This application claims the benefit of U.S. provisional patent application serial no. 61/568,335 filed on December 8, 201 1 , and U.S. utility patent application 13/705,335, filed December 5, 2012.

METHOD TO DETERMINE THE DRA IN A HYDROCARBON FUEL

FIELD OF THE INVENTION

The invention relates to the detection of "drag reducer additives" (DRA) in liquid hydrocarbon fuels. More specifically, the invention relates to a method to determine the presence, quantity and manufacturer of DRA Dissolved in a Hydrocarbon Fuel.

BACKGROUND OF THE INVENTION

In order to move fluid through pipelines, into or out of wells, or through equipment, energy must be applied to the fluid. The energy moves the fluid, but is lost in the form of friction. This frictional pressure drop, or drag, restricts the fluid flow, limiting throughput and requiring greater amounts of energy for pumping.

Materials can be added to flowing fluids in order to reduce the energy lost due to friction, or drag, thus permitting the movement of more fluid at the same differential pressure. The resulting reduction in frictional pressure drop improves pumping efficiency, lowers energy costs, and increases profitability. Materials for reducing drag in flowing fluids are generally known as "drag reducing agent (or additive)" (DRA).

DRA is found in two forms, sheared and unsheared, which currently require separate methods for detection. The current detection methods are time consuming, up to 48 hours, and require large quantities (up to 1 quart) of sample to be used for detection.

DRA, whether in the sheared or unsheared form, is a contaminate in liquid hydrocarbon fuels, and has the potential to cause numerous problems. In 2010 liquid hydrocarbon fuel was delivered to retail locations with unsheared DRA present. There is a need for an efficient inexpensive method for detecting DRA in hydrocarbon fuels.

Methods of detecting and quantifying drag reducer additive in liquid hydrocarbon fuels commonly are time consuming and expensive. Often, large samples are used.

SUMMARY OF THE INVENTION

DRA (Drag Reducing Agent (or Additive)) is used within the pipeline industry to lower the cost of transporting hydrocarbons through the system by reducing pumping forces. The additive is either a singular or multi-type of polymerized alpha olefin(s). DRA is usually added to fuel between 0.5 ppm and 15 ppm polymer content, however, concentrations as high as 60 ppm have been found. Because of this low concentration, and the polymer's chemical similarity to the hydrocarbon fuel, detection by normal analytical methods is extremely difficult. A pyrolysis attachment onto a Gas Chromatograph-Mass Spectrometer (GC-MS) that can fractionate the sample into various boiling point ranges to remove most of the hydrocarbon fuel may be utilized to detect the DRA polymer. This leaves the polymer at sufficiently high enough concentrations to analyze. It does not matter if the DRA polymer is in the relatively inert "sheared" state (molecular weight c.a. 1 - 5 mega Daltons) or the "unsheared" state (molecular weight c.a. 50 - 500 mega Daltons). It is not uncommon for both types of DRA polymers to be found in a fuel supply.

The current methods require samples of 1 quart and can take up to 48 hours to process. The current methods also require different analysis for sheared and unsheared DRA. The form of the DRA is often unknown to the user often requiring redundant testing.

A single testing method requiring no sample preparation has been developed to detect the presence of DRA (whether in the sheared for unsheared form), and to determine the manufacturer(s) of the DRA. To date, there is no available method to quickly and easily perform this analysis. Only 60 microliters of sample are needed for the determination, which can be performed within two hours.

In the preferred embodiment a Quantum Analytics Pyrolysis add-on is attached to a Gas Chromatograph-Mass Spectrometer that can fractionate the sample into various boiling point ranges to remove most of the hydrocarbon fuel, leaving the polymer, which is at a sufficiently high concentration level to analyze.

Other objects and advantages of the present invention will become apparent to those skilled in the art upon a review of the following detailed description of the preferred embodiments and the accompanying drawings.

IN THE DRAWINGS

Fig. 1 shows a schematic of the instrument combination.

Fig. 2 shows a multi-functional pyrolyzer coupled with chromatograph.

Fig. 3 shows a calibration curve for DRA polymer content.

DETAILED DESCRIPTION OF THE INVENTION DRA (Drag Reducing Agent (or Additive)) is used within the pipeline industry to lower the cost of transporting hydrocarbons through the system by reducing pumping forces. The polymer can be found in a singular or multi-type of polymerized alpha olefin(s). It is not uncommon for both types of DRA polymers to be found in a fuel supply. DRA is usually added to fuel between 0.5 ppm and 15 ppm polymer content, however, concentrations as high as 60 ppm have been found. Because of this low concentration, and the polymer's chemical similarity to the hydrocarbon fuel in which it is dissolved, detection by normal analytical methods is extremely difficult. A pyrolysis attachment onto a Gas Chromatograph-Mass Spectrometer (GC-MS) that can fractionate the sample into various boiling point ranges is employed. The system then removes most of the hydrocarbon fuel, leaving the polymer, which is at sufficiently high enough concentration to analyze. This instrumental method requires no sample preparation to determine whether a fuel contains DRA. The instrument also determines the manufacturer(s) of the DRA. The present invention provides a single testing method for detecting DRA in hydrocarbon fuel regardless of whether the DRA is in the relatively inert "sheared" state (molecular weight c.a. 50- 500 mega Daltons) or the "unsheared" state (molecular weight c.a. 50-500 mega Daltons). To date, there is no available method to quickly and easily perform this analysis. Only 60 microliters of sample are needed for the determination, which can be performed within two hours.

