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The history of acidizing can be traced back more than 100 years when the first US patents (Frasch 1896; Van Dyke 1896) were issued to Herman Frasch and John W. Van Dyke of Standard Oil. Though well-known for their invention of removing sulfur from crude oil produced in Ohio, these two inventors proposed the acidizing methods that have impacted upstream oil and gas exploration and production for a century. Working together, the two inventors filed the two patents on the same date on 27 June 1895, and both were issued patents on 17 March 1896. Strictly speaking, Frasch proposed using hydrochloric acid (HCl), whereas Van Dyke proposed using sulfuric acid (H2SO4) to increase flow of oil wells in limestone formations. Nonetheless, Frasch and Van Dyke each assigned one-half of the inventor rights to the other. The books by Williams et al. (1979), Kalfayan (2008), and Kalfayan and Martin (2009) summarized these inventions, as well as the later developments in field treatments using corrosion inhibitors with HCl. This treatment solution was supplied by Dow Chemical Company, which later created Dowell Incorporated. Application of these early acid jobs was rudimentary at best, but HCl provided improvements in flow in enough cases to create interest in nonexplosive well stimulation.

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