rI

SPE 49172 Multiphase transportation: hydrate plugging prevention

E.M. Leporcher, SPE/Elf Petroleum Norge,J.L. Peytavy/Elf Bergen, C. Labes-Carrier/Elf Petroleum Norge

I Society of Petroleum Engineers I

I .- ..

through crude oil natural surfactants

of

Exploration Production, Y. Mollier/Elf Exploration Production, J. Sjoblom/University

~pflaht

i998, s~iety

Of p~mleum

Enofnee~,

Inc Conference and Exhibhion held in

This parer was prepared

(or presentation

at the 199.9 SPE Annual Technlwl 1998. by an SPE PrWram towmetion Petroleum Committee by{he

New Odeans. Louisiana, 27-30 Septemkr rni &[he paper was selected SOcie[y of Petroleum nemSatily Eledronic refleti for prssentaffon EnQlnees anywsMon

foffowing

review

oi in fonnafion aspresen fed, Papm Fupses in Mnl of Petroleum

rnntained doesnot Wsented EWinee=. is@tifid4to mnsplwous

in an ab31racS submitted

by the author(s), Contents of the P8PC, as piesented, andaresubjed of the Sodetyof orstocage author(s) Engineer, tisofiWm,

have not b.3en reviewed ormemks

first years of production and thus result in large savings. With the present development of subsea-water separation technology, this process could firther become a stand alone alternative.
Introduction

Thematerfal, of fhe ?.odtiy

at SPE meetings are subject to pub fi-fion reprcdud[on, did ffbufion, cnnsent of the Sodelyof

review by Editorial Committees of anypafl Engineer3is prohibited

of this paper forcommerclal Pennisslonto reptiuce

without thewriften

Petroleum

anabstrad ofnotmom than 300wotis: acknM&gment ofwhere atibywhom TX 75083.3836, U.

illustrations maynot Mmplti Theabstrad must cnntain thepaper was presented Wtite Libradan. SPE, PO Box

83383-S. Ri&afd30n,

S. A.,ax 01-S72.952-9435 f

Abstract

Multiphase transportation is more and more contemplated in the development of oil and gas fields both in conventional and frontier areas (from remote satellite fields to deep offshore). This new environment has set forward new challenges in the field of hydrate plugging prevention in subsea flowlines. Increases of transportation distances and water depths place the fluids well inside the hydrate formation domain, and hence threaten flow in multiphase export lines. In such conditions, conventional hydrate prevention (alcohols, insulation, heating) can become very expensive and can in some cases jeopardize the economy of the project. To challenge this anticipated situation, the oil and gas industry has been looking for low dosage inhibitors : kinetic inhibitors which can delay hydrate crystallization, anti-agglomerants which let the hydrate crystallize but ensure their transportability in a slurry. This second process creates a water-in-oil emulsion which remains a transportable suspension afier crossing the hydrate equilibrium curve. We have investigated whether this process could occur by itself with some surfactants naturally present within some crudes. Some research works have confirmed that some natural surfactants such as resins and asphaltenes have properties similar to synthetic surfactants. Since 95, extensive experimental work has been done at the University of Bergen (1, 2) and Elf research center (3) on a 1 loop with different crudes and fluid blends. The hydrodynamic tests have demonstrated the capability of natural surfactants to prevent hydrate plugging. Based on these results, an experimental methodology to evaluate hydrate transportability of a given crude has been developed. This method could reduce the need of inhibitors during the
509

Subsea oil and gas transportation pipelines in cold waters are often under thermodynamically suitable conditions for the formation of gas hydrates. Traditionally, the industry has designed pipelines and processing facilities to operate outside the hydrate formation pressure-temperature region. This is accomplished by the injection of thermodynamical inhibitors, by the dehydration of the gas/condensate fluids in order to get a water-free flow, or by some isolation or heating device to keep the fluids out of the hydrate area. These alternatives may become very expensive for longer and larger pipelines or higher water flow rates with important subcooling. Several research projects have been launched in order to replace these conventional solutions at lower cost. Projects dealing with low dosage inhibitors for hydrate prevention have shown that some lipophilic surfactants are able to prevent hydrate plugging (8). These so-called Anti Agglomerants form stable and fine water in oil (W/0) emulsions. In addition, the dispersion of water into small and independent units surrounded by surfactant layer will prevent their agglomeration when the fluid enters the hydrate formation zone. Hydrates are then transportable under the form of a slurry, as long as the viscosity remains acceptable. It has been observed that some emulsions are very diff]cult to break. Their stability depends on the nuture and quality of natural surfactants naturally present in the crude. This observation convinced us to investigate if such natural properties could be used to prevent hydrates agglomeration and pipeline plugging. Should these natural surfactants emulsify the water in the oil phase, transport of hydrates in the form of a tine suspension could be possible. If correlation could be established between transportation ability and physiochemical properties of the crude, it would reduce the cost of hydrates prevention. It is known that asphaltenes and resins contained in some crudes are responsible of very stable W/O emulsions. In order to use the potential of these heavy polar components to form steady water in oil emulsion it is necessary to understand the

