SPE 67326 Factors Affecting the Performance of Crude Oil Wax-Control Additives

John S. Manka, SPE, and Kim L. Ziegler, The Lubrizol Corporation

Copyright 2001, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the SPE Production and Operations Symposium held in Oklahoma City, Oklahoma, 24-27 March 2001. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words: illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A. FAX 01-972-952-9435.

affect the performance of crude oil wax control additives and what contributes to crude oil specificity. Crude Oil Pour Point Depressants. The pour point of crude oil is the lowest temperature at which movement of the crude is observed. In this test, after preliminary heating, the crude is cooled at a specific rate and examined at intervals for movement. The lowest temperature at which movement of the specimen is observed is recorded as the pour point. When the crude reaches its pour point, the sample is not frozen solid. What actually happens is that the paraffins in the crude crystallize and form a matrix of wax crystals. The wax crystal matrix holds the bulk of the liquid portion of the crude within it. By trapping the liquid portion within the wax crystal matrix, the wax crystals prevent the liquid in the crude from flowing and the sample no longer moves. Anything that disrupts the formation or the properties of the wax crystal matrix, such as pour point depressants, will affect the pour point of the crude. Wax control additives, which include crude oil pour point depressants, are polymers with pendant hydrocarbon chains that interact with the paraffins in the crude and thus inhibit the formation of large wax crystal matrices, (Figure 1). The interaction retards wax crystal formation and growth, alters the paraffins heat of crystallization and subsequently depresses the crudes pour point while affecting the size and shape of the wax crystals2. Examples of the types of chemistries used as crude oil pour point depressants include ethylene vinyl acetate copolymers, vinyl acetate olefin copolymers, alkyl esters of styrene maleic anhydride copolymers, alkylesters of unsaturated carboxylic acids, polyalkylacrylates, polyalkylmethacrylates, alkyl phenols, and alpha olefin copolymers. Crude Oil Specificity. Wax control additives for crude oil are plagued by "specificity". Specificity is exhibited when a cold flow package will work only for a specific crude oil. Even slight changes in the crude oil wax composition can cause a reduction or a total loss of performance.

Abstract Crude oil producers have used pour point depressants with great success for several decades. However, chemical wax control packages can be plagued by crude oil specificity, large package treat rates, and waxy components that can be hard to apply. This paper discusses what factors affect the performance of crude oil wax control additives and what contributes to crude oil specificity. This study investigated the effects of the wax control additives' polymer backbone, pendant chains, and molecular weight on cold flow performance. The impact of the solvents used, the extent of the packages' dilution and the effect of proper additive dosing is addressed. Introduction Handling and transporting crude represents a major challenge for crude oil producers. Transporting crude from its source to the refinery can involve sub-sea umbilicals, pipelines, intermediate storage tanks, and transportation vessels, all of which depend on the crude oil remaining liquid in the various environments and conditions of transportation. Oil producers use several methods to ensure a liquid product and an uninterrupted flow of crude. These methods include heating, dilution with lighter stocks, and the preferred method, additizing with pour point depressants. Pour point depressants have been used with great success for several decades. However, they can be plagued by crude oil specificity, large package treat rates, and waxy components that can be hard to apply1. This paper discusses what factors

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Specificity arises from the interaction between the pendant chains of the wax control additives and the waxes present in the crude oil. The waxes in the crude are specific to the crude, but can and do change over time. If the crude's characteristics change, i.e. the wax distribution changes, the wax control additive may no longer be well matched and pour point performance suffers. If the crude change is slight, an increase in the wax control additive's treat rate often restores the performance but if the change is more significant, a change to a new wax control additive package may be needed to restore the pour point depression. Experimental A modified ASTM D97-96A Standard Test Method For Pour Point Of Petroleum Products was used to determine the pour point of the crude oils tested. In this test, after preliminary heating, the sample is cooled at a specified rate and examined at intervals of 1C for flow characteristics (in the unmodified test 3C intervals are used). The lowest temperature at which movement of the specimen is observed is recorded as the pour point. The repeatability of this measurement is less than 2.52C and the reproducibility is less than 6.59C. The ASTM D 445 Standard Test For Kinematic Viscosity Of Transparent And Opaque Liquids was used to measure the viscosity of the diluted pour point packages. The gel permeation chromatography molecular weight determinations were done using a Waters 2690 unit equipped with a Water 410 refractometer. Molecular weight determination was made on the analytical sample and the values reported are given relative to polystyrene standards. The relative calibration curve was derived from a set of 12 narrow polystyrene standards (PSS ReadyCal) injected in duplicate. The crude oil pour point depressants used in this study (PPD A through H) included both experimental and commercially available packages. The solvents were commercial grade and were used as received. The crudes employed were chosen because they represented a variety of different geographical areas of North America, Europe and Asia. Factors That Affect The Performance Of Crude Oil Wax Control Additives Crude oil pour point depressants are polymers made from discrete monomers. The polymers have three variable characteristics that may affect their performance; the polymer backbone, the length of the pendant chains and the polymer molecular weight. The backbone and pendant chain length can be changed by using different monomers. The polymer molecular weight can be changed by adjusting reaction conditions, amount of initiator used, etc. The Effect Of The Polymer Backbone. The polymer backbone is not believed to play a large role in the pour point depression performance of "comb" type polymers. It is believed that the backbone only provides a structure from which the important pendant chains are suspended3. This is not necessarily the case in ethylene vinyl acetate co-polymer

