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United States Patent (19) 11) Patent Number: 4,764,231 Slawinski Et Al

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United States Patent (19) 11) Patent Number: 4,764,231 Slawinski Et Al United States Patent (19) 11) Patent Number: 4,764,231 Slawinski et al. 45 Date of Patent: Aug. 16, 1988 (54) WELL STIMULATION PROCESS AND LOW Development, 3rd Edition, 1952 McGraw Hill, "Use of VELOCITY EXPLOSIVE FORMULATION Explosives in Well Completion," pp. 588-593. (75) Inventors: Frank E. Slawinski, Carl Junction, Uren, Petroleum Production Engineering-Oil Field Mo.; William L. Frantz, New Exploitation, 3rd Edition, 1953 McGraw Hill, pp. 165 Ringgold, Pa. and 419-424. Primary Examiner-Stephen J. Lechert, Jr. 73) Assignee: Atlas Powder Company, Dallas, Tex. Attorney, Agent, or Firm-Richards, Harris, Medlock & (21) Appl. No.: 97.530 Andrews 22 Filed: Sep. 16, 1987 57 ABSTRACT Well stimulation involving use of a liquid explosive 51) Int. Cl.".............................................. CO6B 25/14 composition in the explosive fracturing of subterranean 52 U.S. C. ...................................... 149/104; 149/11; formations such as oil and gas bearing formations. An 149/88; 149/101; 149/109.6; 102/301; 102/313 explosive formulation comprising a nitrate ester explo 58 Field of Search ................... 149/11, 88, 101, 104, sive component and a phlegmatizer component is intro 149/109.6; 102/301, 313 duced into a well penetrating the formation to be frac (56) References Cited tured. The phlegmatizer component is an alkyl or alk U.S. PATENT DOCUMENTS oxy diester which is mixable with the nitrate ester and can be varied in concentration to control the detonation 3,116,188 12/1963 Austin ................................... 149/88 velocity and maximum explosive pressure. Examples of 4,092, 187 5/1978 Hildebrant et al. ... 149/11 4,106,960 8/1978 Brachert et al. ...... ... 149/11 phlegmatizing agents include alkyl or alkoxy alkyl es 4,163,681 8/1979 Rothenstein et al. ............... 49/113 ters of adipate or azelaic acids such as dibutoxy adipate 4,292,098 9/1981 Mastroianni et al. ................. 149/89 or diisobutyl azelate or polyethylene glycoxy-based 4,490,196 12/1984 Funk .........were sessess ... 149/92 diesters such as triethylene glycol dipelargonate. After 4,555,279 11/1985 Funk ..... ... 149/92 the formulation is detonated to fracture the formation, 4,595,430 6/1986 Baker .................................... 149/88 the well is placed on production to recover hydrocar bons at an increased rate. OTHER PUBLICATIONS Uren, Petroleum Production Engineering-Oil Field 35 Claims, 1 Drawing Sheet 15 O KOOOO 5000 20000 25OOO U.S. Patent Aug. 16, 1988 4,764,231 5OOO OOOO 15OOO 2OOOO 25OOO V 4,764,231 1. 2 characteristics such as velocity or rate of detonation WELL STMULATION PROCESS AND LOW velocity buildup. The diester desensitizer of U.S. Pat. VELOCITY EXPLOSIVE FORMULATION No. 4,595,430 is employed in the dynamite in relative small amounts; in a range of 0.5-5.0 wt.% preferably TECHNICAL FIELD 1.5 to 2.5 wt.%. The desensitizers disclosed there in This invention relates to the explosive fracturing of clude diesters of dibasic acids having from 5 to 12 car subterranean formations and, more particularly, to the bon atoms, including diesters of glutaric, adipic, and explosive stimulation of wells penetrating subterranean sebacic acids. Triesters or polyesters, exclusive of those hydrocarbon bearing formations and formulations use containing benzene rings can also be employed as de ful in such processes. 10 sensitizers. Preferred desensitizers include triethylene glycol caprate caprylate, mixed diesters produced by ART BACKGROUND reacting isodecyl and 2-ethylhexanol with a mixture of In the petroleum industry it is a well known practice C4-C9 dicarboxyalic acids and triethylene glycol dipe in the completion of new wells and the workover of largonate, glyceryl triacetate or glyceryl triproprionate. existing wells to employ explosives to stimulate the flow 15 U.S. Pat. No. 3,116,188 to Austin discloses the use of of oil and/or gas from hydrocarbon bearing formations. surface active agents to desensitize liquid explosives Various types of explosive formulations have been used such as ethylene glycol dinitrate and nitroglycerine to in such procedures. Historically, explosives used in well impact detonation. Included as desensitizers are polyes stimulation have taken the form of high energy explo ters of polybasic aliphatic acids in which the esterifying sives of high detonation velocities. Uren, L. C. "Petro 20 portion contains from 3 to 7 carbon atoms. Specifically leum Production Engineering-Oil Field Development,” disclosed are tributyrin, tricaproin, and di-n-butyl seba 3rd Edition, 1952 McGraw Hill, under the heading cate used in amounts of 10-30%. "Use of Explosives in Well Completion', pages U.S. Pat. No. 4,292,098 to Mastroianni et al discloses 588-593, discloses use of explosives such as dynamite, liquid gun propellants based upon liquid nitrate esters or nitroglycol or nitroglycerin having detonation veloci 25 nitroparaffins containing a diluent or desensitizing agent ties in excess of 20,000 feet per second. The use of such in the form of a diester of C7-C9 dicarboxylic acids and explosives is also disclosed in the companion volume by C3-C5 alcohols. The preferred esters are azelates with Uren, "Petroleum Production Engineering-Oil Field isopropyl or isobutyl ester groups. The desensitizing Exploitation', 3rd Edition, 1953, at pages 165 and ester is present in an amount within the range of 5-25 419-424. Emphasis is placed not only on fracturing the 30 wt.