A Quantum Analytics Pryolysis add-on, containing an autosampler, multiple-zone furnace, and cryogenic trapping apparatus is fitted to a Gas Chromatograph with Mass selective detector as shown in Fig. 6.

Most liquids and solids can be chemically characterized using five powerful thermal techniques:

1. Evolved Gas Analysis (EGA) provides a thermal profile of the sample. A short 2.5m deactivated capillary tube connects the Multi- Functional Pyrolyzer and the GC detector. As the sample temperature increases, compounds "evolve" from the sample matrix and are detected. EGA enables one to determine the complexity of the sample, the presence of volatile compounds and the proper pyrolysis temperature.

2. In Thermal Desorption Analysis the furnace temperature is programmed up and compounds are desorbed as a function of their boiling points. The compounds are first cold trapped at the head of the column and then chromatographically separated and detected.

3. "Single Shot" Analysis, pyrolysis is used for macromolecular and other non-volatile materials. When a sample is rapidly heated to high temperatures, chemical bonds are broken. The resulting fragments are chromatographically separated, producing a pyrogram. The pyrogram is used to characterize the nature of the original sample.

4. "Double-Shot" is the unique combination of Thermal Desorption and Pyrolysis. Thermal Desorption is used to identify volatile compounds in the sample such as residual solvents, reaction products, monomers, and additives like antioxidants and stabilizers. Pyrolysis is used to characterize the polymer.

5. EGA GC/MS Analysis is used to profile the sample components. Each fraction of the sample can be automatically collected, analyzed and characterized using heart cutting techniques.

A search for polymer identification utilizes an algorithm to tentatively identify samples based on their GC/MS program or EGA profile.

The instrumentation of the present invention has a number of potential variations or additional equipment which could be added to streamline the process. Some of those additional variations and add-ons include, but not limited to:

- A carrier gas selector enables the operator to select between two whole gases. Helium is normally used, air and oxygen are used when performing reaction pyrolysis.

- An auto-Shot sampler analyzes up to 48 samples using three different operating modes.

- With μ-jet cryo trap compounds are focused at the head of the column prior to analysis using nitrogen cooled to -196°C.

- Sample fractions can be automatically vented (i.e., cut) or directed to the analytical column.

- Ultra Alloy EGA tube and capillary columns is multi-step process yields a deactivated stainless steel surface which is stable at temperatures greater than 400°C.

- Vent-free GC/MS adapter enables the operator to change the columns without venting the MS.

In thermal desorption, the sample cup is dropped into the μ-furnace at 40°C. The furnace is programmed to 320°C at 20°C/min. The volatile compounds are reconcentrated using the μ-jet cold trap. The GC subsequently separates the desorbed volatile compounds. The mass spectra are used to identify each compound.

Once the thermal desorption is complete, the sample cup is lifted out of the μ-furnace. The furnace is heated to 600"C and the sample cup is dropped back into the furnace. The non-volatile portion of the sample is pyrolyzed. The resulting pyrogram can be matched with standard pyrograms using the pyrolysis library.

The search may consist of two libraries based on GC/MS data: one contains EGA thermograms and the other pyrograms. The libraries use a search algorithm which enables one to identify unknown polymeric materials rapidly. The libraries contain averaged GC/MS data for hundreds of polymers. One can easily edit or customize the libraries to fit specific applications.

The practice of injecting a known amount of a single compound along with the unknown compound is known as Internal Standard. This negates any deviation in detector sensitivity or total volume of fuel used. Selection of an Internal Standard provides numerous challenges because it must be; a compound that is robust enough to survive the first phase of the analysis, which is to drive off any solvent or fuel. This phase effectively leaves only the DRA polymer and the Internal Standard left for subsequent analysis. This phase is necessary for the low limits of detection of DRA polymer. The Internal Standard must be non-interfering. The presence of the Internal Standard must not affect the detection of the DRA polymer. The Internal Standard must be different enough from both the fuel being analyzed and the DRA polymer so that it can be distinctly identified. The Internal Standard must be soluble in fuel and the solvent used to build the calibration curve. The Internal Standard must be added directly to the fuel. Initially, the Internal Standard must be injected into the GC-MS during the same temperature window that carries the DRA polymer into the GC-MS. This combination of factors makes finding an appropriate Internal Standard difficult. A number of suitable polymers exist including, but not limited to polyproplylene, polyethylene, and polyester. While these polymers are suitable, polystyrene is optimal in this application. Fig. 1 shows the instrument combination of a multi-functional pyrolyzer 2 combined with a gas chromatograph 4 and a mass spectrometer 6. The instrument combination may be attached to a computer 8 for analysis. The combination of instruments is used as a DRA detector 10. The DRA detector 10 is capable of determining if DRA is present in hydrocarbon fuel regardless of the form, and determining the manufacturer of the DRA if present.