E.M. LEPORCHER, J.L. PEY7AW, Y. MOLLIER, J. SJOBLOM, C. LABES-CARRIER

SPE 49172

interactions between surface active components when they form fihn at the water/oil interface (ref UiB). Their interracial activity has been well demonstrated in water in oil model emulsions (ref UiB). Asphaltenes and resins are directly involved in the stabilizing mechanism and are called Natural Surfactants. This paper addresses this problem by investigating experimentally the ability of natural surfactants contained in some crudes to transport hydrates in the form of a slurry. The cost for inhibition could be significantly lowered by taking advantage of the self hydrate blockage prevention capability of natural surfactants. The University of Bergen (Pr. Sjoblom) studied natural surfactants in term of hydrates agglomeration prevention capability. Hydrodynamic experiments were performed on an Elf test rig with different crudes in order to demonstrate the natural surfactant ability to prevent hydrate plugging. Tests were performed at different water cuts with different crudes enriched or not with natural surfactants. Test rig, procedure, experiments and results are presented for different crudes and blends.
Description of the test rig

A simplified flow sheet of the hydrate pilot loop at Elf Lacq is given Fig. 1. This test rig includes : a loop of 1 in diameter and 22 m long, a 90 1 tank is used to store the adequate amounts of liquid hydrocarbon , deionised water and gas (buffer tank, MWP :80 bar), one Moineau pump to circulate the liquid phase (emulsion) through the loop from 0.5 to 3m/s, a sapphire window located at the inlet of the pipe, a Coriolis flow meter, a thermostatic device to adjust the temperature of the loop, a computerized data acquisition system to monitor the test rig and to store and process the experimental measurements.
Operating procedure. About 40 kg of liquid are needed to operate properly. Standard commercial gas (G20 : CHi 96.2Yq CzHb 3.2%, C3H8 O.1%, N2 0.5%) is admitted at a pressure of 75 bar resulting in a hydrates thermodynamic equilibrium temperature of 13 C. A certain gas make-up (depending upon the nature of the crude or condensate) is needed to maintain the pressure at 75 bar while temperature decreases from 20 C to 4 C. This amount accounted for the proper volume of oil in the loop will be subtracted from the total gas make-up when calculating conversion rate for test with hydrates formation (with a given watercut). Liquid velocity is fixed at 1 or 2 m/s and temperature is initially set at 20 C. Gas-liquid equilibrium and stabilized operating conditions are reached by pumping the liquid blend through the loop and the tank for several hours. The maximum differential pressure drop acceptable for the Moineau pump is 5 bar. 510

The tank is then set off-stream and the liquid phase saturated with gas is recirculated through the loop only. Liquid velocity is set at the selected value. The loop temperature is then decreased at a constant rate of 10C/hour from 20 C down to 4 C. Then this temperature is kept constant during the whole test period, i.e. about 20 hours if pipe plugging does not previously occur. At the end of each test the loop is heated up to 25 C and maintained at this temperature for several hours in order to ensure a complete hydrate dissociation. The loop is then ready for a next test after a new stabilization period at 20 C. During a complete trial mass flow rate is controlled by means of a Coriolis type flowmeter, pressure drop of the loop is measured by a differential pressure cell and make-up gas is added to the loop in order to keep constant the static pressure when hydrates crystallize. Measurement of the make-up gas flow rate is a way to observe the hydrate growth kinetics and amount formed. Knowing the amount of gas necessary to saturate the oil phase at 75 bar, when temperature decreased from 20 C down to 4 C, and assuming that crystals of hydrates form in stoechiometric conditions, it is possible to evaluate the rate of conversion and the mass of water consumed. Continuous monitoring of pressure, temperature and flow rates allow the follow-up of the test conditions. Hydrates formation is detected by the mean of three variables : sharp increase in gas consumption as it goes from thermodynamic saturation of the gas to the compensation of the gas trapped in hydrates, increase of temperature profile (exothermicity of the reaction), - abrupt increase and irregularities in pressure loss caused by appearance of solid particles in the flow, viscosity change, deposition and plugging. Qualification of a test. Based on carefil analysis of the parameters monitored during the tests and on experience, it is possible to quali~ each test in terms of transportabili~ of the hydrate slurry. The main objective of the tests is to answer yes or no to the following question: is the hydrate slurry transportable? The answer is no, i.e. the test is considered as failed under the following conditions : - The pipe is plugged : the pressure drop through the loop exceeds 5 bar (differential pressure through the pump), - hydrates are crushed by the pump : a significant increase of pressure drop followed by a slight decrease and stabilization is observed, - there is accumulation and/or deposition of hydrates. The criteria is an increase of the static pressure due to partial dissociation. The answer is yes, i.e. the test is considered as passed if during the course of the test every parameter is kept constant for several hours (we tolerate a slight increase of the pressure drop in the magnitude of + 15 V.).

SPE 49172

MULTIPHASE TRANSPORTATION: HYDRATE PLUGGING PREVENTION THROUGH CRUDE OIL NATURAL SURFACTANTS

Experimental

procedure

Crudes are tested with increasing watercuts in order to establish their capability to transport hydrate slurry (maximum acceptable watercut). Then crudes with low potential for hydrate transportation are doped with surfactants (in order to enhance their hydrate transportability properties by increasing their natural surfactants content). The following alternatives are contemplated.
Addition of natural surfactants.

