Petroleum Science and Technology, 24:673688, 2006 Copyright Taylor & Francis Group, LLC ISSN: 1091-6466 print/1532-2459

9 online DOI: 10.1081/LFT-200041172

Effects of Demulsier Structure on Desalting Efciency of Crude Oils

Xinru Xu, Jingyi Yang, and Jinshen Gao
Research Institute of Petroleum Procession, East China University of Science & Technology, Shanghai, P.R. China

Abstract: The desalting and dewatering of six crude oils with deferent properties have been studied. The contents of asphaltene and resin of #1, #2, and #4 crude oil are high; the demulsiers with higher lipophilic values than others in the same series such as DA2, DB2, and DC2 can be easily absorbed on the interface of a wateroil emulsion and reveal better dewatering and desalting efciency. The carbon atom number of alkyl on phenol core in nonyl-alkylphenol formaldehyde resin, which is the initiator of the DC series, is more than that of the DB series. DC was easier to diffuse into the interface of water in oil, and the dewatering efciency increased. Because more multipoint adsorbed, their dewatering rate was slower, and the salts can dissolve in washing water and be removed with water. The density and viscosity of #3 crude oil are lower, and wax content is high. The hydrophilic group and lipophilic group in the molecular of DA4, DB4, and DC4 demulsier can well be absorbed on the interface of wateroil emulsion of #3 crude oil, which have better efciencies of desalting and dewatering than other demulsiers of their same series. The density, viscosity, and wax content of #5 and #6 crude oils are lower; however, sulfur content is high. The self-made demulsiers have excellent dewatering efciency for #5 and #6 crude oil, but the desalting efciency is unsatised, because the content of salts sulfate and sulde in #5 and #6 crude oil is high as shown in the analysis of anion content before and after desalting. It can be improved by adding acid assistant TJ1, TJ2, and TJ3, thus indifuent salts sulfate and sulde transform into difuent salts that can be removed, so the desalting efciency obviously increases. Keywords: desalting, dewatering, demulsier, crude oil

Address correspondence to Jinshen Gao, Research Institute of Petroleum Procession, East China University of Science & Technology, Meilong Rd. 130, Shanghai, 200237, P.R. China. E-mail: gjs@ecust.edu.cn 673

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INTRODUCTION Crude oil from underground reservoirs contains water to form water-in-oil emulsion. The majority of the salts, such as sodium, magnesium, and calcium chloride, are dissoluble in water. In oil elds, the newly exploited crude oil has to be treated to remove water and salts. Its water content is limited to less than 0.5% and salt content less than 50 mg/L. But this salt content of crude oil is still high for the renery. Therefore, pretreatment of crude oil in which the salts are removed is the rst operation in petroleum rening (Barnett, 1988). Formerly the desalting of crude oil was conducted only as a measure to decrease corrosion and stabilize operation. In recent years, desalting technology has played an important part in protecting catalysts in the latter rening operations, because after distillation, the majority of salts are left in residual and heavy stocks which leads to the poisoning and deactivation of catalysts in the heavy oil catalytic cracking, hydrocracking, and hydrorening (Sams and Zaouk, 2000). Another noticeable problem is that a series of enhanced recovery technologies have been widely applied in oil elds (Zheng and Wu, 2000), for example, using surfactant, polymer, and alkali ooding to drive heaver oil. At the same time, they can enter into the oil layer and make the emulsion more stable. During the past decades, nonionic surfactants have been widely used as demulsiers. Nowadays, alkoxylated polyhydric alcohol, alkoxylated alkylphenol formaldehyde resin, alkoxylated polyethylenemine, and their derivatives are main demulsiers for the desalting and dewatering of crude oil (Sams and Zaouk, 2000; Talor, 1992). As the properties of crude oils from different oil elds are different, a demulsier tted to one type of crude oil is usually not as effective with other types. Attempts have been made to correlate the efciency of demulsiers with their surface, interfacial, and chemical properties (Chen, 1993; Mohammed, 1993, 1994; McLean and Kilpatrick, 1997; Ovalles, 1998; Acevedo, 1999; Goldszal and Bourrel, 2000; Runac and Tabakovic, 1978; Aveyard et al., 1990; Zaki et al., 2000; Wu, 2003). Runnac and Tabakovic (1978) reported a correlation between demulsication and the size of the hydrophilic group for block copolymers. Aveyard et al. (1990) and Zaki et al. (2000) described the correlations between demulsication efciency and HLB of demulsier. Wu (1993) investigated whether a relationship exists between demulsication performance and the properties of the demulsier, including relative solubility number (RSN) value and molecular weight. However, there are many works researching the relation between the property of crude oil and the molecular structure of demulsiers. In this paper, three series demulsiers are synthesized, and the effect of the molecular structure of these demulsiers on their desalting and dewatering abilities for Shengli, Luning, Daqing, Cabinda, Saudi, and Iran crude oil are

