Santana , Bruna V. de Lima , Luciana V. Amorim3, Rosangela de C. Balaban4

Copyright 2012, Instituto Brasileiro de Petróleo, Gás e Biocombustíveis - IBP Este Trabalho Técnico foi preparado para apresentação na Rio Oil & Gas Expo and Conference 2012, realizado no período de 17 a 20 de setembro de 2012, no Rio de Janeiro. Este Trabalho Técnico foi selecionado para apresentação pelo Comitê Técnico do evento, seguindo as informações contidas no trabalho completo submetido pelo(s) autor(es). Os organizadores não irão traduzir ou corrigir os textos recebidos. O material conforme, apresentado, não necessariamente reflete as opiniões do Instituto Brasileiro de Petról eo, Gás e Biocombustíveis, Sócios e Representantes. É de conhecimento e aprovação do(s) autor(es) que este Trabalho Técnico seja publicado nos Anais da Rio Oil & Gas Expo and Conference 2012.

Nesse trabalho, um copolímero graftizado de poli (N-isopropilacrilamida) sobre carboximetilcelulose sódica (CMC-gPNIPAM) foi sintetizado e avaliado como inibidor de inchamento de uma argila expansiva. A argila foi previamente triturada até passar em uma peneira de 200 mesh. O grau de inchamento da argila foi avaliado por imersão em diferentes fluidos aquosos contendo CMC (Carboximetilcelulose sódica), CMC-g-PNIPAM, inibidor comercial e diferentes concentrações de sal. As propriedades reológicas dos fluidos foram investigadas com o objetivo de avaliar o efeito da viscosidade sobre o grau de inchamento. De acordo com os resultados obtidos, tanto a CMC quanto o seu derivado apresentaram boa eficiência de inibição de inchamento da argila. A CMC e o copolímero CMC-g-PNIPAM mostraram uma redução nos valores do percentual de inchamento em torno de 10 e 5 %, respectivamente, em relação ao inibidor comercial.

In this work, a graft copolymer of poly (N-isopropylacrylamide) onto sodium carboxymethylcellulose was synthesized and evaluated as inhibitor of expansive clay. The clay was previously crushed to pass through of 200-mesh sieve. The swelling degree was evaluated in presence of CMC (sodium carboxymethylcellulose), CMC modified with PNIPAM (CMC-g-PNIPAM), commercial inhibitor and different concentrations of salt. Rheological properties of the fluids were investigated aiming to correlate the viscosity to the swelling degree of clay. According to the obtained results, both CMC and CMC-g-PNIPAM showed good swelling inhibition efficiency. CMC and CMC-g-PNIPAM presented a reduction in the percentage of clay swelling around 10 and 5 %, respectively, compared to the commercial inhibitor.

Keywords: CMC-g-PNIPAM, clay swelling, rheological properties

______________________________ 1 Mestre, Professora do Curso de Engenharia de Petróleo da UFERSA 2 Mestre, Doutoranda em Química da UFRN 3 PHD, Professora do Curso de Engenharia de Petróleo da UFCG 4 PHD, Professora do Curso de Química da UFRN

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1. Introduction
The CMC structure is based on the β-(1 4)-D-glucopyranose polymer of cellulose. Different preparations lead to different degrees of substitution (DS). However, the DS is generally found in the range 0.6 - 0.95. The literature has showed innumerous applications of this polymer in different areas depending on the degree of substitution. Carboxymethylcellulose and their derivatives frequently are used in drilling fluids as viscosifiers and fluid-loss reducers (Thomas and Amoco, 1982). In this paper, it has been proposed a new application to this polymer in water-based drilling fluids. When water-based drilling fluids are employed, clay swelling can have an adverse impact on the drilling operation, significantly increasing well construction costs. Clay swelling may result in wellbore instability problems, hole closure causing tight hole and problems when running casing. It can also cause agglomeration of drilled cuttings leading to reduced hole cleaning efficiency, build up of thick cuttings beds and reduced rates of penetration arising from balling of the drill bit with sticky clay. In the worst case, wellbore instability can result in the loss of the drilling assembly, well side-tracks or total abandonment of the well. All of these problems can dramatically reduce drilling rates and significantly increase exploration and production costs (Anderson et al., 2010). There are chemical additives, organic and inorganic, that minimize the interactions between the rock (shale) and fluid. These inhibitors act on the active clay ionic/polar sites in the basal spacing and the lateral edges, hindering the water molecules entry, reducing the clays hydration (Bassi et al., 2009; Retz et al., 1991; Serra, 2003). In this context, the main objective of this work was to evaluate the efficiency of CMC and CMC-g-PNIPAM as inhibitors of clays expansion for application in water-based drilling fluids.