Natural surfactants (mainly asphaltenes and resins) are extracted from one crude and added to a lighter crude or a condensate. This extraction (done at the Universi~ of Bergen at laborato~ scale) is sophisticated and time consuming. It results in very small amounts of available natural surfactants, thus reducing the concentration range feasible. Several tubes of a mixture made of 10 ml of crude oil plus 50 ml of pentane are centrifuged at 2000 rpm for 10 minutes. The asphaltene fraction is precipitated. Silica gel is then added to the remaining liquid until the liquid becomes transparent : silica absorbs resins, the particles are separated from the remaining liquid composed of pentane plus the crude oil without asphaltenes and resins. The pentane is extracted from this liquid under low pressure. Resins are desorbed from the silica gel with a blend of dichloromethane and methanol (93 % and 7 Yo). This solvent is evaporated under low pressure to recover the resins.

North Sea was selected as a good candidate because of previous good results in terms of hydrates transportation. As it is a waxy crude (Fig. 3), this North Sea crude presents a highly non-newtonian behavior, with a viscosity which depends a lot on temperature and shear rate (Fig. 4). The West African crude nl is classified as a light parafflnic fluid. Its wax content is relatively low, nevertheless wax components are heavy. The West African crude n02 is biodegraded and contains no wax. The North African crude has a high asphaltene content and is very viscous. The condensate from a North Sea gas field has a density of 820 kg/m3.
Tests results Loop tests on individual crudes.

Blend of crudes. Another alternative is to blend different

crudes together, or to blend one crude and a condensate. This second procedure was selected for practical reasons and was mainly used in this study. The results are graphically summarized (Figs. 9, 12 and 18) : the watercut is plotted versus the weight percentage of asphaltenes in the oil phase. In order to qualifi the transportability of the hydrate slurry, the graph is divided in four domains: above the dashed line, the test is considered as failed and the hydrates are not transported, - under the continuous line, the test is considered as passed and the hydrates are transported, - between those two lines is an uncertain area where hydrate blockage might occur, - on the right part of the graph, tests have failed not necessarily because of hydrate formation but because of wax deposition or modification of fluids theological properties: this is ascribed to the experimental limitation of the pilot loop,
Properties of tested crudes and condensate

The main physico-chemical properties of the five fluids used in this study are presented in Table 1. The black oil from South Western France has relatively high amounts of heavy components. and presents a non Newtonian behavior with viscosity depending on temperature (Fig. 2). In spite of low asphaltene content, the crude oil from the 511

viscosity increases Western France crude. Its drastically as temperature decreases (Table 1), the pressure drop exceeds 5 bar in the loop (which is the maximum acceptable) when the W/O emulsion (20 0/0 watercut) turns into a hydrate crystals dispersion. It is therefore not possible to discriminate between the effect of the viscosity and plugging due to hydrates. Anyway, it is clear that hydrates transportation with this crude alone is not feasible under these operating conditions. In order to lower the viscosity and in turn the pressure drop, 10 Y. vol. of a blend of 50 ?/. xylene + 50 ?4 EXXSOL D60 was added to the crude. This improved the behavior of the emulsion but did not significantly modi$ the result of the test, as South Western France crude oil natural surfactants were not able to ensure the transport of hydrates slurry. ,Vorth Sea crude. At 10 and 20 0/0 water cuts (Fig. 5) the hydrate slurry is transportable (Table 3). At 30 % water cut the transportability test was considered as failed even if the circulation did not stop for 16 hours. The pressure drop AP still increases after the end of the hydrates formation, indicating some deposition, and then decreases with time, this phenomenon may be due to the crushing of the hydrates particles and to their dispersion in the flow caused by the high shear rate (Fig. 6) (and to their deposit within the dead volume of the pump). West African asphaltenic crude. Up to 10 % watercut hydrates were transportable under the form of a slurry. At 20 0/0 watercut plugging was not instantaneous, but a slow and continuous deposit was observable. At 30 0/0 water cut, hydrate transportation was not possible, Conversion rate calculations (Table 4) show figures lower than expected. From a thermodynamic point of view, 100 VO conversion rate should be reached for each experiment except if plugging occurred before the gas make up has reached its plateau. Explanations to low conversion rates could be as follow: Either the stoechiometry is not respected and 100 %
South

EM. LEPORCHER, J.L. PEYTAW, Y. MOLLIER, J, SJOBLOM, C, LABES-CARRIER

SPE 49172

conversion rate is effectively obtained with less gas than expected, or free water is still present and transported within a hydrate layer . With 30 % watercut plugging occurred before maximum gas consumption plateau was reached, thus its conversion rate can not be compared with other figures (Table 4).
Condensates and crudes enriched with natural surfactants. North Sea condensate with extracted natural surfactants. An

other alternative to test South Western France crude active components and deal with viscosity problems was to extract and add them to a lighter crude. Asphaltenes and resins were then extracted from this crude and added to a North Sea condensate. Resins (diluted in toluene) were first added to the waterlcondensate blend, corresponding to 1 0/0 wt of North Sea condensate or 4 A wt of water. Then asphaltenes (diluted in toluene) were added to the water/condensate blend, corresponding to 0.9 0/0 wt of North Sea condensate or 3.65 0/0 of water. All the tests showed undoubted plugging of the wt loop. This may be explained by a poor dispersion or volubility of asphaltenes and resins in the condensate. They could act as nucleating agents instead of interracial active fractions. The surfactant concentration might not be sufficient.
Blends of South Western France crude and North Sea condensate. Since extraction and re-solubilization of large