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examined. The impact of an acid assistant on desalting ability for Saudi crude oil and Iran crude oil is also discussed.

EXPERIMENTAL Synthesis of Demulsier In a 500 ml high-pressure reactor tted with a condenser, mechanical stirrer, thermocouple, and manometer, polyhydric alcohol, octyl-alkylphenol formaldehyde resin, and nonyl-alkylphenol formaldehyde resin as initiators were polymerized with a certain amount of propylene oxide (PO) and ethylene oxide (EO) at a proper reactive condition. In order to t the demulsifying behavior to different types of crude oil, the weight ratio of EO/PO was varied. Using this method, a series of block copolymers (DA, DB, DC series) demulsiers were obtained and used for the experiment. Process of Static Electric Desalting of Crude Oil PDY-1 instrument of electric desalting for crude was used in the experiments. Having been preheated and uniformly stirred, the oil sample was delivered into the mixer where a certain amount of washing water was put in, and this was then stirred at 9,000 r/min for 1 min. After that, the emulsion and appropriate demulsier were put into test bottles. These bottles equipped with electrodes were xed in the oscillator and shaken for 1 min then stored in a constant-temperature bath at 85 2 C for 10 min, and shaken again for 1 min, which ensured uniform distribution of the demulsier in the emulsion. These bottles were placed on the DPY-1 for 20 min at 2,100 V/cm electric eld and 85 C, then the electric was remoed and then stored 15 min at 85 C. The volume of the separated water was recorded; the salt content in oil after desalting was analyzed.

Analysis of Salt Content in Crude Oil In the experiment, WC-2 microcoulometric detector of salt content was used to detect the salt content in crude oil. The principle of the WC-2 microcoulometric detector is that crude oil mixed with polar solvent was rst heated to extract the salt and then centrifuged. A small amount of extracted liquid was taken out with an injector and delivered into the ethanoic acid electrolyte containing a certain amount of silver ion, so chlorine ion in the sample can react with silver ion as follows: Cl + Ag+ AgCl

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The lost silver ion for the reaction will be supplied by electrode, so according to Faradays law (of electrolysis), the salt content in the sample will be obtained by measuring the change of electric quantity for supplying silver ion.

Analysis Method of the Anion Concentration of Crude Oil The instrument of ion chromatogram (DIONEX Model 500) was used to detect the anion concentration of crude oil. The analyses conditions for ion chromatogram were provided as follows: separate column is AS4A-SC4 mm, ow of Na2 CO3 /NaHCO3 is 2 ml/min, washing liquid is NaCO3 , the detector is restrain conductivity. A 12.00 g oil sample, 18 ml xylene, and 18 ml deionized water were delivered into a cylinder and stored in a constant-temperature bath at 80 C for 15 min. Then 6 ml ethanol was added, and it was shaken for 4 min in an oscillator and again placed in water bath for 30 min at 80 C. The extracted water was taken out by using an injectorthe left oil was extracted twice by the same method. The three extracted water samples were put together and taken for detection on the ion chromatogram.

Properties of Several Crude Oils The desalting and dewatering of Shengli (#1), Luning (#2), Daqing (#3), Cabinda (#4), Saudi (#4), and Iran (#5) crude oils, which are typically found in Chinese reneries, were studied, and their properties are shown in Table 1.

