GAS PROCESSING DEVELOPMENTS

SPECIALREPORT

Use online analyzers for successful monitoring

Improved analytics measure moisture and dew points for natural gas components
A. BENTON, Michell Instruments Ltd., Ely, Cambridgeshire, United Kingdom; and C. VALIZ, PDVSA, Jose Complex, Venezuela

sing advanced online water and hydrocarbon dew-point analysis techniques is critical to the efficient and reliable operation of natural gas liquid-extraction processes, producing valuable light alkane liquids while the remaining gas is suitable for sales distribution. At its San Joaquin facility, Petrleos de Venezuela, S.A. (PDVSA) initially processed raw wellhead natural gas by separating residual hydrocarbon (HC) condensates, followed by glycol dehydration to reduce the water dew point. Reduced temperature separation was used to decrease the HC dew point prior to molecular sieve dehydration. This provided feed gas with moisture controlled to trace levels into the primary liquid-extraction process. Maintaining moisture concentrations to less than 0.1 parts per million (ppm) by volume is essential for reliably operating turbo expanders. The turboexpanders function is to use the depressurization of natural gas to achieve deep cooling of the process flow to 80C. Avoiding ice formation within the separation processparticularly the turboexpanderis critically important for continuous plant operations and to prevent astronomical maintenance costs. Online measurement of dew point temperature within the feed gas, containing water precipitate and hydrocarbon condensate, enabled PDVSA process operators to extend the lifetime of the desiccant beds while protecting the turboexpanders from risk of damage. The San Joaquin plant (Fig. 1) started operation in 1985 and currently provides a third of the total Venezuelan production of natural gas liquids, roughly 43,000 barrels per day, transferred

via pipeline to the PDVSA Jose Complex, near Barcelona. The Jose fractionation plant extracts butane, iso-butane and other individual alkanes. Residual gas production at 1,000 million standard cubic feet per day (MMf 3d) enters the Venezuelan market network.
The extraction process. The production train at the San Joaquin process plant is shown in Fig. 2, while Fig. 3 illustrates a schematic of an individual train. Unprocessed wellhead natural gas (two-phase gas flow with entrained hydrocarbon liquids and water) enters the San Joaquin facility. It is initially processed using separation vessels to collect the bulk-entrained natural gas liquids that flow in the feed pipeline. The gas at this point is highly corrosive and saturated with moisture, and is prone to hydrate formation. Hydrate formation is crystalline solids that form from condensed liquid water in combination with methane under pressurized conditions, even at temperatures above freezing. Initial dehydration is carried out at the earliest stage by a glycol contactor where liquid triethylene glycol (TEG) is spray injected as a desiccant into the gas flow rising through a process column contactor (Fig. 4). Moisture-laden TEG is collected from the contactor for heat regeneration greater than 200C, so boiling off the adsorbed moisture is done in a continuous circulation process. At this stage, the gas is drythe water dew-point temperature is lower than 0C, below the process temperature conditions at

FIG. 1

PDVSA San Joaquin extraction plant.

FIG. 2

Production train at San Joaquin.

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SPECIALREPORT

GAS PROCESSING DEVELOPMENTS

Joule-Thomson valve 58 bar 66 bar 11C 18C 1 2 Silica gel x 2 Seperator J-T inlet 55 bar -33C 17 bar -79C Turbo-expander Compression Expansion Residual gas to national distribution system 69 barg

Wellhead natural gas

Separator J-T outlet

12

34

Glycol (TEG) dehydration contactor Glycol regeneration system Natural gas liquids Liquid stabilizer Molecular sieve columns x 4

Separator T-E inlet

Separator T-E outlet

Deethanizer Natural gas liquids

FIG. 3

Process train schematic.

140 120 Process pressure, bar 100 80 60 40 20 0 -100 FIG. 5

Hydrocarbon dew-point reduction at process stages Residual gas Outlet J-T seperator Gas entering plant

-80

-60 -40 -20 0 20 40 Hydrocarbon dew-point temperature, C

60

80

Phase envelop (HC dew point curves) at stages throughout the liquid extraction process.