pour point depressants so these co-polymers will not be considered here. To investigate the effect of the polymer backbone, pour point depressants with the same pendant chain lengths, but different backbones were tested. Every effort was made to keep the molecular weight of the polymers the same (vida infra). Table 1 shows the performance testing of the pour depressants with different polymer backbones. The data show that the polymer backbone has a slight but statistically significant effect on the performance of the wax control additive. The Effect Of The Length Of The Pendant Chains. The interaction between the wax control additives and the paraffin in the crude oil is crucial and the additives work best when they are matched to the paraffin distribution in the crude. Figure 2 shows the effect on performance that qualitatively matching the pour point depressants' pendant chain length to the wax in crude oil has on the additized crude's pour point. The various pour point depressants were dosed into the crude at equal active chemical. As the average carbon number of the pendant chain on the pour point depressant increases, the pour point of the additized crude drops until it reaches a minimum and then increases again. The minimum in the data shows that PPD Es average pendant chain length is most closely matched with the paraffin distribution in the crude and the greatest pour point depression results. The Effect Of Polymer Molecular Weight. The molecular weight of the wax control polymer may affect the interaction of the polymer with the paraffins. A very short, low molecular weight polymer may not have the molecular volume to disrupt the paraffin crystals as it co-crystallizes within the paraffin matrix. A very long, high molecular weight polymer may be so large that it interacts with itself instead of the crude oil paraffins or the polymer's solubility in the crude oil may be limited and actually initiate paraffin crystallization and thus raise the pour point of the crude oil. Table 2 shows the effect of molecular weight on the pour point performance of a family of pour point depressants. The backbone and side chain lengths are the same for each polymer, only the molecular weight varies. The data show that, over the molecular weight range tested, neither weight average molecular weight, number average molecular weight nor peak molecular weight affects the pour point performance of the wax control additives. The monomer has no pour point depression activity as one would expect. Although the monomer may interact with the paraffins, the monomer's "molecular volume" is apparently too small to disrupt paraffin crystal formation. The Effect Of Solvent And Dilution On The Performance Of Crude Oil Wax Control Additives. Undiluted pour point depressants are waxy materials that are often solids at ambient temperature. To pump these products in the field, they usually need to be drastically diluted with solvent. Therefore, solvents

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comprise a very large portion of these finished formulations to make a handlable product. Much research has gone into developing and testing new and existing polymers, additives and formulations for this application. However, very few studies have examined the role that solvent plays on the performance of the cold flow polymer 3,4. The Effect Of Solvent On Performance. It is generally accepted in polymer science that solvents have a large effect on the physical properties of polymers. It is known that solvent influences the effective hydrodynamic specific volume of the polymer. The effective hydrodynamic specific volume is indicative of the degree that a polymer interacts with the solvent, and is a measure of how coiled or uncoiled the polymer is in that solvent. The degree of polymer coiling may be important because a solvent that causes the polymer to be highly coiled and interact predominantly with itself may be less likely to interact with the paraffins of the crude and may have less pour point performance than the same polymer dissolved in a solvent in which the polymer is well solvated, uncoiled and readily accessible. In a "good" solvent, the polymer maximizes its interaction with the solvent and the polymer is uncoiled and has a large radius of gyration and thus a large effective hydrodynamic specific volume. In a "poor" solvent, the polymer minimizes interaction with the solvent leading to a coiled conformation which exhibits a small radius of gyration and thus a small effective hydrodynamic specific volume. The concept of radius of gyration and effective hydrodynamic specific volume is shown schematically in Figure 4. Package viscosity is used to determine which solvents are "good" and "poor" solvents for the polymers. "Good" polymer solvents exhibit a higher package viscosity than "poor" solvents. "Good" solvents cause the polymer to be fully expanded, maximizing their interaction with the solvent. This expansion causes the polymer/solvent complex to act like a very large molecule with an effective increase in viscosity. In an analogous manor, "bad" solvents cause the polymer to act as a small molecule with a corresponding lower apparent viscosity. To investigate the effect of the solvent used on the performance of the wax control package, pour point depressants C and D were dissolved in various solvents and their package viscosity and pour point depression performance were assessed. Table 3 shows the viscosity of the polymers at equal actives in various solvents. The data show that the viscosity of the solvent-polymer package varies greatly with solvent. The solvents that exhibit high package viscosity are "good" solvents for this particular polymer and those with low package viscosity are "poor" solvents for this particular polymer. Based on the viscosity data in Table 3, pour point packages using heptane, No.2 diesel fuel and methylene chloride were chosen and additized into crude oil and their pour points determined. Heptane, diesel fuel and methylene

