Abstract
Beginning in the 1860s, fracturing was used to stimulate or rather shoot rock formations for oil production. To increase both initial flow and ultimate extraction, liquid and solidified nitroglycerin was used in these years. The concept of (hydraulic) fracturing with pressure instead of explosives grew in the 1930s. Beginning in 1953, water-based fluids were developed using different types of gelling agents. Nowadays, aqueous fluids such as acid, water, brines, and water-based foams are used in most fracturing treatments. The breakdown of the fluids to decrease viscosity is mostly carried out by use of oxidizing agents. Thereby, the technology is facing concerns regarding microseismicity, air emissions, water consumption, and the endangerment of groundwater due to the risk of perforating protective layers and the ooze of chemicals through the surface. Furthermore, particularly both cross-linking and breaking agents pose serious risks for humans respectively are environmentally hazardous in terms of eco-toxicity—while the degradation effect of common oxidizing agents is relatively low in cases of high-temperature fracturing treatments. According to our comparative viscosity tests, the viscosity of both common hydrogels with and without oxidizing agents can be reduced to the same level when heated to 130 °C or above. Furthermore, in both cases no non-Newtonian behavior could be observed after the temperature treatment (anymore). Therefore, we developed a hydrogel that allows for optimized cross-linking without toxic linkers and that can be dissolved without environmentally hazardous chemicals. Furthermore, it avoids the clogging of pores by hydrogel residues and improves oil and gas exploitation.
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Notes
The terms (hydraulic) "fracturing" and "fracing" are used interchangeably in the literature and practice. Accordingly, we follow the same approach. The term "fracking" is, however, only common in Germany. Thus, we use “fracking” only in case we cite a corresponding reference.
With an overview on applied hydraulic fracture models allowing for the primary physical mechanisms involved (deformation of the rock, fracturing of the rock, flow of viscous fluid within the fracture, and leak-off) and a new single expansion framework which describes the interaction between several physical processes see Mitchell et al. (2007). On diffusion in a fractured medium, see Cannon and Meyer (1971).
TSO is a technique used in moderate to high-permeability reservoirs to form proppant bridges at the end of the cracks to cause a widening of the cracks instead of further longitudinal growth. For a more comprehensive insight, see Čikeš and Plantić (2005, 1, 5 et seqq.); Smith et al. (1984, 95–103); Smith and Hannah (1996).
An employee of Stanolind Oil and Gas Corporation (a Standard Oil (of Indiana)/Amoco (now BP) subsidiary founded in the 1920s).
Depending on the definition, foams can be defined as a separate category (foam-based fluids, e.g., see Meiners et al. 2013, A75) or a subcategory of water-based fluids, as they are largely based on water.
With an analysis of oil flow in fractured oil reservoirs using foam injections Choi et al. (2013).
For the stressed state of a rock mass, corresponding measurements and planning decisions, e.g., see Kurlenya et al. (1994); Fallahzadeh et al. (2015). For the use of fuzzy logic in candidate-well selection for hydraulic fracturing in oil and gas wells, e.g., see Zoveidavianpoor et al. (2012). For predicting the behavior of rock masses and related uncertainties in modeling, e.g., see Elmouttie and Poropat (2014).
For the simulation of the nonlinearity and discontinuity of a rock mass, e.g., see Pan et al. (2013).
For the governing of fluid flow through porous media under the usage of mathematics and its development over time, e.g., see Cannon and Meyer (1971); Dupuy et al. (1973); Chen et al. (1974); Wassermann et al. (1975); Durrer and Slater (1977); Mitchell et al. (2007); Rahman and Rahman (2010); Gordalla et al. (2013); Yusof and Mahadzir (2014).
For microscopic modeling of the hydraulic fracturing process, e.g., see Eshiet et al. (2013).
For a comparison between neural networks and multiple regression analysis to predict rock fragmentation, e.g., see Enayatollahi et al. (2014).
1.000 m3 or more of water per fracturing stage or 10,000 m3 or more of water during the entire process. See EU (2014).
Regarding microseismic monitoring during oil well stimulation by hydraulic fracturing, e.g., see Ilinski and Krasnova (2010).
With a review about recent seismic activity possibly related to hydraulic fracturing Ellsworth (2013).
In the form of solids, such as coal, iron, sand, and gravel; liquids, such as crude petroleum; and gases, such as natural gas. The category includes quarrying, milling of mined materials, injection of water for secondary oil recovery or for unconventional oil and gas recovery (such as hydraulic fracturing), and other operations associated with mining activities (Maupin et al. 2014).
