CHAPTER 2 5 ACIDIZING 2.1 INTRODUCTION ‘Acid is used to remove damage near the wellbore in all types of wells. In carbonate formations, acid may be used to create linear flow systems by acid fracturing. Acid fracturing is not applicable to sandstone. “The two basic types of acidizing are characterized through injection rates and pressures. Injection rates below fracture pressure are termed matrix acidizing, while those above fracture pressure are termed fracture acidizing. Matrix acidizing Itis applied primarily to remove skin damage caused by drilling, completion, workover orwell-killing fluids, and by precipitation of deposits from produced water. Dueto the extremely large surface area contacted by acid in a matrix treatment, spending time is very short, Therefore, it is difficult to affect formation more than a few feet from the wellbore. Removal of severe plugging in sandstone, limestone, or dolomite can result in a very large increase in well productivity. Ifthere isno skin damage, a matrix treatment in limestone or dolomite could stimulate natural production no more than one and one-half times. Matrix treatments tend to leave zone barriers intact if pressures are maintained below frac pressures. Fracture acidizing Itis an alternate to bydraulic fracturing and propping in carbonate reservoirs. In fracturing acidizing, the reservoir is hydraulically fractured and then the fracture faces are etched with acid to provide linear flow channels to the wellbore. Two major problems involved in acid fracturing are fracture closure after etching relatively homogeneous carbonates, and plugging of the fracture if appreciable undissolved fines are released by the acid. For relatively heterogeneous carbonates, nonuniform etching of fracture faces may provide good flow channels after fracture pressure is removed. To combat fracture closure in uniformly soluble carbonates, hydraulic fracturing and propping should be considered, as well as special acidizing techniques designed to provide flow channels. If the release of excessive fines is the problem, suspending agents are used to reduce settling and bridging of fines in the fracture during clean-up after acidizing2.2 ACIDS USED IN WELL STIMULATION Hydrochloric Acid (HCI) Hydrochloric acid used in the field is normally 15% by weight HCI; however, acid concentration may vary between 5% and about 35%, HCl acid will dissolve limestone, dolomite, and other carbonates. The chemical equation for the reaction between HCI acid and limestone is as follows: 2HCI+ CaCO, > CaCl, +H,0+ CO, . (2.1) 73 100 nbn 18 44 Except in the case of the two molecules of HCI, the figures shown below each of the compounds are their molecular weights. They represent the relative weights of the individual molecules and therefore the relative weights of the substances which react or are formed as products of the reaction, Eq. (2.1) may be interpreted as saying that 73 Ib of HCl acid react with 100 Ib of calcium carbonate to form 111 Ib of calcium chloride, 18 Ib of water, and 44 Ib of carbon dioxide. The usual acid treating solution contains 15 per cent HCI by weight and has a specific gravity of 1.075. In 1000 gal of this acid solution there are 1000 x 8.34 x 1.075 x 0.15 = 1344.8 lb of HCI acid. From the relative weights of the substances involved in reaction Eq.(2.1), it can be calculated by proportion that 1344.8 Ib of HCl reacts with 1842.2 Ib of calcium carbonate to form 2044.8 Ib of calcium chloride, 331.6 Ib of water, and 810.6 Ib of carbon dioxide, As the average density of limestone is 170 Ib per cu ft, the 1842.2 Ib of calcium carbonate represents a volume of 10.84 cu fi. When dolomite reacts with HCI acid, the products are the same as in the limestone reaction, except that magnesium chloride is also formed, as shown by the following equation 4HCI + CaMg(CO,), -> CaCl,+ MgCl, + 2H, + 2CO, (2.2) 146 184.3 A 95.3 36 83 Magnesium chloride is quite soluble in water, and so, as in the case of pure limestone, all the products of the reaction are soluble in spent acid, or are gaseous, From Eq.(2.2) it can be calculated that 1000 gal of 15 per cent HCl acid solution will react with 1697.6 Ib of pure dolomite to form 1022.4 1b of calcium chloride, 877.7 lb of magnesium chloride, 331.5 1b of water, and 810.4 1b of carbon dioxide. Acetic Acid (HAc) Acetic acid (CH,COOH) is a weakly-ionized, slow-reacting organic acid. A thousand gallons of 10% acetic acid will dissolve about 704 Ib. of limestone, The cost of dissolving @ given weight of limestone is greater with acetic acid than with HCI acid ‘Acetic acid is relatively easy to inhibit against corrosion and can usually be left in contact with tubing or casing for days without danger of serious corrosion. Because of this characteristic, acetic acid is frequently used as a perforating fluid in limestone wells. Other advantages of acetic acid in comparison to HC! acid are: 1, Acetic acid is naturally sequestered against iron precipitation. 2. It does not cause embrittlement or stress cracking of high strength steels. 3. [twill not corrode aluminum. 4. It will not attack chrome plating up to 200 °F.35 Formic Acid Formic acid (HCOOH) is a weakly-ionized, slow reacting organic acid, It has somewhat similar properties to acetic acid, However, formic acid is more difficult to inhibit against corrosion at higher temperatures and does not have the widespread acceptance and use of acetic acid. Hydrofluorie Acid Hiydroftuorie acid used in oil, gas, or service wells is normally 3% HF combined with 12% HCL It is employed exclusively in sandstone matrix treatments to dissolve either natural clays or clays which have migrated into the formation, One thousand gal of 4.2% HF acid will dissolve 700 Ib of clay, Fast reaction time and precipitants make HF acid undesirable in carbonate-containing sands having more than 20% solubility in HCl, HF acid should never be used in carbonate formations. Sulfamic Acid Sulfamic acid, a granular-powdered material, reacts about as fast as HCL, The primary advantage of sulfamic acid is that it can be hauled to the location as a dry powder and then mixed with water, Unless sulfamic acid is modified, it will not dissolve iron oxides or other iron scales, Because of its molecular weight, the amount of calcium carbonate dissolved by one pound of sulfamic acid is only about one-third that dissolved by an equal weight of HCI acid. Acidizing with sulfamic acid is normally much more expensive than with HCI acid. Sulfamic acid is not recommended for temperatures above 180 °F because it will hydrolyze to form sulfuric acid. When H,SO, reacts with limestone or CaCO, scale, calcium sulfate will be precipitated. 2.3 ACID ADDITIVES . ‘The use of acid can create a number of well problems. Acid may (1) release fines that plug the formation, (2) form emulsions, (3) oreate studge, and (4) corrode steel. Additives are available to correct these and a number of other problems Surfactants ‘Surfactants should be used on all acid jobs to reduce surface and interfacial tension, to prevent emulsions, to water wet the formation, and to safeguard against other associated problems. Swabbing and clean-up time after acidizing oil and gas wells can be reduced by lowering surface tension. Suspending Agents Most carbonate formations contain insolubles which can cause blocking in formation pores or fractures if the fines released by acid are allowed to settle and bridge. Suspension should be differentiated from dispersion. Dispersed particles usually settle in a short time. Clean-up after fracture acidizing can be accelerated by use of a suspending agent. Sequestering Agents Sequestering agents act to complex ions of iron and other metallic salts to inhibit precipitation ofiron as HCI spends. During acidizing if hydrated oxides of iron arenot pr evented from dropping out, these insoluble iron compounds may be redeposited near the wellbore and cause permanent plugging, Sequestering agents should always be used if rusty tubing or casing is to be contacted.