With 10 % of South Western France crude in North Sea crude oil at 20 VO watercut (Fig. 11), some irregularities appear in the pressure drop, the conversion ratio of water into hydrates (gas consumption) is lower and the temperature is higher. Under such conditions the transportation is difficult to achieve with 20% of water. This unexpected result may be due to different reasons. Some incompatibility between the h~o crudes may destabilize the heavy components and lower their activity. As a matter of fact, South Western France crude and North Sea crude asphaltenes are quite different and then may have different properties. This stresses the fact that quantitative considerations might not be the only ones to take into account. Another reason may be that the continuous phase reaches such a high viscosity that the slurry can not flow correctly in the 1 loop, North Sea crude is very viscous at low temperature (table 1) and the pressure drop we observed much higher than that with the North Sea condensate / South Western France crude blends. It appears that mixing both crudes did not improve the transportation of hydrates.
Blends of West African non waxy crude and North African crude. The fust experiments started with the West African non

quantities of natural surfactants is difficult and therefore limits the range of concentration available, we decided to blend some fluids. Thus North Sea condensate and South Western France crude were blended in order to increase the contents of resins and asphaltenes in the condensate. Hence two parameters were evaluated : concentration of South Western France crude in the and water cut. liquid (from 5 YOupto507.), Test with pure North Sea condensate and 20 % water cut failed as soon as the hydrates formed (Fig. 7). Complete plugging did not occur (too high shear rate) but hydrates started to agglomerate and were crushed by the pump until overpressure was reached. This test showed that the condensate is not self inhibited. If we add 05 V. of South Western France crude to the condensate (Fig. 8), the same amount of hydrate form (same gas consumption), but no agglomeration or deposition is observed for 4 hours. However the overpressure observed afier 6 hours indicates that the slurry is not totally stable. When increasing the amount of South Western France crude oil diluted in the condensate to 10 0/0, 25/0and 35 0/0 we contemplate the transportability of the hydrate slurry at least for 16 hours and for watercuts of 20 Y. and 25 YO (Fig. 9).For watercuts above 30 0/0 the tests failed because of an over pressure. We have demonstrated that by adding natural surfactants to this North Sea condensate, transportation of the hydrate SIUW was made possible. This transportation was previously observed by using a selected commercial surfactant (Fig. 10).
Blends of South Western France crude and North Sea crude. 512

waxy crude alone. This crude being poor in natural surfactants, hydrates transportability was quickly not ensured even with low water cut (1O%). Then the West African non waxy crude was blended with the rich asphaltenic North African crude in order to increase gradually the content of surfactants in blend (Figs. 12 and 13). Volume added has been calculated on the basis of the n-C5 asphaltenes contents given in Table 1. Tests with 10 % water-cut and 0.5 V. of n-C5 asphaltenes indicate that hydrates are transported during more than 20 hours after their formation. Instabilities in the pressure drop before stabilisation around 3 bar are probably due to hydrate agglomeration up to a certain size which allow their transport inside the fluid. The restart test with the same fluid confirms the previous test since hydrates are transported for more than 14 hours. The pressure drop and the gas make-up are slightly different than in flowing conditions, indicating that more water is converted into hydrates. Tests with 15 % water-cut and 0,5 YO of n-C5 asphaltenes (Fig. 14) show that increasing the water-cut by 5 VO significantly modifies the result. The pressure drop quickly reaches 4 bar and then abruptly decreases, indicating that hydrates are crushed in the pump. The pressure drop is then slowly decreasing until the high pressure security system operates. Tests with 15 % water-cut and 1 % of n-C5 asphaltenes showed (Fig. 15) that hydrates are transported. The pressure drop of the flowing test smoothly increased up to 2.4 bar and then stabilised at 2.2 bar. An important deviation of the temperature on the cold step may indicate some hydrate deposits on the pipe wall. Tests with 20 V. water-cut and 1 A of n-C5 asphaltenes showed that both the restart test and the flowing test failed quickly (about 3 hours after hydrates formation). Tests with 20 ?4 water-cut and 1.5 Aof n-C5 asphaltenes