RESULTS AND DISCUSSION Effect of DA Series Demulsiers on the Desalting and Dewatering of Crude Oil Generally, a small proportion of washing water is mixed with crude oil so that the salts and impurities in oil can be dissolved, the washing water should be dispersed in crude oil to form emulsion, which extracts the salts from oil. However, these brine droplets are prevented from coalescing due to the elastic lm on the interface between water and oil. Normally, this lm is stabilized by natural emulsiers in crude oil, such as wax, resin, asphaltene, naphthenic acid, and so forth. The demulsier usually has a higher surface activity than these natural emulsiers, so it can displace them and weaken the lm, thereby promoting the droplets of brine to coalesce when they contact each other (Figure 1).

Table 1. Properties of several crude oils #1 #2 #3 #4 #5 #6

Crude oil

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Density (g/cm3 ) 20 C Viscosity (mm2 /s) 50 C 100 C Solidication point ( C) Acid umber (mgKOH/g) Wax (w%) Resin (w%) Asphaltene (w%) S (w%) Salt (mg/L) Principle character 0.9156 98.13 17.03 15 1.46 9.66 27.30 1.82 0.91 14.96 h-density h-viscosity h-contents of resin asphaltene 0.9108 90.96 14.49 21 1.02 12.34 32.06 2.52 0.21 6.97 h-density h-viscosity h-contents of resin asphaltene 0.8609 25.44 7.48 34 0.05 27.39 16.72 0.55 0.19 7.63 h-wax content 0.8930 7.60 2.86 1 0.12 5.58 22.97 2.28 0.50 8.24 h-contents of resin asphaltene

0.8603 23.48 6.34 6 0.32 4.12 20.97 2.74 2.71 12.23 h-sulfur content h-contents of resin asphaltene

0.8573 5.00 9 0.24 6.84 8.51 0.92 1.61 19.99 h-sulfur content h-salt content

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Figure 1. Water in oil emulsion.

DA series demulsiers were synthesized using alkoxylated polyhydric alcohol. Polyhydric alcohol, as an initiator, was polymerized with an appropriate amount of propylene oxide (PO) to form the intermediate polymer, with the weight ratio of polyhydric alcohol and propylene oxide at 1:90. Then the intermediate prepolymer was polymerized with an appropriate amount of ethylene oxide (EO), and the DA series demulsiers, DA1DA5, were obtained. The weight percents of EO/PO in them successively were 15%, 30%, 40%, 48%, and 60%. Relatively speaking, its structure is illustrated as follows:

The EO chain is a hydrophilic group, and the PO chain is a lipophilic group in the molecular structure of demulsiers. With the weight ratio of EO in copolymer increasing, the hydrophilic property of demulsier increases. Figures 2 and 3 and Table 2 show the effect of DA series demulsiers on the desalting and dewatering of demulsiers for several crude oils. The #1, #2, and #4 crude oils contain high contents of asphaltene and resin. The basic structure of asphaltene is considered as having condensed aromatic rings as a core, linked with many naphthenic, aromatic rings in

Table 2. Dewatering efciency of DA series demulsiers for several crude oils Demulsiers DA1 DA2 DA3 DA4 DA5 #1 70.0 80.0 80.0 78.0 76.0 #2 75.0 84.0 80.0 80.0 70.0 #3 85.0 90.0 90.0 94.0 92.0 #4 90.0 95.0 95.0 90.0 90.0 #5 80.0 84.0 90.0 94.0 90.0 #6 84.0 90.0 96.0 94.0 80.0

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Figure 2. Desalting efciency of DA series demulsiers for #1, #2, #3 crude oils.

addition to naphthenic rings, which carry many chains of different length. Asphaltenes also contain many groups of sulfur, nitrogen, oxygen, and even many metal complexes of iron, nickel, and vanadium, so they have high surface activity and can be strongly absorbed on the interface of the oil water emulsion. DA2 with a low EO/PO weight ratio of 30% is provided with a superior lipophilic property. Its molecular can be easily absorbed on the interface of oilwater through the oil phase, which peptizes the hydrophobic gelatinous lm surrounding the water droplets in the emulsion and weakens the rigidity of the interfacial lm by a diffusion partitioning process. The desalting efciency, salt content, and dewatering efciency of demulsier DA2 for #1 crude oil, respectively, were 75.00%, 3.74 mg/L, and 80.0%; for #2 crude oil, respectively, were 67.00%, 2.30 mg/L, and 84.0%; for #4 crude oil, respectively, were 64.47%, 2.91 mg/L, and 95.0%.