chloride were selected because they represent a "poor", an intermediate and a "good" solvent for these particular polymers. The results in Table 4 show that, within repeatability of the ASTM D97-96A Standard Test Method For Pour Point Of Petroleum Products, regardless of whether a "good" solvent, an intermediate solvent or a "poor" solvent for the polymer is used, the wax control performance is the same. The solvent has no effect on pour point performance because the solvation from the solvent used in the package is immediately lost upon addition to the crude. Upon additization, the wax control polymer is solvated exclusively by the crude. Subsequently, the identity of the solvent used in the package is not important to ultimate pour point performance. The Effect Of Polymer Dilution On Performance. It is generally accepted in polymer chemistry that the concentration of a polymer in a solvent has a large effect on the physical properties of the polymer 5. The concentration of the polymer in the solvent will affect the extent of interaction of the polymer with itself. At high concentrations the polymer may interact with other polymer molecules and become entangled. This entanglement may impact the accessibility of the polymer to the paraffin in the crude and, thus, may impact the performance of the cold flow modifier package. At low concentrations, the polymer is fully solvated and should not interact with other polymer molecules and should be very accessible to the paraffins in the crude oil. Table 5 shows the effect that dilution has on the performance of wax control additives in a Gulf of Mexico crude. PPD G and PPD H were diluted with xylene. The effect of xylene is also shown. Within repeatability of the ASTM D97-96A Standard Test Method For Pour Point Of Petroleum Products, the extent of dilution of a wax control product has no effect on the performance of the package. Upon additization, the wax control polymer is "infinitely dilute" at the typical treat rates for pour point depression performance of these polymers in crude oils. "Infinitely dilute" means that one polymer has no interaction with, nor any effect on, another polymer in the solution. Subsequently, the extent of dilution of the pour point depressant package is not important to ultimate pour point performance. The Effect Of Mixing On Performance. People have reported that dilute cold flow packages actually had better performance than concentrated packages even when additized into crude at equal polymer actives. These results led some to believe that dilution was beneficial5,6. In the previous section, we showed dilution had no effect on performance. To explain why some labs have seen this apparent "dilution benefit", we studied the mixing of the cold flow polymer into the crude to see if more efficient mixing was the cause of the enhanced performance of diluted polymers. For this investigation, the extent of mixing was varied and the effect on pour point performance was noted. To investigate the effect of mixing, three samples of the crude oil

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used in Table 4 were additized with 200ppm of PPD C. For Sample #1, PPD C was additized into the crude via micropipette and the additized crude was not mixed. Sample 2 was additized the same way but was gently mixed by hand for five seconds. Sample 3 was additized the same way but was mechanically shaken for 5 minutes. ASTM D97-96A pour points were then run on these three additized crude oil samples. Next, the effects of mixing and polymer dilution were determined by making three samples of the same crude oil additized with 800ppm of a three fold diluted version of PPD C. This delivers that same amount of active pour point polymer as in the mixing study in the previous paragraph. Again the extent of mixing was varied. In the preparation of sample 4, the diluted PPD C was additized into the crude via micropipette and the additized crude was not mixed. Sample 5 was additized the same way but was mixed by hand for five seconds. Sample 6 was additized the same way but was mechanically shaken for 5 minutes. Pour points were then run on these three samples. Table 6 shows the effect that mixing and dilution have on the performance of wax control additives in this crude. The data shows that the extent of mixing has a great effect on the performance of the pour point depressants. Again, dilution has no effect on pour point depression provided mixing is efficient.