As boron compounds typically sodium tetraborate (Borax Anhydrous, CAS Number 1330-43-4) is used. According to the Material Safety Data Sheet (MSDS) sodium tetraborate is toxic to fish (LC50). It is classified as irritating and harmful, causing serious eye irritation (risk phrase H319 (EG) Nr. 1272/2008) and harming fertility or damaging the unborn child (risk phrase H360 (EG) Nr. 1272/2008). Furthermore, it can cause nausea, vomiting, diarrhea, gastrointestinal cramps, erythematous lesions of the skin and mucous membranes, and liver irregularities. Other symptoms include circulatory collapse, tachycardia, cyanosis, delirium, convulsions and coma. According to reports, less than 5 g can cause the death of infants and 5–20 g the death of adults. See MSDS (2015a).
Furthermore, boric acid (CAS Number 10043-35-3) is used. According to the MSDS boric acid is toxic to fish (LC50, LC0), and daphnia, and other aquatic invertebrates (LC50, EC50). It is classified as harmful and toxic for human reproduction, harming reproduction and fertility or damaging the unborn child (risk phrase H360FD (EG) Nr. 1272/2008) as well as having acute toxicity (LD50 oral—rat). Furthermore, it can cause nausea, vomiting, diarrhea, gastrointestinal cramps, erythematous lesions of the skin and mucous membranes, and liver irregularities. Other symptoms include circulatory collapse, tachycardia, cyanosis, delirium, convulsions and coma. According to reports, less than 5 g can cause the death of infants and 5-20 g the death of adults. Beyond this, for most toxicity test categories (MSDS Class 11 and 12), no data are available for both chemicals. See MSDS (2014a)
Zirconium compounds used, e.g., are zirconyl chloride hydrate (CAS Number 15461-27-5). Zirconyl chloride hydrate is classified (in the MSDS) as dangerous, explicitly causing severe skin burns and eye damages (risk phrase H314 (EG) Nr. 1272/2008). It can cause cough, shortness of breath, headache, nausea, and vomiting. Eco-toxicity tests (MSDS Class 12) have not been performed. Same applies to the rest of the toxicity tests/test categories according to MSDS Class 11. See MSDS (2014b).
Titanium(IV) oxide (a titanium compound used, CAS Number 13463-67-7) is toxic to fish (LC50), daphnia, and other aquatic invertebrates (EC50, EC0) according to the MSDS. Furthermore, it has germ cell mutagenicity (hamster, ovaries, micronucleus test; hamster, lungs, DNA inhibition; hamster, ovaries, sister chromatid exchange; mouse, micronucleus test). See MSDS (2016a).
As bromate, e.g., sodium bromate (CAS Number 7789-38-0) is used. According to the MSDS it is classified as oxidizing (risk phrase H272 (EG) Nr. 1272/2008) and irritating, causing serious eye irritation (risk phrase H319 (EG) Nr. 1272/2008), skin irritation (risk phrase H315 (EG) Nr. 1272/2008), airway irritation (risk phrase H335 (EG) Nr. 1272/2008) as well as being deleterious when swallowed (risk phrase H302 (EG) Nr. 1272/2008) and having acute toxicity (LD50 intraperitoneal—mouse). Beyond this, for most (human-)toxicity test categories (MSDS Class 11) no data are available. Eco-toxicity tests (MSDS Class 12) have not been performed at all. See MSDS (2013).
As persulfates typically sodium persulfate/peroxodisulfate (CAS Number 7775-27-1), ammonium persulfate/peroxodisulfate (CAS Number 7727-54-0) or potassium persulfate/peroxodisulfate (CAS Number 7775-21-1) are used.
According to the MSDS sodium persulfate is toxic to fish (LC50), algae (EC50), and daphnia, and other aquatic invertebrates (EC50). It is classified as oxidizing (risk phrase H272 (EG) Nr. 1272/2008), irritating and harmful, explicitly causing serious eye irritation (risk phrase H319 (EG) Nr. 1272/2008), skin irritation (risk phrase H315 (EG) Nr. 1272/2008), airway irritation (risk phrase H335 (EG) Nr. 1272/2008), allergic skin reactions (risk phrase H317 (EG) Nr. 1272/2008), as well as being deleterious when swallowed (risk phrase H302 (EG) Nr. 1272/2008) and having acute toxicity (LD50 oral—rat; LC50 inhaling—rat; LD50 skin—rabbit). Furthermore, it can cause allergy, asthmatical symptoms and dyspnea when inhaled (risk phrase H334 (EG) Nr. 1272/2008). Reiterated exposition can cause asthma. See MSDS (2012a).
