Sandstone acidizing using mud acid is a quick and complex process where dissolution and precipitation occur simultaneously. Retarded mud acids are less reactive with the rock reducing the reaction rate hence increased penetration into the formation to remove deep damage. To understand thoroughly the retarded mud acid system, an in-depth investigation of the reaction of HF (hydrofluoric) and H2SiF6 (fluorosilic acid) with alumino silicates and the retarded system is undertaken using coreflood analysis and mineralogy analysis using the inductively coupled plasma. Coreflood analysis is used to understand and investigate the permeability changes in the sandstone rock as the retarded mud acid is injected at different conditions and the inductively coupled plasma (ICP) is used to investigate the effluent samples from the coreflood analysis to properly understand this system. Several issues that have not been addressed previously in literature are identified and discussed, including an optimum flowrate when sandstone is acidized, by acidizing the sandstone rock with a retarded acid system at various flowrates and determining the initial and final permeabilities. Also investigated is the retarded acids compatibility with ferric iron and a comparison of the retarded acid system to regular acid to consequently enable a thorough understanding of the retarded mud acid system using aluminum chloride (AlRMHF). Based on the work done, it is found that the absence of a hydrochloric (HCl) preflush is very detrimental to the sandstone core as calcium fluoride is precipitated and the retarded acid system is found to be compatible with iron(III) as an impurity. The regular acid (RMHF) dissolves considerably more silicon and produces more fines than the AlRMHF. 1cc/min is found to be the optimum flowrate when a sandstone core is acidized with AlRMHF. At this low flowrate, less silicon is dissolved, more aluminum is seen in the effluent and more calcium is dissolved. The retarded aluminum acid system considerably reduces the rate of reaction as evidenced in the dissolution reaction when compared to a regular mud acid system. This reduced rate of reaction implies deeper acid penetration and ultimately deeper damage removal.

Acidizing sandstone reservoirs is a complex process. If not fully studied, it could lead to formation damage. A combination of HCl/HF has been widely used to stimulate sandstone reservoirs. However, the success rate is low due to the complexity of the reactions involved in this process. These reactions result in potentially damaging precipitation and cause formation damage. The problem is more severe when dealing with Bandera sandstone formations that contain a high concentration of carbonate minerals and clay particles. The purpose of this study is to present and evaluate multi-stage acid injection into the Bandera sandstone cores to remove formation damage. In this study, coreflood experiments were conducted on Bandera sandstone cores (1.5 in. x 6 in.) at a flow rate of 4 cm^3/ min and temperature of 140°F. A mixture of formic acid and HF was used as an organic mud acid. Preflush of hydrochloric and formic acid was employed to remove carbonate minerals. Bandera sandstone cores contain a considerable amount of HCl sensitive clays. So another stage was employed to cover clay minerals and prevent HCl attack on the surface of clay particles. Different clay stabilizers as well as preflush pore volume were examined in this study. At the end, this multi-stage treatment design was tested on a Berea sandstone core to investigate the impact of mineralogy. During each experiment effluent samples were collected. Samples were analyzed using Inductively Coupled Plasma (ICP) and Scanning Electron Microscopy (SEM) to investigate reaction kinetics and chemistry of precipitation. Chemical analysis confirmed incompatibility of HCl with clays in Bandera cores at 140°F. Clay stabilizer CSA showed the ability to prevent HCl attack on the clay particle’s surface. As a result, a coreflood experiment conducted using CSA led to permeability improvement. The result of the coreflood experiment conducted using CSC indicated that this chemical is able to exchange cations with clay particles, however permeability decreased due to an insufficient injection of preflush. As in another experiment, increasing preflush pore volume using CSC resulted in permeability improvement. CSB completely failed to cover clay minerals and permeability decreased drastically at the end of the treatment.

Cement slurries are used in oil wells to isolate the production area from the rock formation. An important property of these materials is their durability. Due to the interactions of the cement slurries with aggressive media in the oil wells, the durability can be threatened or lost. Cement slurries modified with polymers are promising materials candidates for cementing oil wells. Thus, it is necessary to evaluate new materials in hostile environments. In this work, new cement slurries were prepared with the Epoxy resin and the ethylenediamine hardener in two different media: distilled water and sea water. The new slurries were tested for their mechanical properties and characterized before and after interaction with the following media: production water, hydrochloric acid solution and mud acid solution. After 365 days of contact with the production water, the modified slurries showed greater chemical and mechanical resistance compared to the slurries without the polymer network (Standard slurries). Moreover, for the modified slurries after contact with the production water, a decrease of 9% in the compressive strength occurred, whereas for the slurries without the polymer network, the reduction reached 40%. Kinetic studies, chemical and thermodynamic equilibrium were carried out in the investigation of the interaction of the cement slurries with the solutions of HCl and mud acid. The results have suggested that the interactions between the modified slurries and the acid media are due to surface reactions with preservation of the hydrated compounds of the cement, causing a mass loss around 25%. For the standard slurries, the mechanism is predominantly diffusion, with structural deterioration of these slurries and mass loss of approximately 46%. Thus, the modified slurries with the polymer network Epoxy-EDA presented good characteristics to be used in the oil well procedures. / Pastas de cimento são utilizadas em poços de petróleo para isolar a zona de produção da formação rochosa. Uma propriedade importante desses materiais é sua durabilidade. Devido suas interações com meios agressivos, essa propriedade pode ser ameaçada ou perdida. Pastas de cimento modificadas com polímeros são materiais promissores candidatos à cimentação de poços de petróleo. Assim, é necessário avaliar novos materiais em meios hostis. Neste trabalho, novas pastas de cimento foram preparadas com a resina Epoxy e o endurecedor Etilenodiamina em dois meios distintos: água destilada e água do mar. As novas pastas foram testadas em relação às suas propriedades mecânicas e caracterizadas antes e após a interação com os seguintes meios: água de produção, solução de ácido clorídrico e solução de mud acid. Após 365 dias de contato com a água de produção, as pastas modificadas apresentaram maior resistência química em comparação com as pastas sem a rede polimérica (pastas padrão). Além disso, para as pastas modificadas após o contato com a água de produção, ocorreu uma diminuição de 9% na resistência à compressão, já para as pastas sem a rede polimérica, a redução atingiu 40%. Estudos cinéticos, equilíbrio químico e termodinâmico foram realizados na investigação da interação das pastas de cimento com as soluções de HCl e mud acid. Os resultaram sugerem que as interações entre as pastas modificadas e os meios ácidos são devido a reações superficiais com preservação dos compostos hidratados do cimento, ocasionando uma perda de massa em torno de 25%. Para as pastas padrão, o mecanismo é predominantemente por difusão, com deterioração estrutural dessas pastas e perda de massa de aproximadamente de 46%. Desta forma, as pastas modificadas com a rede polimérica Epoxy-EDA apresentaram boas características para serem utilizadas em ambientes subterrâneos dos poços de petróleo. / São Cristóvão, SE