SPE 49172

MULTIPHASE TRANSPORTATION: HYDRATE PLUGGING PREVENTION THROUGH CRUDE OIL NATURAL SURFACTANTS

got a circulation for more than 20 hours after hydrates formation. Nevertheless, even if increasing the asphaltene content prevented the experiment from failing quickly, the variations observed on the pressure drop indicate that crystals are probably crushed within the pump and deposit in its dead volume, before the system reaches a steady state. An additional test has been performed with a different fluid sample, composed of the same fluids proportions. The test failed after only 5 hours. Results of both experiments suggest that 20 0/0 water-cut is a limit, the system not being stable any more, as if small changes in the experiment parameters (temperature regulation...), could lead the test either to pass or to fail. Tests with 20 Y. water-cut and North African crude oil in order to get 2 Aof n-C5 asphaltenes showed that adding 0.5 YO of asphaltenes does not modify significantly the results, measurements compared to those of the previous test are similar, indicating that whatever the asphaltenes content, 20 A water-cut is a limit of hydrate transportability for this blend of oils. To evaluate the rate of conversion and the mass of converted water, stoechiome~ hypothesis is not realistic, the margin of error is significant ; moreover in order to add North African crude oil, we have used condensate which has modified the overall liquid properties (volume of saturation gas for instance). Nevertheless from conversion rate calculations (Table 5) we can underline the following tendency when increasing the water-cut and the asphaltene content, the conversion rates decrease resulting in a fairly stable mass of water turned into hydrate. Hydrates form at the interface between oil and water. In the case of an emulsion of water in oil, the bigger the droplets of water, the smaller the interface surface. By increasing the asphaltenes content, we increase the size of the droplets of water within the emulsion, reducing that way the surface of exchange and the conversion rate. Moreover, acting like surfactants by surrounding the hydrate crystals, they reduce significantly the kinetic of gas diffision.
Wax related effects

North African crude blends, the velocity is calculated from the average mass flowrate and is fairly constant at 2 m/s. Since either starting or final temperatures are equal, the pressure drop differences are related to fluid property variations. Analysing the three first data in Table 6, both initial and final pressure drops increase with asphaltene content or the watercut. Adding asphaltenes or water modi~ the overall fluid properties, in particular its viscosity increases. Pressure drops of the two last set of data are lower than what could be expected. Concerning those tests, the tank volume is nearly fill. A first explanation could be that separation occurs in it, due to high residence time, resulting in a different fluid in terms of water-cut than what was expected. Comparing tests done with the second load (where the tank is nearly empty), and tests done with the first load, this explanation can be rejected since both results are similar. Another explanation could concern a variation of flow regime in the loop. For instance, when reaching a given water-cut, the upper part of the pipe becomes free of suspension/emulsion, modifying that way the flow regime. The maximum watercut seems to be 30 YO in all cases. It is known that for water in oil emulsions there is an inversion point at which a slight increase in water content turns the continuous phase from oil into water. At this inversion point the viscosity of the emulsion reaches a maximum. It is possible that a comparable phenomenon occurs for hydrates slurry. At 30% water-cut, the dispersion of hydrates solid particles in the oil phase might be close to its inversion point, so the hydrates particles start to drop out of the slurry. The graph in Fig. 17 (for the blend North Sea condensate and South Western France crude in the proportion of 75/25) shows the pressure drop in the loop for the emulsion and the hydrate dispersion, at different watercuts. This differential pressure can be correlated with the viscosity. The emulsion (internal phase liquid at 20 C) and the dispersion (internal phase solid at 5 C) show different viscosity profiles as a function of the watercut.
Conclusions

To avoid wax deposition during test with North Sea crude, it was decided to add antiwax to the crude. Injection of 500 ppm of SWIM 5X chemical did not modi~ the hydrodynamics. However, the conversion rate becomes higher (Table 2) and pressure drop increases slowly all along the test period. This may indicate that waxes play a role in the dispersion of hydrates particles, as it was previously suspected. When the transportation is not limited by the viscosity, it seems that waxes favor the transportability of hydrate slurry. Results from West African non waxy crude oil, the West African crude and North Sea crude (Fig, 16) illustrate this tendency: as the wax content increases, the maximum transportable watercut increases.
Hydrodynamic aspects

For all measurements on West African non waxy crude and 513

These tests (Table 7) led to a better understanding of the mechanisms and better identification of some key parameters. It has been noticed that paraffin may have positive interactions with the natural surfactants of the oil to stabilise the slurry. The North Sea crude experiments demonstrated that one crude can be self-inhibited against hydrate blockage, up to a certain watercut. From the tests based on South Western France crude when mixed with a low asphaltenic crude (such as North Sea crude or a condensate), it is shown that if the amount of asphaltenes in the mixture is high enough (1.5 0/0 - 2 /o by weight) the system can transport up to 30 YO of water under hydrate conditions. This result is very important because it indicates that an appropriate blend of a condensate (North Sea condensate) and a crude (South Western France crude) can behave similarly to a real crude, like North Sea crude which