%. A stabilizer such as 2-nitrodiphenylamine, resor surrounding subterranean formation, but also on form cinol or ethyl centralite may also be employed in an ing cavities in the well to enlarge the effective diameter amount of 1-4%. of the well at the formation face. A somewhat different approach in explosive well DESCRIPTION OF THE INVENTION stimulation involves the use of explosives of relatively 35 low detonation velocity as disclosed in U.S. Pat. No. In accordance with the present invention, there is 4,490,196 to Funk. The compositions in Funk are for provided a new and advantageous well stimulation mulated from a first explosive component mixture, spe process employing a liquid explosive composition in the cifically, a 40-60/60-40 mixture of metriol trinitrate and explosive fracturing of subterranean formations. The diethylene glycol dinitrate; a second component explosive composition comprises a nitrate ester explo (termed an ester component although not all of the sive component selected from the group consisting of second component compounds are esters) taking the nitroglycerine, ethylene glycol dinitrate, propylene form of an aromatic diester, a trialkylaryl phosphate glycol dinitrate, diethylene glycol dinitrate and trimeth such as tricresyl phosphate, or a mono or polyacetyl ylolethane trinitrate and mixtures thereof in combina alkane; and an organic stabilizer component such as 45 tion with a phlegmatizer component which is soluble in ethyl centralite. The explosive formulations disclosed in the explosive component. The phlegmatizer component Funk are said to have slow detonation velocities within is at least one compound having the formula: the range of about 1200-2500 meters/second. The low O O (1) detonation velocity explosive formulations exhibit a I small shockwave component in relation to the total 50 explosive energy and provide a maximum pressure less R2-O-C-R-C-O-Rs than the yield stress of the rock formation surrounding OT the wellbore in which the charge is detonated. This O O (2) minimizes formation of a residual stress field due to I plastic deformation of the rock and minimizes direct 55 borehole damage at the rock face. U.S. Pat. No. 4,555,279 to Funk is a continuation in part of Funk 196 wherein: and discloses an alkylaryl dinitrate as an alternative to R1 is a C4-C9 alkyl group, the ester components of Funk 196. The explosive com R2 and R3 are each independently alkyl or alkoxyal ponent may be metriol trinitrate, diethylene glycol dini 60 kyl groups containing from 3-11 carbon atoms, trate, or nitroglycerine. R4 is an alkyl or alkoxy group, preferably ethyleneg Whereas the patents to Funk disclose the use of dies lycoxy or polyethyleneglycoxy, containing from ters of polybasic aromatic acids to arrive at explosive 2-6 carbon atoms, and formulations of reduced detonation velocity, U.S. Pat. R5 and Ró are each independently alkyl or alkoxyal No. 4,595,430 to Baker discloses the use of diesters in 65 kyl groups containing from 3-11 carbon atoms. which the acid component does not contain a benzyl Preferably, the explosive formulation also contains a group to desensitize a dynamite composition to impact stabilizer such as ethyl centralite in an amount ranging detonation while only minimally reducing explosive up to about 1-2%. The explosive component may be 4,764,231 3 4. present in an amount of about 65% or more with the The phlegmatizing agents employed in the present remainder being the phlegmatizer and the stabilizer, if invention may be characterized generally as esters of any. The phlegmatizer concentration may be varied in dibasic acids, specifically C6-C11 organic acids which order to arrive at the desired velocity of detonation and meet certain criteria of nitrate ester miscibility, stability peak detonation pressure. The explosive formulation 5 and cold temperature flowability. Certain of the phleg can be formulated with excellent low temperature flow matizing compounds for dynamite disclosed in the ability characteristics. Preferably, it has a viscosity at aforementioned U.S. Pat. No. 4,595,430 can be used as minus 20 F. of no more than 500 centipoise (cp). phlegmatizing agents in the liquid formulations of the The phlegmatized explosive composition, as de present invention. However, in contrast to the teachings scribed, above is introduced into a well in proximity to O in this patent respecting the use of such compounds to the subterranean formation and then detonated to ex produce impact insensitivity without having a signifi plosively fracture the subterranean formation.
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