According to the MSDS ammonium persulfate is toxic to fish (LC50), and daphnia, and other aquatic invertebrates (EC50). It is classified as oxidizing (risk phrase H272 (EG) Nr. 1272/2008), irritating and harmful, explicitly causing serious eye irritation (risk phrase H319 (EG) Nr. 1272/2008), skin irritation (risk phrase H315 (EG) Nr. 1272/2008), airway irritation (risk phrase H335 (EG) Nr. 1272/2008), allergic skin reactions (risk phrase H317 (EG) Nr. 1272/2008), as well as being deleterious when swallowed (risk phrase H302 (EG) Nr. 1272/2008) and having acute toxicity (LD50 oral—rat; LD50 skin—rat). Furthermore, it can cause allergy, asthmatical symptoms and dyspnea when inhaled (risk phrase H334 (EG) Nr. 1272/2008). See MSDS (2016b).
According to the MSDS potassium persulfate is toxic to fish (LC50), bacteria (EC50), and daphnia, and other aquatic invertebrates (EC50). It is classified as oxidizing (risk phrase H272 (EG) Nr. 1272/2008), irritating and harmful, explicitly causing serious eye irritation (risk phrase H319 (EG) Nr. 1272/2008), skin irritation (risk phrase H315 (EG) Nr. 1272/2008), airway irritation (risk phrase H335 (EG) Nr. 1272/2008), allergic skin reactions (risk phrase H317 (EG) Nr. 1272/2008), as well as being deleterious when swallowed (risk phrase H302 (EG) Nr. 1272/2008) and having acute toxicity (LD50 oral—rat; LD50 skin—rabbit). Furthermore, it is harmful to aquatic organisms. Moreover, it can cause allergy, asthmatical symptoms and dyspnea when inhaled (risk phrase H334 (EG) Nr. 1272/2008). For the rest of the toxicity test categories (MSDS Class 11 and 12) no data are available. See MSDS (2014c).
Hydrochloric acid (CAS Number 7647-01-0) is toxic to fish (LC50) as well as to daphnia and other aquatic invertebrates (EC50). It is classified as irritating and caustic, explicitly causing severe skin burns and eye damages (risk phrase H314 and H318 (EG) Nr. 1272/2008), and airway irritation (risk phrase H335 (EG) Nr. 1272/2008). It is corrosive (risk phrase H290 (EG) Nr. 1272/2008). Under MSDS category “additional information” (Class 11) the following afflictions and characteristics are listed: ardor, coughing, wheezing, laryngitis, shortness of breath, convulsions, inflammation and edema of the larynx, spasms, edema and inflammation of the bronchi, pneumonitis, pulmonary edema, extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin. For the remaining toxicity test categories (MSDS Class 11 and 12) no data are available. See MSDS (2016c).
Hydrofluoric acid (CAS Number 7664-39-3) is classified life endangering, explicitly when swallowed (risk phrase H300 (EG) Nr. 1272/2008) or inhaled (risk phrase H330 (EG) Nr. 1272/2008) as well as in cases of skin contact (risk phrase H310 (EG) Nr. 1272/2008), and caustic, explicitly causing severe skin burns and eye damages (risk phrase H314 (EG) Nr. 1272/2008). Under MSDS category “additional information” (Class 11) the following afflictions and characteristics are listed: possibly reducing serum calcium levels and potentially causing fatal hypocalcemia, possibly causing severe burns and blisters, extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes and skin, causing skin necrosis. For almost all of the remaining toxicity test categories (MSDS Class 11 and 12) no data are available. See MSDS (2015b).
Certainly a variety of other corporations and institutions is developing, or at least trying to develop, corresponding new fluids. However, corresponding undertakings are justifiably kept secret respectively are not progressed far enough yet.
For example, tetraethylenepentamine (No. 1 on the list) (CAS Number 112-57-2). It is toxic to fish (LC50), daphnia, other aquatic invertebrates (EC50), and to algae (IC50). It is classified as harmful if swallowed or in contact with skin (risk phrase H302 and H312 (EG) Nr. 1272/2008), explicitly causing severe skin burns and eye damages (risk phrase H314 (EG) Nr. 1272/2008), as well as allergic skin reactions (risk phrase H317 (EG) Nr. 1272/2008). It is toxic to aquatic life with long lasting effects (risk phrase H411 (EG) Nr. 1272/2008). It is classified as having acute toxicity (LD50 oral—rat). Under MSDS category “additional information” (Class 11) the following afflictions and characteristics are listed: extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin; spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi, pneumonitis, pulmonary edema, burning sensation, cough, wheezing, laryngitis, shortness of breath, headache, nausea. For the remaining toxicity test categories (MSDS Class 11 and 12), no data are available. See MSDS (2012b).
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The patent described in Section C (Kreipl and Luinstra 2016) is held by AME Trade & Development GmbH (applicant). Both authors own stocks of the company.
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Kreipl, M.P., Kreipl, A.T. Hydraulic fracturing fluids and their environmental impact: then, today, and tomorrow. Environ Earth Sci 76, 160 (2017). https://doi.org/10.1007/s12665-017-6480-5
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DOI: https://doi.org/10.1007/s12665-017-6480-5