E.M. LEPORCHER, J.L. PEYTAW, Y. MOLLIER, J, SJOBLOM, C. LABES-CARRIER

SPE 49172

performed quite well. Results show that oil from West A&lcan non waxy crude is not able by itself to transport hydrates with 10 0/0 water-cut. When adding asphaltenic crude oil the hydrate transportability limit has been extended to 20% watercut. Self-remediation by crude natural surfactants against hydrates blockage is then demonstrated. It is strongly connected to the physico-chemical properties of the crude. Unlike commercial surfactants, natural surfactants represent a class of components rather that a pure substance. Natural surfactants have different composition and properties from one crude to an other. As shown Fig. 18 where transportability is plotted as a fiction of asphaltene concentration and watercut for two different systems, the nature of asphaltenes is probably as important as tie concentration of this surface active agent. Asphaltenes are proactive species in water in oil emulsion stabilization, but other factors have to be assessed such as resins, waxes, aromatics, water quality ..... It has also been demonstrated that it was possible to enhance the hydrates transportability properties of a crude by increasing its natural surfactartts content. This was achieved by different crudes. In all cases it seems that hydrates slurry transportation is limited to 30 % watercut. A difference of viscosity between emulsion and dispersion has been observed, this should be taken into account for multiphase flow modeling. Further work is needed in order to make predictive evaluation of crude ability to transport hydrates.
Acknowledgments The authors would like to tiank Elf Norge, Total Norge and

References

1.

Schildberg,Y., Sjoblom, Christy, A,A., Voile, J.L, Rambeau, 0.. (1995)Characterization interraciallyactivefractionsand of their relation to water-in-oilemulsionstability, J Dispersion
Science and Technolo~, 16 (7), 575-605,

2.

Fardedal, H., Schildberg,Y., Sjoblom, J., Voile, J.L. (1996) Crude oil emulsions in high electric fields as studied by
dielectric spectroscopy. Influence of interaction between commercial and indigenous surfactants, Colloid and Surfaces,
A : PhysicochemicaI and Engineering Aspects, 106,33-47.

3.

4.

5.

6,

7,

8.

Peytavy, J:L, Roche, J. (1995) Hydrates inhibition: study of crude oil natural surfactants - Case 1: South Western France crude oil, Elf EP Internal Report PRO/EPS-RGS no 95.5.096. Fourest, J:M, Roche, J, (1996) Hydrates inhibition: study of crude oil natural surfactants - Case 2: North Sea crude oil , Elf EP Internal Report PRO/EPS-RGS no 96.5.108. FouresL J:M, Roche, J. (1996) Hydrates inhibition: study of crude oil natural surfactants - Case 3: Blends of condensate and asphaltenic crude oil, Elf EP Internal Report PRO/EPS-RGS no 96,5.136 Mollier, Y., Roche, J. (1998) Hydrates inhibition: study of crude oil natural surfactants - Case 4: African crude oil, Elf EP Internal Report PRO/EPS-RGS n 98.5.024 Mollier, Y,, Roche, J. (1998) Hydrates inhibition: study of crude oil natural surfactants - Case 5: Blends West African non waxy crude oil and North African crude oil, Elf EP Internal Report PRO/EPS-RGS n 98.5.038 Peytavy, J:L, Roche, J. (1994) Hydrate prevention Qualification of a commercial additive at high watercuts, Elf EP Internal Report EP/P/PRO/EPS-RGS Ref. JLP/JR/mp n 94.5121.

University of Bergen for their sponsoring, stimulating discussions and permission to publish this work.

T.ABLE CRIIDESCHARACTERISTICS 1Density (~m3) }riscosity (Cp) Wax appearance temp. ~C) Asphaltene (in C5) Resins Paraffins (wt)
(clO+)

(on
sili ca)
20%

SouthWestern France crude North Sea waxy crude West African crude nl West .African non waxy crude n2 North African asphaltenic

890

70 at 20C 310at3C 15 at 20C 200 at 3C 35

5V0

5%

838 861
900

().s~o

1 5%

12%

0.5V0 0.3%

7%

6,5%
0%

922

18%

12%

4%

514

TABLE 2- RESULTS FOR NORTH SEA CRUDE OIL.

Water cut

T crystal growth

Conversion rate & hydrate quantity North Sea North Sea crude oil crude oil with Swim 5X alone

hydrates transport

10% 20% 30%

8.2 C 8.8 c 9.6 C

38% (10 kg) 36% (1.9 kg) 27%

50% (1.4 kg) 44% (2.4 kg) 30%

yes (> 15h) yes (> 15h) no

T.4BLE 3- PRESSURE DROP DURING LOOP TEST WITH NORTH SEA CRUDE OIL

Water cut

o%
0.85 2

10%
0.9
2.5

AP of the emulsion at 20 C (bar)

Apparent viscosity(cp) AP of the dispersion at 5 C (bar) Apparent viscosity (cp)

20% 0.98
3

30~o

1.1
4.5

40% 1.2
6

1
4

1.8 40

3 70

4.9 110

TABLE 4- WEST AFRICAN CRUDE OIL : CONVERSION

RATE

Water-cut
10

~/0)

conversion rate

(0/0)

20
30

54 38 17

TABLE 5- BLENDS OF WEST AFRICAN NON WAXY CRUDE OIL .AND NORTH AFRICAN CRUDE OIL: CONVERSION

RATE

Water-cut

(V.)

10 15 20

n-C5 asphaltenes 0.5

(O/.)

conversion rate 68.4

(0/0)

equivalent mass (kg) 1.85

1 1.5

55.3 37.9

2.20 2+10

TABLE 6- BLENDS OF WEST AFRICAN NON WAXY CRUDE OIL AND NORTH AFRICAN CRUDE OIL: HYDRODYNAMICS

CONSIDERATIONS

Water-cut (%)

n-c5 aspha.