FIG. 4

Glycol contactor tower.

the prevailing process pressure. Therefore, while not entrained with liquid water, the gas is still heavily laden with HC liquids as a potential two-phase flow. The liquid content of the gas is suppressed through two stages of separation, before and after a Joule-Thomson (J-T) expansion valve that generates moderate
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cooling of the gas by approximately 7 Kelvin through partial pressure reduction at 8 bars. This yields part of the natural gas liquid production while reducing the HC dew-point gas temperature. The effect of this separation process is illustrated in Fig. 5. Reducing the HC dew point is important for the next stage of the processdehydration to trace moisture concentration through molecular sieve columns (Fig. 6). Reduction in the liquid loading of the gas is critical to the molecular sieves drying efficiency. If liquids are present, it adversely affects the moisture adsorption properties of the materials lattice structure and the overall operation lifetime of the sieves. Reduction in the water dew point below 80C (at process pressure equating to a moisture concentration of less than 0.1 ppmV) is critically important for operating the turboexpanders. Turboexpanders, (Fig. 7) or expansion turbines, recover useful work from the expansion of a gas stream while lowering the process temperature, resulting in partial liquefaction of the bulk stream. As the expansion nears isentropic, the turboexpander reduces the process gas temperature significantly more than

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SPECIALREPORT

GAS PROCESSING DEVELOPMENTS

FIG. 6

Molecular sieve dehydration columns.

FIG. 8

Hydrocarbon and water dew-point analyzer with a sampling system.

FIG. 7

Turboexpander and a deethanizer column.

expansion across a J-T valve for the same 38-bar pressure drop. The consequences of higher moisture concentrations within the process gas can be catastrophic, as the lowest temperatures in the liquid extraction process approaches 79C. If the gas water dew point rises above that temperature, then rapid ice formation will bring a high risk of physical damage to the rotating blades on the turboexpander. The deep cooled natural gas goes through multiple stages of liquid separation as the temperature cascades downward into a deethanization column. The result is a lean natural gas with only C1 and C2 hydrocarbons and some residual CO2 (Fig. 5). Compression of this remaining gas into the national distribution system is carried out by a centrifugal compressor linked to the shaft of the turboexpander, therefore capturing useful work from the gas expansion. A rich blend of propane, butane and heavier hydrocarbons forms the natural gas liquids transferred by pipeline to the fractionation plant.
Online dew-point analysis. Close monitoring of the dew-

point levels at critical points across the San Joaquin extraction facility requires 12 combined hydrocarbon and water dew-point analyzers (Fig. 8). PDVSA installed two analyzers on the glycol dehydration contactors and five on each production train. Each train had four individual molecular sieve columns that needed to be monitored continuously along with the common header outlet feed to the turboexpander plant. Dew point is the temperature where a vapor or the combination of vapors condense to form a liquid, seen as dew drops, when the gas is cooled. When the dew-point temperature is below freezing, ice crystals form. HC
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dew point is the condensation temperature of the heaviest HC components. Often, molecules with greater than 10 carbon atoms, present in ppm and sub-ppm concentrations, will condense to form HC condensates. The analyzer (Fig. 7) will simultaneously measure HCs and water dew point using two discrete sensor cells applying dedicated sensor technologies (Fig. 9). A direct fundamental principle adapted from the optical cooled mirror technique is applied for the HC dew-point measurement. An abraded optical surface with a conical depression profile has been developed specifically for the detection of the low surface tension films that are characteristic of the precipitation that occurs at the HC dew point. A visible red spectrum source directed onto the abraded surface scatters the light. A photo detector is positioned so that it captures the scattered light. It diminishes rapidly as the condensate film forms on the surface, cooling down to the temperature region of the HC dew point by a heat pump under the automatic control of the analyzer firmware. As the condensate film forms, a ring of light develops as the surface within the conical depression becomes more reflective. However, it is the secondary effect of reduction in scattered light intensity that enables the analyzer to detect the HC dew point to a sensitivity of 5 mg/m3 condensate mass per volume of gas. Unlike the HC dew point, an optical condensation technique cannot be applied to the water dew point measurement in this application. The water dew point temperature is significantly lower than the HC dew-point, such that any cooled surface would be flooded with condensate at a temperature far higher than the water dew point. For such measurements, a ceramic moisture sensor is used. Working on a moisture adsorption principle, the sensor adsorbs moisture into a micron-thin hygroscopic metal film in equilibrium with the flowing gas stream. The sensor exhibits an impedance change in proportion to the partial pressure of moisture vapor, the most elementary hygrometric unit. This is directly related to dew-point temperature, the measure-

