Fracking’s More Dangerous Bedfellow: Acidizing by Robert Collier, September 3, 2013, The Next Generation
But in California, at least, the obsession with fracking may be misplaced. In recent months, policymakers have begun to realize that the debate about fracking may be a distraction from the technology that’s the more likely candidate for tapping the Monterey Shale: A technique, already widely in use in the oil industry, known as “acidizing.” It’s not widely discussed in laymen’s circles, but for some time oil companies have found acidizing more effective in the Monterey Shale than fracking.
Acidizing, also referred to as “matrix acidization,” typically involves the injection of high volumes of hydrofluoric acid, a powerful solvent, (abbreviated as “HF”) into the oil well to dissolve rock deep underground and allow oil to flow up through the well. Conventional fracking, in which water and other chemicals are pumped at high pressure to create fissures in the rocks, reportedly does not work well in many parts of the Monterey Shale – a rock formation known for its complexity and low permeability, which makes fracking less effective.
A critical tool – but mistakes can be deadly
In the oil patch, hydrofluoric acid can therefore be a critical tool. But HF is also one of the most dangerous of all fluids used in oil production – and indeed in any industrial process. … Currently, large amounts of HF (precise volumes are an industry secret) are routinely trucked around California and mixed at oilfields. Critics call it a disaster waiting to happen. There have been minor HF leaks in other states, though no major catastrophes in the U.S. such as a recent HF tragedy in Korea. Yet acidizing remains almost totally unregulated. State and federal rules currently being drafted in Sacramento and Washington, DC, make no mention of acidizing. An exception is legislation currently under debate in Sacramento, authored by Sen. Fran Pavley, D-Agoura Hills, who has spearheaded much of the state’s climate laws in recent years. Whether California regulates acidizing may have national and global implications. Although the state appears to be the first to do major experimentation with high-volume acidizing, the rapid expansion of unconventional oil technologies in shale formations in other states suggests that oil companies might try to export any successful California experiments to other locations.
Industry abuzz, but details are secret
Hydrofluoric acid is typically mixed with water and other chemicals, with HF concentration normally less than 9 percent. However, oil company executives have said they are experimenting in California with higher concentrations and pressures, testing the boundaries of geology, engineering — and safety. Exactly how high those experimental concentrations and pressures are is a closely held secret. At a May 2013 industry conference in Bakersfield, executives in attendance speculated nervously about what their competitors were doing. Each company was clearly working on its own secret formula, trying to find its own recipe for success. The buzz among conference attendees was about Occidental Petroleum, which had demonstrated much success with HF acidizing at its Elk Hills field. “As you have seen here, companies are experimenting widely with acidizing,” said Maysam Pournik, a geology professor at the University of Oklahoma who spoke at the event. “Nobody is saying exactly what they are doing, because the Monterey Shale is extremely complex, and companies need to try new methods at the limits.” Some executives said they believe their competitors were experimenting with HF concentrations as high as 30 percent. But others downplayed such talk. “If you use that much HF, you will melt your well casings,” said Paul Gagnon, senior vice president of Central Resources, a Denver-based oil firm. “It’s not doable.” Left unsaid was the environmental danger – that HF could breach the double or triple steel walls of the well casings and enter the surrounding water table, putting local water supplies at risk.
A recognized human hazard
HF is commonly used in oil refineries, where it serves as a catalyst to produce high-octane gasoline. It is one of the most hazardous industrial chemicals in use, according to the U.S. Centers for Disease Control. HF can cause severe burns to skin and eyes, and can damage lungs in ways that may not be immediately painful or visible. Overexposure causes painful, deep-seated and slow-healing burns and ulcers. If absorbed through the skin in even minute amounts and left untreated, HF may cause death.