individual crudes, as one would expect. We see that neither PPD E nor PPD G have a significant effect on the blended crude's pour point. However, combining PPD E and PPD G did successfully depress the blended crude's pour point. These results prove the concept of over coming specificity using additive blends. Conclusions This paper discussed what factors affect the performance of crude oil wax control additives. The data show that: 1) Over the molecular weight range tested, neither weight average molecular weight, number average molecular weight nor peak molecular weight affects the pour point performance of the wax control additives. 2) The polymer backbone has a slight but statistically significant effect on the performance of the wax control additive. 3) The most important variable to wax control performance is the identity of the polymer's pendant chains. 4) The interaction between the wax control additives and the paraffin in the crude oil is crucial and the additives work best when they are matched to the paraffin distribution in the crude. 5) The solvent used in the wax control package has a great effect on the package viscosity but had no effect on the performance of the wax control package. 6) Dilution also had no effect on the performance of the wax control package. 7) Effective mixing of the additive into the crude oil has a great effect on the performance of pour point depressants 8) Specificity can be over come by using mixtures of pour point depressants to be able to treat a broad range of crude oil wax distributions.

Overcoming Specificity Specificity arises from the interaction between the wax control additive's pendant chains and the waxes present in the crude oil. Figure 3 schematically shows how matching the wax control additive to the crude's wax distribution leads to specificity. Wax control additives work best when they are well matched to the wax distribution of the crude they are treating [1]. If the crude's wax distribution changes, the wax control additive is no longer well matched and pour point performance suffers. It may even be necessary to use a different pour point depressant. However, if the wax distribution changes yet again, the pour point depressant may need to be changed again. By using mixtures of wax control additives, a broader range of wax distributions can be targeted, and specificity should often be overcome. To investigate this proposed technique of addressing specificity by using a mixture of pour point depressants, we made a "blended crude oil" by mixing equal proportions of two crude oils, each only responsive to a particular pour point depressant. We used the crude oil already discussed in Table 5 which responds to PPD G and the crude oil described in Figure 2, which responds to PPD E. The blended crude oil made from these crudes will have a different wax distribution than the individual crudes and should not respond to the individual pour point depressants, PPD G or PPD E, but should respond to a mixture of the two pour point depressants. Table 7 shows that the ASTM D97-96A pour point of the blended crude falls between the pour points of the two

Acknowledgments The authors would like to thank Dr. Dennis M. Dishong for his contributions to this paper.

References
1."A Novel Method to Winterize Traditional Pour Point Depressants" John S. Manka, James S. Magyar, and Robert P. Smith, Society of Petroleum Engineers paper # 56571, 1999. 2. "The Effect of Cloud Point Depressants On Diesel Fuel Properties". John S. Manka and Thomas M. Sopko, paper #982575, Society Of Automotive Engineers, 1998. 3. "Crystallization Of N-Dotriacontane From Hydrocarbon Solution With Polymeric Additives" D.H.M. Beiny, J.W. Mullins and K.Lewtas, Journal of Crystal Growth, vol. 102, 801-806, 1990. 4. "Solubility Of Octacosane And Hexatricosane In Different Alkane Solvents", H.E.L. Madsen, J.C.S. Faraday Trans. I, vol. 75, 12541258, 1979. 5. "Solvent Effect On The Action Of Ethylene-Vinyl Acetate Copolymer Pour Point Depressant In Waxy Solutions", J.W. Qian,

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G.R. Qi, Y.L. Xu, and S. L. Yang, Journal of Applied Polymer Science, vol. 60, 1575-1578, 1996. 6. "The Structure and Activity of Polyalphaolefins as Pour Point Depressants", Chong-Xiang Xiong, Lubrication Engineering, page 196, March 1993.

chemistry from Canisius College, Buffalo, New York and a Ph.D. in Organic chemistry from the State University of New York at Buffalo, Buffalo, New York. Kim L. Ziegler is a laboratory technician in the Process Chemicals Group of The Lubrizol Corporation. Mrs. Ziegler has 6 years experience in additive research including four years in the area of Fuels, Refinery and Oilfield products. The Lubrizol Corporation is a worldwide supplier of performance chemicals for fuel, lubricants, and other specialty markets.