Figure 3. Desalting efciency of DA series demulsiers for #4, #5, #6 crude oils.

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The wax content with 27.3% in #3 crude oil is high. Wax, a high-melting parafn, easily forms many ne and net-like wax crystals in crude oil, which makes a barrier on the interface beween the brine droplets and crude oil. Such a barrier increases the strength of interfacial lm and hinders the aggregation of the drops, so the emulsion becomes right stable. The weight percent of EO/PO in DA4 is 48%, and its hydrophilic property is higher. It can be absorbed on the interface and displace the wax crystals and other original emulsifying impurities, which is appropriate for #3 crude oil with high wax content. For #3 crude oil, the desalting efciency, salt content, and dewatering efciency of demulsier DA4, respectively, were 67.63%, 2.47 mg/L, and 94.0%. Effect of DB Series Demulsiers on the Desalting and Dewatering of Crude Oils DB series demulsiers are synthesized as follows: octyl-alkylphenol formaldehyde resin, as an initiator, was polymerized with an appropriate amount of propylene oxide to form the intermediate polymer, with the weight ratio of octyl-phenolic resin and propylene oxide is 1:10. Then the intermediate polymer, polymerized with an appropriate amount of ethylene oxide, allowed for the DB series demulsiers, DB1DB5, to be obtained. Their EO/PO wt% in them successively is 15%, 30%, 40%, 48%, and 60%. Its structure is described as follows:

The octyl-alkylphenol formaldehyde resin is synthesized by octyl-alkylphenol, paraformaldehyde, and acid catalyst. The net structure was formed by the initiator, which is lipophilic property polymerized with PO and EO. Figures 4 and 5 and Table 3 show the effect of desalting and dewatering of DB series demulsiers for several crude oils. DB2, similar to DA2 and with the same EO/PO weight ratio of 30%, has better lipophilic property and is also appropriate for #1, #2, and #4 crude oils with high contents of asphaltene and resin. These demulsiers contain a phenol structure with aromatic ring and polarity which have stronger afnity with asphaltene and resin. The demulsier DB2 formed multipoint absorption on the interface of wateroil emulsion, which affected the coalescence of the brine droplets, so the dehydration rate was slower. The dewatering efciency

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Figure 4. Desalting efciency of CB series demulsiers for #1, #2, #3 crude oils.

Figure 5. Desalting efciency of DB series demulsiers for #4, #5, #6 crude oils.

Table 3. Dewatering efciency of DB series demulsiers for several crude oils Demulsiers DB1 DB2 DB3 DB4 DB5 #1 65.0 70.0 68.0 65.0 65.0 #2 72.0 75.0 75.0 70.0 70.0 #3 70.0 75.0 80.0 85.0 80.0 #4 80.0 82.0 82.0 80.0 76.0 #5 75.0 78.0 76.0 76.0 75.0 #6 80.0 82.0 82.0 80.0 80.0

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of DB series demulsiers is lower than DA series demulsiers for these crude oils. For #1 crude oil, the desalting efciency, salt content, and dewatering efciency of demulsier DB2, respectively, reached 70.00%, 2.50 mg/L, and 70.0%; for #2 crude oil, respectively, 64.13%, 2.50 mg/L, and 75.0%; for #4 crude oil, respectively, 61.17%, 3.20 mg/L, and 82.0%. The weight percent of EO/PO in DB4 is 48%, its hydrophilic property is higher, and it is appropriate for #3 crude oil with high wax content. The dehydration rate of DB4 was lower, which favored dissolving salts into freshwater. The desalting efciency, salt content, and dewatering efciency of demulsier DB4 for #3 crude oil, respectively, reaches 76.67%, 1.78 mg/L, and 85.0%. Effect of DC Series Demulsiers on the Desalting and Dewatering of Crude Oils DC series demulsiers are alkoxylated nonyl-alkylphenol formaldehyde polymer, which are synthesized using nonyl-alkylphenol formaldehyde resin as an initiator, and polymerized with appropriate amount of propylene oxide to form the intermediate polymer, with the weight ratio of nonyl-alklyphenol formaldehyde resin and propylene oxide being 1:10. Then the intermediate polymer is polymerized with an appropriate amount of ethylene oxide, and a DC series of demulsiers, DC1, DC2, DC3, DC4, and DC5, was obtained. EO/PO wt% in them successively is 15%, 30%, 40%, 48%, and 60%. Its structure is presented as follows:

Figures 6 and 7 and Table 4 show the effects of desalting and dewatering of DC series demulsiers for several crude oils. Nonyl-alkylphenol formaldehyde resin is synthesized by nonyl-alkylphenol, paraformaldehyde, and acid catalyst. The structure with net form was formed by the initiator which has better lipophilic property polymerized with PO and EO. The carbon atom number of alkyl on phenol core in nonyl-alkylphenol formaldehyde resin is more than that of the DB series, so the lipophilic property of DC was higher than that of DB. DC was easier to diffuse into the interface between water and oil, and the dewatering efciency increased. Because the demulsier DC formed multipoint adsorption on the interface between the water and crude oil, the dehydration rate was

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Figure 6. Desalting efciency of DC series demulsiers for #1, #2, #3 crude oils.

Figure 7. Desalting efciency of DC series demulsiers for #4, #5, #6 crude oils.

Table 4. Dewatering efciency of DC series demulsiers for several crude oils Demulsiers DC1 DC2 DC3 DC4 DC5 #1 75.0 78.0 78.0 75.0 75.0 #2 75.0 80.0 80.0 78.0 75.0 #3 76.0 76.0 80.0 80.0 78.0 #4 80.0 85.0 85.0 80.0 78.0 #5 80.0 80.0 85.0 80.0 80.0 #6 85.0 84.0 85.0 86.0 85.0

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slower, and salts were dissolved into freshwater. The demulsier DC2 is the appropriate demulsier in DC series demulsiers for #1, #2, and #4 crude oil. The desalting efciency, salt content, and dewatering efciency of demulsier DC2 for #1 crude oil, respectively, reaches 77.07%, 3.43 mg/L, and 78.0%; for #2 crude oil, respectively, reaches 77.91%, 2.47 mg/L, and 85.0%; for #4 crude oil, respectively, reaches 70.02%, 2.47 mg/L, and 85.0%. The demulsier DC4 with a higher EO/PO ratio is the appropriate demulsier for #3 crude oil in DC series demulsiers. The desalting efciency, salt content, and dewatering efciency of demulsier DC4 for #3 crude oil, respectively, reaches 72.08%, 2.13 mg/L, and 80.0%. Effect of Assistant on the Desalting of Crude Oils In the above experiments, all demulsiers have excellent dewatering efciency for #5 crude oil and #6 crude oil, but the desalting efciency of the DA4 demulsier for #5 crude oil is 40.15%, and that of the DC2 demulsier for #6 crude oil is 31.22%. Inorganic salts in crude oil include chloride, carbonate, phosphate, nitrate, sulfate, and sulde, most of which can dissolve in water. With the temperature increasing, the solubility of most salts increases. However, some sulfates and suldes are difcult to dissolve and to be removed with water. From Table 5, it is concluded that the content of sulfate and sulde in #5 crude oil and #6 crude oil are higher than in other salts, which is the predominant cause of poor desalting efciency. Three assistantsammonium nitrate (TJ1), N-2 carboxyl diaminoethane triacetic acid (TJ2), and nitric acid (TJ3)are used to improve the desalting efciency for those two crude oils. Figure 8 showed that TJ1 and TJ3 have better desalting efciency for #5 crude oil. When the concentration of demulsier DA4 is 50 ppm in #5

Table 5. Anion concentration in various crude oils Cl (g/ml) #5 crude oil 1 2 3 1 2 3 5.40 3.84 1.86 8.22 6.32 2.12 Br (g/ml) 0.04 0 0 0.06 0 0 NO 3 (g/ml) 0.80 0.65 0.20 0.79 0.31 0.20 PO3 4 (g/ml) 1.22 0.55 0 0.98 0.12 0 SO2 + S2 4 (g/ml) 9.87 7.98 4.53 17.60 14.52 2.73

#6 crude oil

1: Before desalting process; 2: after desalting process, only used demulsier; 3: after desalting process, used demulsier and assistant.