2. Methodology
2.1. Materials Expansive clay from BUN (Bentonite Union Northeast) was crushed to pass through of 200-mesh sieve prior to laboratory tests. Carboxymethylcellulose (CMC) and Sodium Chloride were purchased from Sigma Aldrich. CMC modified with PNIPAM (CMC-g-PNIPAM) was synthesized via free radical polymerization method as described in literature (Lee et al., 2003; Moura et al., 2008), but with some modifications (Lima, 2012). 2.2. Sample preparation About 5g of clay were subjected to a pressure of 10,000 psi in a compactor of Fann 9, during 90 minutes. Afterwards, the samples were coupled to the linear swelling meter (LSM Model 2000, Fann). Subsequently, the pellets were immersed in 250 mL of a given fluid at 25°C for 180 minutes. 2.3. Determination of swelling degree The swelling degree of the clay was investigated at different aqueous solutions containing sodium chloride (NaCl), CMC, CMC-g-PNIPAM and Clay inhibitor (Table 1). Around 5g of compacted clay was immersed in 250 mL of each solution and swelling measurements were carried out by using a Linear Swelling Meter equipment (model 2000, FANN). The Degree of Swelling (S) was calculated as a function of time, during 180 minutes at pre-determined intervals. Table 1. Additives concentration used to evaluate the swelling degree and rheological properties Additive Clay inhibitor CMC CMC-g-PNIPAM NaCl Concentration 8 lb/bbl 3 lb/bbl 3 lb/bbl 0.5; 0.75; 1; 3 M


Rio Oil & Gas Expo and Conference 2012 2.4. Determination of rheological properties The rheological properties of aqueous dispersions of clay were evaluated in a Thermo Fisher Scientific HAAKE MARS rheometer, equipped with coaxial cylinders DG41-Ti. All rheological measurements were performed at 25°C.

3. Results and Discussion
The fractional swelling was evaluated as a function of time. The Equation 1 has been used to describe the water diffusion into clay in contact with different formulations (Table 1). The Table 2 shows the kinetic parameters of swelling degree with regard to the clay. S180 refers to the swelling degree of pellets at 180 minutes; n’ describes the water transport model in the medium, the values of n’ close to 0.5 indicate a fickian diffusion mechanism, whereas in the range of 0.5 – 1 show an anomalous mechanism. The k constant is an intrinsic parameter characteristic of the system. These constants can be calculated by Equation 1 (Katime et al., 2001; Maltais et al., 2010).

Ft =

St =kt n' S180
Table 2. Swelling kinetic parameters Fluid Clay inhibitor CMC CMC-g-PNIPAM 0.5M NaCl S180 (%) 41.02 31.78 36.92 41.47 n’ (*) 0.5265 0.5906 0.5997 0.6132 k (10³ min-n) 2.7921 1.5812 1.7716 1.8188 R² 0.9822 0.9893 0.9815 0.9921



According to results presented in Table 2, CMC and CMC-g-PNIPAM showed to be more efficient in terms of inhibition of swelling degree than the commercial inhibitor and sodium chloride solution. The clay swelling can be controlled primarily by the composition of aqueous solutions that come into contact with clays (Amorim et al., 2007). Since these clays consist of negatively charged silicate layers and the negative charges are compensated by interlayer counterions. These counterions and the charged clay mineral surfaces interact strongly with polar solvents, most notably water (Hensen et al., 2001). The development of swelling inhibitors with improved technical and environmental performance represents a challenge to organic oilfield chemistry due to the complex and heterogeneous nature of clay minerals and the careful balance of properties that must be maintained for a drilling fluid to be effective. According to Table 2, clay inhibitor showed similar inhibition of water sensitive shale compared to NaCl, probably due to the similar valences between the two cations types. On the other hand, in this case, effective method of inhibiting clay swelling was achieved through the use of polymers which incorporated appropriate functional groups that interact favorably with clays to reduce swelling, i.e, preventing their hydration (Anderson et al., 2010). The k values, that are associated to the water saturation in the clay, were higher in formulations containing commercial inhibitor and sodium chloride than CMC-g-PNIPAM and CMC. High k values indicate that water transport in the medium was easier than in other cases. There is no significant difference between values of diffusional exponent (n’) with regard to these fluids (n’ = 0.5 – 0.6). However, the fluid containing commercial inhibitor displays diffusion behavior closer to fickian model than in other fluids. The n’ value close to 0.6 is indicative of anomalous diffusion behavior. This result might be associated to interactions of this clay with each additive (either polymer or salt concentration).