(O/.)

Initial Temp (C)

Initial AP (b)

Final Temp. (C)

Final AP (b)

10

10
15 15 20

0.3 (West African non waxy crude oil alone) 0.5 0.5 1 1

19,29

1.15

4.71

2.54

19.8 18,92 19.29 19.29

1.32 1.41 1.25 1.32

5.59 4.34 5.15 3.69

3.07 >4 2.12 2,55

515

E.M. LEPORCHER, J.L. PEYTAW, Y. MOLLIER, J. SJOBLOM, C. IABES-CARRIER

SPE 49172

TABLE 7- SUMMARY OF THE EXPERIMENTAL

RESULTS

water cut (%)

South Western France crude

North Sea crude oil

North Sea condensate+ South Western France crude

North Sea crude oil + South Western France crude

West African Crude

West African non waxy crude oil + North African crude oil

10 15 20 25 30 40

+ + . -: tests failed + +

+ +

+ +/-

+ +

+: tests passed

Flow-meter Pressure control

N2 To vent

Gas make-up

d,

To vent

1
.. -.-,--.-, -----PT sensor -, !
I

t
I

I I

Loop Length
Liquid N2 gas Nz

q,, 22m

:
t
I

( Cooling fluid /1

1%

--------

1.

-------

-._. t

Coriolis Flow-meter

. Moineau pump Fig. 1- Elf hydrate loop at Lacq,

Ap

Drain

516

SPE 49172

MULTIPHASE TRANSPORTATION: HYDRATE PLUGGING PREVENTION THROUGH CRUDE OIL NATURAL SURFACTANTS

. .
14,00 % !Z,m %

. ..

to,w %
8,01 %

6,DI %

4,W %

2,W %

o,moh

br
m

,....+=r _ . u.
.
. .

Fig. 2- Distribution of n-paraffins in South Western France crude.

Fig. 3- Distribution of n-paraffins in the North Sea crude.

1000,

I
I I I . . . . . . . . .. I .. . I I

:100 g
,g

a o : .>

10
I ,

10

20

30

40

50

60

Temperature

(C)

Fig. 4- North Sea crude : viscosity versus temperature.

517

10

E.M. LEPORCHER, J.L. PNAW,

Y. MOLLIER, J. SJOBLOM, C. LABES-CARRIER

SPE 49172

10.00

8.00

I I

s s

Pressure/10 (bar) -s-sCurrent intensity (A) = =9Gas make-up/l OO-(Nl) ---s

Mass flowrate (t/h) Differential pressure (bar) emperature/10 (oc)

6.00

@
!

. ...=

..==

=.9 ==9====. .= =====

q **
4.00

2.00

0.00 0.00 4.00 8.00 12,00 16.00

Time (h)
Fig. S - Ratio Water/North Sea crude 20/80.

10.00

q s s s

Pressure/l O(bar) --1Current intensity (A) - Gas make-up/100 (Nl) -----

Mass flowrate (t/h) Differential pressure (bar) emperature/10 (c)

8.00

6.00

4.00

2.00
,+~..p.*

.:L.@ ..-,; ~., J.._:+

..-..

+---

.4..

-.9

... .

.. .

..-

..~-w..

0.00 0.00 4.00 8.00 12.00 16.00

Time (h)
Fig. 6- Ratio Water/North Sea crude 30R0.

518

SPE 49172

MULTIPHASE TRANSPORTATION: HYDRATE PLUGGING PREVENTION THROUGH CRUDE OIL NATURAL SURFACTANTS

11

10.00
Pressure/10 (bar) Mass flowrate (t/h) 1-0- Differential pressure (bar) Current intensity (A) -=- Gas make-up/100 (Nl) Temperature/10 (C) I

8.00

6.00

4.00

2.00

0.00 0.00 1.00

Fig. 7- Ratio Water/Noti

2.00

3.00

4.00

Time (h)
Sea condensate 20/80.

10.00
Pressure/l O (bar) Current intensity (A) -- =- mGas make-up/100 (Nl) *-c
----

Mass flowrate (t/h) Differential pressure (bar) Temperature/10 (c) .-. . m

8.00

6.00

4.00
q

8 &*
q

4---**m&.d*d*,_,n.
_,N.J *. -**

48

2.00

;~,_,-,
L., \,

_,*,;g
q* ..\*%*

---

q *
. .* .=4-.. _.._: . ..+..-..* ,.- ~.... d.. . .&.. _..\-. ..4-. +..

0.00 0.00

4*.*

2.00

4.00

6.00

Time (h)
Fig. 8- Ratio Water/(95Y. North Sea condensate+ 5% South Western France crude) 20/80.

519

12

E.M. LEPORCHER, J.L. PEYTAVY, Y. MOLLIER, J. SJOBLOM, C. LABES-CARRIER

SPE 49172

40 35 30 25 20

Hydrates not transported

-r \

q Transport

sNo transport
&p g Iirnitatio

Wa?e? 10 5 0

/
o
0,5 1 1,5

I
1 2 % asphaltanas in the blend.