A gas chromatograph 4 (GC) is a common analytical chemistry tool which separates and analyses compounds that can be vaporized without decomposition.

The mass spectrometer 6 (MS) is a common analytical tool that measures the mass to charge ratio of charged particles. The mass spectrometer 6 can be combined with a gas chromatograph 4 (GC-MS) to positively identify the presence of a particular substance in a given sample.

A pyrolyzer 2 is analytical tool that thermo chemically decomposes an organic material at elevated temperatures without oxygen.

In the preferred embodiment, a raw sample is fed into a multi-functional pyrolyzer 2. A programmatic method is enabled on the instrument which fractionates the raw sample into three cuts (fractions) based on boiling point. The first fraction (fraction A) contains mostly fuel and may be analyzed on the gas chromatograph 4; however, this is not necessary to obtain DRA information. The second fraction (fraction B) contains some of the fuel and, depending on the type of DRA, may contain information on solvent carrier. For example, manufacturer X may make two different DRAs that vary only by solvent carrier, the active polymer will be identical. One solvent is heavy soy oil, and the other is a light ketone. The soy oil will appear in fraction B, while the ketone will not. The third fraction (fraction C) contains information about the polymer (the active ingredient of interest) in the DRA. This fraction is heated to temperatures high enough to pyrolyze the polymer, thereby breaking it into smaller molecule fractions that can be analyzed by a gas chromatograph-mass spectrometer. These molecular fractions form the fingerprint that is unique to each manufacturer. Known samples from the manufacturer have been compiled to create "library" of results. The results from the third fraction (fraction C) are compared against the library of results to determine who manufactured the DRA.

For DRA is very low concentrations (less than 4 part per million), the mass spectrometer may be operated in select ion monitoring mode, because there is a unique distribution of pyrolyzed polymer, and there is a predominate peak on the gas chromatograph that contains a unique ion distribution.

Another multi-functional pyrolyzer and gas chromatograph uses quantum analytics. Quantum provides an array of sample preparation and introduction of products. Products available include: pyrolysis, thermal desorption, headspace, purge and trap, high throughput autosampling, RFID tracking, large volume inlets, and preparative fraction collection. An example of pre-injection liquid manipulation is as follows. A sample of derivatization agent may be added, the sample vial heated, mixed and then injected into the system.

Still another gas chromatograph and pyrolyzer is based upon a vertical μ-furnace pyrolzer. The sample goes from ambient to the furnace temperature in less than 20ms. The sample falls to the same position within the furnace every time, and the furnace temperature is calibrated at the sample location so that the selected temperature is the actual temperature. A separate interface heater ensures thermal homogeneity. There is no transfer line and no polymeric material in the sample path. All contact surfaces are quartz.

Only the compounds evolving from the sample over a selected temperature range are transferred to the column and chromatographically separated. Analyzing each zone independently generally results in a simple chromatogram. Analysis time is sharply reduced and instrument contamination essentially is eliminated by analyzing only the portion of sample that is of interest. EXAMPLE 1

To test the instrumental method and Internal Standard derived in the present invention a calibration curve was built using samples of unsheared DRA dissolved in a solvent (toluene). A sample of diesel with a known amount of sheared DRA polymer was analyzed.

Internal

Standard Corrected

Run DRA DRA

No. Cone Peak Area Area DRA Peak Area

1 0 1425283 0 0

2 22.8 2918321 71215 0.02440273

3 56.7 2262470 138149 0.061061141

4 100 2981729 432912 0.145188245

Fig. 3 shows the calibration curve for DRA polymer content. The analysis returned the result of 52 ppm.

EXAMPLE II (PRIOR ART

A fuel terminal comprises a DRA adsorption unit comprising a cylindrical Vessel containing 10,000 pounds of an effective removal agent comprising activated carbon A. The vessel is constructed in an upflow design that allows liquid hydrocarbon fuel to enter at the bottom of the vessel and leave from the top. The DRA adsorption unit is located between the fuel storage tanks and the loading rack used by customers that purchase tanker truck quantities of fuel. The adsorption unit further comprises a bypass valve and loop that allows fuel to bypass the adsorption unit as it is pumped from a given terminal storage tank to the loading rack.

Each terminal tank of fuel is tested using activated carbon A as a detection agent. When the test indicates that DRA is present in a tank of liquid hydrocarbon fuel, the bypass valve to the adsorption unit is closed, thereby directing the liquid hydrocarbon fuel containing the DRA to pass from the tank and through the adsorption unit. When the test indicates that DRA is not present, the bypass valve is opened, thereby causing the fuel to bypass the adsorption unit as it is pumped from that terminal storage tank to the loading rack.

The 10,000 pound vessel of activated carbon removes the DRA from up to 372,000 gallons of the gasoline in the terminal tank.

The above detailed description of the present invention is given for explanatory purposes. It will be apparent to those skilled in the art that numerous changes and modifications can be made without departing from the scope of the invention. Accordingly, the whole of the foregoing description is to be construed in an illustrative and not a limitative sense, the scope of the invention being defined solely by the appended claims.