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Figure 1. Swelling degree of clay as a function of time for all the fluids According to Figure 1, the clay basal spacing initially expanded very rapidly under contact with the solution, with the rate of expansion slowing considerably after 180 min. The swelling degree is controlled by crystalline swelling and double-layer swelling. Initially, the interlayer space between clay layers is occupied by adsorbed water under moderate humidity conditions, while the micropores remain dry (stage I). After the contact with the solution, although the particles swell and fill the micropores, the swelling aggregates can no longer be recognizable beyond this point (stage II). At stage III, particles swelled further after filling micropores in aggregates, resulting in the mesoscopic swelling of the aggregates. Suzuki and co-workers (2005) have proposed this mechanism to explain the microstructural evolution and hydraulic conductivity of bentonite in NaCl solution. Rheological properties have been investigated with the objective of understanding the dynamic of interactions between clay and the additives (Sodium chloride, commercial inhibitor, CMC and CMC modified with PNIPAM) and to associate the swelling degree to viscosity. Figure 2 indicates the simple correlation between viscosity and swelling degree as a function of salt concentration.

Viscosity Swelling degree

Figure 2. Apparent viscosity of clay aqueous suspension ( 100 s-1) and swelling degree as a function of different salt concentrations Figure 2 shows that as the viscosity increases, the swelling degree has the tendency of increasing too. Salt concentrations above 1M promoted higher viscosity values than low concentrations, since clay particles presented 4

Rio Oil & Gas Expo and Conference 2012 greater hydrodynamic volume above salt concentration of 1M. It seems that the random orientation of clay microcrystals into aggregates is possible in high salt concentrations. Another important aspect is the possibility of predicting optimum inhibitor concentration as a function of viscosity. Preliminary results confirm the correlation between viscosity and swelling degree. Experiments are currently underway in order to correlate the optimum amount of CMC-g-PNIPAM with regard to viscosity and swelling degree. The apparent viscosity values of CMC and CMC-g-PNIPAM are plotted against temperature in Figure 3.

Figure 3. Apparent viscosity values of CMC and CMC-g-PNIPAM, at 6 g/L and 7.3 s-1 According to Figure 3, CMC aqueous solution has higher viscosity than CMC-g-PNIPAM in the same total polymer concentration, at different temperatures. This could be attributed to the greater expansion of CMC chains, due to electrostatic repulsion between carboxylate groups (COO-) located along the CMC backbone. The apparent viscosity of CMC aqueous solutions decreases as the temperature increases. This is in accordance with standard behavior described by the Arrhenius equation, typical for hydrophilic polymeric chains (Bokias et al., 2001). According to this study, the viscosity of aqueous solution of the copolymer CMC-g-PNIPAM also decreases following the Arrhenius behavior. This result indicated that the CMC-g-PNIPAM copolymer used in this work is not thermothickening, probably due to the small content of PNIPAM (Shi et al., 2007).

4. Conclusions
In this work, we report a promisor application of CMC and CMC modified with PNIPAM for clays inhibition. According to results, it has been observed that water diffusion during clays swelling follows an anomalous mechanism, no fickian, being influenced by presence of the additives used. Besides, it is possible to predict the optimum concentration of inhibitor, as well as its efficiency as a function of rheological properties. The fluid flow in this clay should be expressed as a function of pore geometry and pore size. The microstructures and molecular-scale properties will thus be needed to further analyze the water diffusion kinetic.

5. Acknowledgements
The authors are grateful to CAPES, PRH30/ANP/MCT and PETROBRAS for financial support and the Laboratory of Petroleum Research (LAPET-UFRN) for their support in carrying out this work.

6. References
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