At the Statoil-operated Heidrun-field in the Norwegian Sea, naphthenate deposits were first observed during a maintenance shutdown in September 1996. Thereafter the problem increased, and by the end of 1997 it was recognised as a constant threat against continuous production. The present paper describes both the short-term measures taken to gain control of the problem in the early days, and the quest for a more elegant long-term solution. Statoil is continuously working to increase its fundamental understanding of the naphthenate problems and to improve the naphthenate inhibitors used at the Heidrun field. Introduction Among the oilfields found and developed around the world, an increasing fraction contains naphthenic acids and has a high TAN-value (Total-Acid-Number). A high TAN-number in a crude oil is probably a result of aerobic bacterial degradation and is often linked to high densities and sulphur contents. There are several problems that are specific to these kinds of crudes;During production these crudes tend to react with the calcium-ions in the formation water and form naphthenates that deposit and plug the process equipment.1–3Naphthenic acid corrosion is a major concern to the refining industry. The presence of naphthenic acids and reactive sulphur compounds considerably increases the corrosion rates in the high temperature parts of the distillation units.4Jet fuels, diesel fuels, and heating oils do all have specifications that limit the maximum acid contents in these products. The present paper addresses itself to the calcium naphthenates formation during crude oil production at the Heidrun oilfield in the Norwegian Sea. The appearance of the naphthenate problem will be described in detail. Then both short-term and long-term remedies for control are presented. The Heidrun field The Heidrun field in the Norwegian Sea has been producing oil and gas since October 1995 from a floating tension leg platform with a concrete hull. Heidrun was discovered in 1985 by Conoco, which served as operator for the exploration and development phase. Statoil took over in 1995 as production operator. Oil from the field is primarily shipped by shuttle tankers to Statoil's Mongstad crude oil terminal near Bergen for onward transport to customers. Gas from Heidrun is piped to Tjeldbergodden in mid-Norway and serves as the feedstock for the Statoil methanol plant there. From 2001, the field has also been connected to the Åsgard Transport pipeline. Heidrun gas is piped through this trunkline to Kårstø north of Stavanger and on to Dornum in Germany - a total distance of roughly 1400 kilometers. A total of 76 wells are planned on the main field, including 51 producers, 24 water injectors and one gas injector. The north flank of Heidrun was brought on stream in August 2000, enabling Statoil to maintain plateau production for 4 more years until 2004. Some of the Heidrun crude oil's characteristics are given in Table 1. Of special importance is the combination of a high acid content (TAN = 2.7 mg KOH/g) with relatively low density (0.90 g/cm3) and hetero-element (S, N, Ni, V) content typical for North Sea crude oils. Normally, oils with high acid numbers also have high densities, as is evident from Table 2. A simplified flow scheme of the liquid treatment systems at the Heidrun platform is showed in Fig. 1. Three gravitation separators constitute the main separator train. The separators have centre inlets, and are fitted with Mellapak (polypropylene) internals (Fig. 2). The well stream enters the inlet separator at 64°C, and is heated further to 77°C upstream of the 2nd stage separator. The water cut is about 18% and 2% at the 1st stage separator inlet and outlet, respectively. The next two separators reduce the water content of the oil to less than 0.5%.

The amount of acidic crude oils produced worldwide is increasing. These oils introduce problems throughout the hydrocarbon value chain due to their high content of carboxylic acids, examples of which are naphthenate deposition in production facilities and refinery corrosion. In order to deal with these problems, it is often necessary to isolate the carboxylic acids in different fluid streams or solids to allow further analysis without interference from other compounds. This paper presents and verifies an ion-exchange method that can be used for selective isolation of carboxylic acids from crude oils, distillate fractions and other organic solvent. The efficiency and selectivity of the method have been demonstrated as >98 mol-% using two synthetic carboxylic acids. Its usefulness for isolation of carboxylic acids from solids and non-organic solvents has also been demonstrated, exemplified by calcium naphthenate deposits and water. Introduction Among the oilfields found and developed around the world, an increasing fraction contains naphthenic acids and has a high TAN-value (Total Acid Number). Producing and refining high-TAN crude oils introduces a number of problems, e.g. calcium naphthenate deposition in process facilities offshore,1–4 and corrosion in refinery equipment.5 In order to understand the mechanisms behind these and other naphthenic acid-related problems, it is of utmost importance that the acids can be isolated selectively, thereby allowing for thorough characterization of the acids. Through the years, a number of works dealing with isolation and characterization of acids in crude oils, base oils, oil shale, etc. have been published. The different methods are most easily grouped into the categories solid/liquid extraction,6–12 liquid/liquid extraction,13 and chromatography.14,15 Methods for direct extraction of acids from water are also described.16–18 The idea of using a sugar-based QAE Sephadex A-25 ion exchange resin (Acid-IER) was presented to Statoil by private consultant Bjørn A. Ardø, who also worked with Statoil to develop the idea into a working procedure for isolating carboxylic acids from crude oils. The fact that it is sugar-based makes the IER hydrophilic, and, therefore, more selective towards carboxylic acids than hydrophobic IERs. The present paper describes the Acid-IER method in detail, and gives examples of its use for isolating acids from a crude oil and its distillates as well as from water and calcium naphthenate deposits. The high efficiency and selectivity of the Acid-IER method has been demonstrated using two synthetic acids dissolved in an acid-free crude oil. Laboratory equipment The experimental set-up and equipment used during carboxylic acid isolation are ordinary laboratory equipment, e.g. filter funnels, filtering flasks, and round flasks. During the filtering process two filter paper qualities were used - 5891 Black Ribbon and 5893 Blue Ribbon from Schleicher & Schuell - hereafter referred to as coarse and fine filter paper, respectively. Solvent evaporation was done using a rotavapor (Labrota 4003 equipped with rotacool and rotavac, Heidolph). The rotation and temperature set points were 120 rpm and 60°C, respectively. The pressure was reduced gradually to 35 mbar. The acids were dried further in a heating chamber (60°C) until the weight was stable.

The effect of reaction pressure in catalytic reforming was studied in a pilot reactor with a commercial Pt−Re/Al2O3 reforming catalyst and a hydrotreated naphtha from a North Sea crude. Reformate and hydrogen yields, research octane numbers (RON), and reformate composition at reactor pressures in the range of 12−25 bar were measured as a function of temperature in the range of 95−105 RON. Reformate and hydrogen yields increased as the pressure was reduced. This effect was more pronounced at high severity and in the high-pressure range. For the lower reaction pressures the hydrogen yields increased with increasing severity, but for the higher pressures the hydrogen yields started to decline above certain severities. RON was linearly dependent on the concentration of aromatics in the reformate, although the selectivity toward aromatics depended on both pressure and temperature. Less hydrodealkylation of C8 and heavier aromatics to benzene and toluene resulted in a shift toward xylenes and heavier aromatic components when pressure was lowered. Variations in the degree of paraffin isomerization did not influence RON significantly at those severities.

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