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GAS PROCESSING DEVELOPMENTS

ment unit where each sensor is calibrated. These sensors have an extremely wide sensitivity range, being calibrated traceable to national metrology standards from 100C to +20C dew point. They also have the capability to measure directly at process pressure conditions representing greater than 20,000 ppmV moisture content at full scale compared to less than 0.01 ppmV at the low endthis is important for measuring the turbo expander feed gas.
In-situ measurement verification.
FIG. 9 Permeable gold lm Hygroscopic mono-layer Base electrode Ceramic substrate Moisture molecules

SPECIALREPORT

Although the sensors performing the online water dew point measurement are factory-calibrated traceable to national metrology standards, the critical nature of the water dew-point measurement for the turboexpander feed gas demands that PDVSA site personnel carry out periodic verification of the online analyzers during field operation. This is done in-situ using a portable dew point analyzer. Given the extremely low level of water dew point within the process (< 80C dew point) and the process pressure of 60 barg, equating to less than 0.1 ppmV, it is advantageous to carry out the verification measurement by installing a reference dew-point sensor within the online analyzer on a temporary basis. This enables both online and reference sensors to be in total equilibrium with the process gas sample under the same conditions over the duration of some hours. Through this method, PDVSA was able to maintain the highest level of confidence in the measurements.

Schematic diagrams of ceramic impedance moisture (left) and HC dew-point detection technique (right).

FIG. 10

Traces from molecular sieve capacity tests. Note: the Y-axis is scaled in F dew-point temperature.

Process plant proving field trials. During June and July

of 2009, PDVSA carried out trials to determine the operational status of the molecular sieve desiccant within the four drying columns on Train B at the San Joaquin facility. During normal plant operation, the columns were operated in an overlapping sequence for 36 hr before going offline for regeneration by heating to 300C and back-flushing during an 8-hr period. At least three of the columns were in process operation in parallel at one time. During the plant-proving trials, the total adsorption capacity of each column was assessed through continuous operation until moisture breakthrough was detected by the online monitoring of dew point analyzers. After three years of use for the current molecular sieve material and an expected operational lifetime prediction of 3 yrs, the purpose of the test was to determine the capacity of each bed and the urgency of scheduling when to replace each desiccant. Furthermore, the regeneration cycle times were reassessed to optimize the sequence throughout the remaining lifetime of the existing bed material. Fig. 10 illustrates the moisture breakthrough on two individual desiccant beds occurring after 30 hr and 32 hr of continuous adsorption. The red trace shows the increase in the gas dew point in the common header resulting from these high moisture excursions. Given similar findings on the other two desiccant beds, PDVSA

reduced the operational adsorption period for each column to 27 hr, with a 9-hr regeneration sequence, to extend the useful life of the molecular sieve material through the intended replacement date of February 2010. The proving trials served to reaffirm to the PDVSA plant operations and laboratory staff. It was shown that the performance of the analyzers after the first 18 months of successfully monitoring the dew-point conditions was critical to the continuous process operation and the reliability of key plant equipment. HP

Andy Benton joined Michell Instruments Ltd in 1983, initially

in the R&D section. Throughout his career he has specialized in devising innovative solutions to applications for online process gas and liquid analysis. Most particularly for the natural gas industry, Mr. Benton has advised best practice for water and hydrocarbon dew-point control and measurement to producers, pipeline operators and large scale end users covering six continents.

Carlos Valiz joined PDVSA Gas 15 years ago as senior chemist

specializing in laboratory analysis. His current position is quality control supervisor for the complete Eastern Venezuela division of PDVSA Gas.

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