The dangers of HF are compounded by its extreme volatility at relatively low temperatures. If temperatures are cool, HF is a liquid. But at 67.1 degrees F, HF boils into a dense vapor cloud that, if released into the open, does not dissipate, hovers near the ground and can travel great distances – meaning the risks of a spill to nearby population centers are significant. The National Fire Protection Association system rates hydrofluoric acid in the most dangerous category of hazardous materials. Hydrofluoric acid also is recognized on the Superfund list of Extremely Hazardous Substances. As a powerful corrosive, it dissolves nearly anything – research on matrix acidizing lists “corrosion” as one of the primary challenges. There appears to be no research or other publicly available information about HF’s use in oil and gas production or its potential effects on groundwater supplies. But the risks are clear. [Emphasis added]
Why Oil Companies Want to Drop Acid in California, In the Golden State, fracking has given way to ‘acidizing’ as a means to extract oil by RL Miller, September 2, 2013, TakePart
Hydrofluoric acid is the most dangerous chemical you’ve never heard of, and it’s being trucked around California’s back roads and injected into oil wells, with virtually no oversight. How bad is it? HF acid is extremely toxic; it can immediately and permanently damage lungs if inhaled, and a spill on skin is easily absorbed deep into the body’s tissues and changes bone calcium atoms to fluorine atoms. Oh, and it corrodes glass, steel, and rock. This makes it attractive to the state’s oil drillers. They’ve been injecting it underground for years in highly diluted quantities to get out the last dregs of oil from a nearly depleted well. Now, they’re finding that injections in stronger concentrations (they’re tight-lipped about how strong) dissolves oil-bearing shale.
Dave Quast, California’s Energy in Depth representative tells TakePart that acidizing uses significantly less water than fracking: the total fluid volume is generally between 750 and 2000 gallons, 85 percent of which is water. In drought-prone California, that’s a point in its favor. Acidizing with HF works much better than fracking in the Golden State because the oil-bearing shale is already naturally fractured and buckled from tectonic activity, Collier tells TakePart. “We know it’s dangerous, but we don’t know what it does downhole. There are known dangers, and then there are unknowns.” It’s known that the acid forms a dense, low-lying cloud at a relatively cool 67 degrees Fahrenheit and that breathing it scars lungs. Much of the Monterey Shale oil drilling is done in Kern County, blazing hot in summer but prone to tule fog during winters much chillier than 67 degrees. HF acid is so worrisome that the United Steelworkers want its use phased out of oil refineries entirely, calling it a risk too great for the steelworkers and the 26 million Americans living near refineries.
But what’s not known about hydrofluoric acid? Three things, mainly: the concentrations used by oil companies, what happens over the long term when a rock-dissolving chemical is injected into rock, and what happens to those 2000 gallons of hydrofluoric acid-laced water?
And then there’s this. The California Occupational Safety and Hazard Administration isn’t tracking HF acid usage underground within the state at all. The state Division of Oil, Gas, and Geothermal Regulations’ oversight has been sketchy—oil drillers must get a permit, but they don’t have to tell the state if they’re fracking, using acid, or something else.
A bill to regulate fracking in California, SB4, is moving through the state legislature, but is attracting some opposition from a coalition of environmentalists who want a moratorium instead of regulations. Acidizing regulations were added after the bill’s introduction, but oil lobbyists oppose even the regulations. Becky Bond, political director of CREDOMobile and a proponent of a moratorium, told reporters this, with a note of disbelief, “when we started the fracking coalition, we had no idea we also needed to tell politicians why it’s a bad idea to pump hydrofluoric acid underground!” Truckin’ and trippin’ the bad acid throughout California’s fractured geology—what could go wrong? [Emphasis added]
The Most Dangerous Chemical You’ve Never Heard Of by Robert Collier, August 15, 2013, The Next Generation
“No industrial process risks more lives from a single accident than does the subject of this report – alkylation using hydrogen fluoride in oil refining. Fifty American refineries use HF alkylation to improve the octane of gasoline. Many are situated in or close to major cities, including Houston, Philadelphia, Salt Lake City and Memphis. In some cases, more than a million residents live in the danger zone of a single refinery. All in all, more than 26 million Americans are at risk.” So says a 2013 survey of 50 U.S. oil refineries by the United Steelworkers union, which represents refinery workers. The survey found that “over a five-year period, the refineries in the study experienced 131 HF releases or near misses and committed hundreds of violations of the OSHA rule regulating highly hazardous operations.”