Loop limitation

2,5

Fig. 9- Hydrate transport for blends of South Western France crude and North aea condensate.

000 9,00
8,00

T------~~-~~l-----~--l

7.00
6,00 5,00

Press urel10 (bar)

00 (Nl) 4,00 3.00 2,00

1,00

(tih) & (A) (bar]

0 (Oc)
0.00 0,00

2,00

4.00

6,00

8,00

10,00

12,00

14.00

16,00

18,00

Time h

Fig. 10- Hydrate transport for North Sea condensate and a commercial eurfactant for 20/0watercut

SPE 49172

MULTIPHASE TRANSPORTATION: HYDRATE PLUGGING PREVENTION THROUGH CRUDE OIL NATURAL SURFACTA~S

13

10.00
-s q s

Pressure/10 (bar) Current intensity (A) 9Gas make-up/100 (Nl)

Mass flowrate (t/h) -c-c- Differential pressure (bar) . Temperature/l O (C)

8.00

6.00
......
...9
9...=.====

,,

.9

. . . . . .

4.00
f
A

A
+ & T

2.00

l,,

\4~
0.00
++

/*@*@s ---

-,
d.. ... * ..%.. +..+.. ..-.

,-,

-,-

a-m-9-a-

,X.P..A.. -.,..,._..--..\.. ,
0.00

..

..

. . _.

._

..-

.,

4.00

8.00

12.00 Time (h)

16.00

20.00

Fig.ll-Ratio

Water/(Notih Seacmde90%

+Southwestem

FmncecmdelO%)

20/80.

Hydrates not transported 20

..- . ,J

,,... .. .

i M-. @ } 1 [ LooD limitation 4

5 .

; .

1 Hydrates transported 1 ;

q Transported KNO transp .~ A loopIimitat]o ,2 1,4 1,6 1,8 2

o 0

0,2

0,4

0,6

0,8

Aephaltene% in the bland

Fig. 12- Hydrate transport for blends of West African non waxy crude and North African crude.

521

14

E.M. LEPORCHER, J,L. PE~AVY,

Y. MOLLIER, J. SJOBLOM, C. LA13ES-CARRIER

SPE 49172

2.0

-----

-----

-----I 1 i I #

----I I I I 1

-----

___

-----

-----I I I I #

-----

---I I I I

1.5

----

-----

I 1
I I I

I---------

J----

1
I I 1 I

----

-----

----

l--------_J I
I I I I

~ I I

Test passed Test failed

1.0

-----

----

I -,---I I
I 1 I

----I
I I I -------I

-----

I --- -,---I 1
I i I I ---------

-----

+ I
I 1 t I t 7 1 I

0.5

------

---

T
I

-----

1
I

---

I
I I

I
I

I 1 I I

I I I I I

I I I 1 I
20

I I I I I
25

I I I I I
30

10

15

Watercut A
Fig. 13- Experimental pati for blends of West African non waxy crude and North African crude.

10.00

8.00

Pressure/l O(bar) -s-o Current intensity (A) =m -- Gas make-up/100 (Nl) ----s q

Mass flowrate (t/h) Differential pressure (bar) Temperature/10 (C)

6.00

4.00

2.00

0.00 0.00 2.00 4.00 6.00

Time (h)
Fig. 14- Blende of Weet Afrlcen non waxy crude and North Africen crude: 0.57, aephaltenes,

522

SPE 49172

MULTIPHASE TRANSPORTATION: HYORATE PLUGGING PREVENTION THROUGH CRUDE OIL NATURAL SURFACTANTS

15

10.00

Pressure/l O (bar)

Current intensity (A) -- ===9Gas make-up/100 (Nl)

--o-..

Mass flowrate (t/h) Differential pressure (bar) emperature/lo (c)

8.00

6.00

4.00

2.00

0.00
0.00 4.00

8.00

12.00

16:00

20.00

Time (h)
Fig. 15. Blends of Weet African non waxy crude and North African crude: 1 % asphaltenee.

n
m
*Wax%

12,0 %

TransPort
10,0
v.

=Notransport

8.07.

6,0%

$ x $

4,0

Y.

2,0 %

0,0 % West African non waxy African crude North Sea crude

Fig. 16- Influence of the wax content.

523

16

E.M. LEPORCHER, J.L. PEYTAVY, Y. MOLLIER, J. SJOBLOM, C. LABES-CARRIER

SPE 49172

3
-

Emulsion

at 20C
. A

-9-

Dispersion at 5C

2.5

2.0

s .-

1.5

# ~ a ---

0.5

0.0
0.,o~
10 20 30 40 50

% Water in total liquid

Flg,17 -Pressure drop lnemulslon anddlapemlon -Blend Notih Seacondensate and SouWWes@rn Fmncecwde 75/26.

9*
5

n
o
0,2 0,4 0,6 0,6 Asphaltenes 1 1,2 weight% 1,4 1,6
Fig. 18- Hydrate transpotiblllty and asphaltenes concentration.

0 transp

s No transp
1,8 2

524