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Figure 8. Desalting efciency of assistants for #5 crude oils.

crude oil, with the concentration of TJ1 increasing, the desalting efciency increases. When the concentration of TJ1 in crude oil is up to 80 ppm, the desalting efciency reaches 58.46%. From Figure 9 it is concluded that TJ3 has better desalting efciency for #6 crude. With the increase of TJ3 concentration from 0 to 80 ppm, the desalting efciency increases from 31.22% to 73.54%, when the concentration of demulsier DA2 in #6 crude oil is 50 ppm. The anions in #5 crude oil and #6 crude oil are mainly chloride, sulfate, and sulde. If only demulsier is used, the content of sulfate and sulde in #5 crude oil or #6 crude oil have only a small decrease in the desalting process. However, after adding assistants, indifuent salt sulfate and sulde

Figure 9. Desalting efciency of assistants for #6 crude oils.

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transform into difuent salts. It makes the contents of sulfate and sulde in #5 and #6 crude oils obviously decreased, so the desalting efciency apparently increases.

CONCLUSION The desalting and dewatering of six crude oils with different properties have been studied. The contents of asphaltene and resin of #1, #2, and #4 crude oil are high; the density and viscosity of #1 and #2 crude oil are large. The demulsiers with higher lipophilic properties than others in the same series, such as DA2, DB2, DC2, which can be easily absorbed on the interface between the water in oil emulsion of #1, #2, #4 crude oil and reveal optimum efciencies of dewatering and desalting. The carbon atom number of alkyl on the phenol core in nonyl-alkylphenol formaldehyde resin, which was the initiator of the DC series, is more than that of the DB series, so the lipophilic property of DC was higher than DB. DC was easier to diffuse into the interface beween water and oil, and the dewatering efciency increased. Because the net form structure was formed, more multipoint adsorbed, their dewatering rate was slower, the salts could well dissolve in washing water and be removed. The lipophilic property of demulsier DC2 with EO/PO weight percent of 30% is superior. Its desalting efciency, salt content after desalting and dewatering efciency for #1 crude oil, respectively, reached 77.07%, 3.43 mg/L, and 78.0%; for #2 crude oil, respectively, 77.91%, 2.47 mg/L, and 85.0%; for #3 crude oil, respectively, 72.08%, 2.13 mg/L, and 80.0%. The density and viscosity of #3 crude oil are lower, and wax content is high. The hydrophilic group and lipophilic group in the molecular structure of DA4, DB4, and DC4 demulsier form a certain hydrophiliclipophilic balance on the interface between water in oil emulsion of #3 crude oil, which leads to better efciencies of desalting and dewatering than other demulsiers of their same series. DA4, with polyhydric alcohol as initiator has better dewatering efciency for #3 crude oil, DB4, with an initiator of octyl-alkylphenol formaldehyde resin, has a slower dewatering rate and better efciency for the desalting of #3 crude oil. The desalting efciency, salt content after desalting, and dewatering efciency of demulsier DB4 for #3 crude oil, respectively, reached 76.67%, 1.78 mg/L, and 85.0%. The density, viscosity, and wax contents of #5 and #6 crude oils are lower; however, the sulfur content is high. The self-made demulsiers showed excellent dewatering efciency for #5 and #6 crude oil, but the desalting efciency was unsatised. By using demulsier and acid assistant TJ1, TJ2, and TJ3, better desalting efciency for #5 and #6 crude oil was obtained. With the concentration of assistant TJ1 increasing, the desalting efciency of #5 crude oil increases. When the concentration of assistant TJ1 in crude oil was

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up to 80 ppm, the desalting efciency increased from 31.22% to 58.46%. With the concentration of assistant TJ3 increasing, the desalting efciency of #6 crude oil also increased. When the concentration of assistant TJ1 in crude oil is up to 80 ppm, the desalting efciency increased from 31.22% to 73.54%. It is concluded that the content of salts sulfate and sulde in #5 and #6 crude oil is high as shown in analysis of anion content before and after desalting. After adding acidic assistants, indifuent salts sulfate and sulde transform into difuent salts that can be removed, so the desalting efciency obviously increases.

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