation requires separate pipelines, blending consists of mixing crude oils, and batching refers to shipping crude in discrete batches. There are a number of methods for enhancing the transportability of heavy crude. These include oil-in-water emulsion formation, droplet suspension, dilution, the use of drag-reducing additives, and heating.

Another method is to establish a two-phase flow. This results in pipeline lubrication. A thin water film is injected around the internal oil core, which leads to the core annular flow regime. Thus the water lubricates the heavy oil, and the longitudinal pressure gradient is largely reduced. This basic method is more than 100 years old and goes back to an early US patent [18]. A sketch from that patent is shown in Fig. 1.3.

Figure 1.3 Piping method.

In Fig. 1.3, A represents a pipeline through which the fluid desired to be conveyed is caused to flow. The flow may be occasioned by the pump B, which draws the fluid by a suction pipe b from a suitable source. With the first fluid delivered to the pipeline A, a second fluid, which must be of greater specific gravity than the first fluid, may be delivered to the first fluid in the pipeline by means of the pump C, with its suction c, encircling sleeve c and holes c ′ in the pipeline A.

Experiments with such systems revealed a pressure-drop reduction of more than 90% compared with the same product without lubrication. These results confirm the effectiveness of such a lubricating process [13].

1.2.5 Emulsions

Water-external emulsions can be transported in pipelines to achieve higher net flow rates of oil than in the transport of dry oil alone [19]. The percentage of oil in water may range between 70% and 80%. The oil is combined with an aqueous solution comprising water, a pH-enhancing agent, and solid particles and is mixed until the solids-stabilized oil-in-water emulsion is formed. The pH of the resulting oil-in-water emulsion should be 7.5–10.

In the propagation of the emulsion through a pipe it is preferred to contact the inner walls of the pipe first with a wettability-altering agent to make the inner walls of the pipe water-wet so as to facilitate the propagation of the oil-in-water emulsion. After the inner walls of the pipe have been contacted with the wettability-altering agent, the oil-in-water emulsion can be pumped through the pipe.

High-oil content, solids-stabilized oil-in-water emulsions are therefore good candidates for transportation in pipelines using flow regimes of either self-lubricating core annular flow or uniform, lower-viscosity water-external emulsions [19]. In core annular flow, the formation of a low-viscosity annulus near the pipe wall further reduces pressure drop.

The viscosity of water (ie, the continuous phase) is not greatly affected by temperature. Therefore the viscosity of a solids-stabilized oil-in-water emulsion is not greatly affected by temperature and such oil-in-water emulsions do not have to be heated to high temperatures to maintain an acceptably low viscosity for economical