The Authors Dr. John S. Manka is the Research Manager for The Process Chemicals Group of The Lubrizol Corporation. He has ten years experience in additive research and formulation including four years in the area of Fuels, Refinery and Oilfield products. Dr. Manka received a BS Degree in

TABLE 1 -- THE EFFECT OF POLYMER BACKBONE ON POUR POINT DEPRESSANT PERFORMANCE

Polymer Backbone None Backbone 1 Backbone 2 Backbone 3 Backbone 4 Pour Point In C 15 -1 -4 -3 -5

TABLE 2 -- THE EFFECT OF MOLECULAR WEIGHT ON THE POUR POINT PERFORMANCE OF 400PPM OF POUR POINT DEPRESSANT E
Batch None Monomer E 1 2 3 4 5 6 7 8 9 10 M number -489 56000 33000 64000 54000 61000 78000 62000 54000 34000 71000 M weight -489 78700 42200 96200 81400 88900 133000 94000 75000 43000 128000 M peak -489 86700 40300 96000 90000 92700 124000 94000 85000 41400 119000 Pour Point in C 24 24 9 11 10 9 10 11 10 9 10 12

TABLE 3 -- THE EFFECT OF SOLVENT ON A 25% VOLUME ACTIVE POUR POINT DEPRESSANT
Solvent Kerosene Heavy Aromatic Naphtha Petroleum Naphtha Light Aromatic Petroleum Naphtha Xylene Heptane Hexane Methylene chloride Methyl Iso-butyl Ketone #2 Diesel Fuel PPD C 9.1 7.3 4.9 7.0 3.9 2.0 4.1 66.7 3.7 18.6 Viscosity In cSt @ 25C PPD D 21.8 16.4 16.0 10.8 8.4 5.5 10.6 218.9 7.7 43.8

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TABLE 4 -- THE EFFECT OF SOLVENT ON POUR POINT DEPRESSANT PERFORMANCE

Pour Point Depressant PPD C Treat Rate --200 ppm 200 ppm 200 ppm --200 ppm 200 ppm 200 ppm --200 ppm* 200 ppm* 200 ppm* Solvent None Heptane Diesel Fuel Methylene Chloride None Heptane Diesel Fuel Methylene Chloride None Heptane Diesel Fuel Methylene Chloride Pour Point In C 13 1 1 1 13 7 7 9 13 11 13 13

PPD D

None

* of the neat solvent

TABLE 5 -- THE EFFECT OF PACKAGE DILUTION ON POUR POINT DEPRESSION

None PPD G % Actives -100 50 5 -100 50 10 -0 0 0 Treat Rate -300 600 6000 -300 600 3000 -300* 600* 6000* Pour Point In C 35 -8 -8 -6 35 1 1 0 35 32 32 33

None PPD H

None Xylene * of the neat solvent xylene

TABLE 6 -- THE EFFECT OF MIXING ON POUR POINT DEPRESSANT PERFORMANCE

Sample --#1 #2 #3 Pour Point Depressant None PPD C Treat Rate --200 ppm 200 ppm 200 ppm Mixing --None 5 seconds 5 minutes Mixing and Dilution --None 5 seconds 5 minutes Pour Point In C 13 12 10 0

--#4 #5 #6

None 1:3 PPD C / Heptane

--800 ppm 800 ppm 800 ppm

13 11 10 1

TABLE 7 -- OVERCOMING SPECIFICTY BY USING MULTICOMPONENT PACKAGES

Crude Crude from Table 5 Crude From Figure 2 Blended Crude Crude from Table 5 Treat Rate --------300 300 --300 300 --600 600 300/300 Pour Point Depressant None None None None PPD G PPD E None PPD E PPD G None PPD E PPD G PPD E and PPD G Pour Point In C 35 24 29 35 -8 34 24 9 25 29 22 19 0

Crude From Figure 2

Blended Crude

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Paraffin In Solution

Pour Point Depressant

Paraffin Crystals

PPD Disrupts Crystal Formation

Figure 1. Idealized Mechanism Of Pour Point Depression.

25 Pour Point In C 20 15 10 PPD A PPD E PPD B PPD C PPD D PPD F PPD G PPD H None 5
Figure 3. Schematic Of Qualitatively Matching The Wax Control Additive To The Crude Oil Wax Distribution.

INCREASING CARBON NUMBER Figure 2: The Effect On Pour Point Of Matching The Pour Point Depressants To The Crude Oil.

Figure 4. Polymer Effective Hydrodynamic Specific Volume and Radius Of Gyration.