A joint investigation in 2011 by ABC News and the Center for Public Integrity came to an equally chilling conclusion:
At least 16 million Americans, many of them unaware of the threat, live in the potential path of HF if it were to be released in an accident or a terrorist attack, a joint investigation by the Center for Public Integrity and ABC News has found. The government maintains closely controlled reports outlining worst-case scenarios involving highly hazardous chemicals. The Center reviewed reports for the 50 refineries that use HF. The reports describe the most extreme accidents anticipated by the plants’ owners. The information is not published and is not easily accessible by the public. A recent spate of refinery equipment breakdowns, fires and safety violations has heightened concerns. Over the past five years, authorities have cited 32 of the 50 refineries using HF for willful, serious or repeat violations of rules designed to prevent fires, explosions and chemical releases, according to U.S. Occupational Safety and Health Administration data analyzed by the Center. These “process safety management” standards require companies to conduct inspections, analyze hazards and plan for emergencies. In all, at those 32 refineries inspectors found more than 1,000 violations, including nearly 600 at the BP refinery in Texas City, Texas, where 15 workers were killed and 180 injured in a 2005 explosion. Although only some of the violations involved HF, they can be an indicator of operational weaknesses, particularly worrisome at refineries using the chemical, industry and government insiders say. …
Clyde Trombetta, Cal-OSHA’s chief supervisor for both oilfield and refining operations, wrote in a June 14, 2013 email that he didn’t know that HF was being used in oilfields. “When it comes to Hydraulic Fracking in California I do not believe the industry uses hydrofluoric acid and hydrochloric acid in its matrix,” he wrote. Chemical safety experts say that California’s pioneering use of HF poses unique challenges. “You have uncounted numbers of trucks moving HF around the state, it’s unclear whether the workers are trained in proper safety protocols, whether local first responders are prepared, or whether anyone is prepared for a potentially lethal accident of significant proportions,” said Kim Nibarger, a health and safety specialist for the United Steelworkers. “It seems totally unregulated.”
In recent years, as the national debate over fracking became a cause celebre from New York to Hollywood, acidizing remained relatively obscure — and cloaked in relative secrecy. In California and elsewhere, oil companies face no disclosure requirements for acidizing. As a result, there is little information available to the public about when, where or what kinds of acids, what depth, what strength, what volumes, or even whether they are doing it. There is no mention of the topic in the U.S. BLM’s new draft rule for well stimulation methods, which includes hydraulic fracturing, on federal and Native American lands. In California, the attention to acidizing came belatedly. After years of being a backwater in the fight over fracking, California entered the fray in earnest in early 2013. A flurry of media coverage about fracking’s potential in the Monterey Shale prompted environmental groups and legislators to jump on the national bandwagon. It was all fracking, all the time. Acidizing, however, was unmentioned.
The door was cracked open in April, when the South Coast Air Quality Management District issued new regulations that would mandate disclosure of “the names and quantities of chemicals, non-trade and trade secret, and other process information within 60 days after completion of well activities.” The measure did not impose any limits on acidizing, but it marked the first time anywhere in the United States that oil companies were even required to disclose acidizing. But soon after, acidizing came into the sphere of interest among activists and legislators. In June, Senator Fran Pavley scheduled a hearing in the state Senate to investigate the use of acidizing. She invited Chevron, Occidental and Venoco and the oilfield services company Halliburton to testify at the hearing, asking them to provide information on “the type and number of oil stimulation treatments, including acid-based treatments” that the companies use and plan to use in California. All three companies declined, deferring to two industry associations to address the panel’s questions. “We use acid because it’s effective,” testified Paul Deiro of the Western States Petroleum Association. … He urged the legislators to avoid “unnecessary” regulation of acidizing.
Faced with stonewalling, Pavley promptly amended her bill – which until then had been focused exclusively on fracking – to add a requirement requiring full disclosure of acidizing activities. She also added acidizing to the bill’s authorization for the state to commission an independent, peer-reviewed study of the environmental health effects of well drilling techniques. This study, to be completed by Jan. 1, 2015, would fill in critical gaps in the nation’s knowledge of fracking’s impacts, which have not been widely studied; it would also be the only study to date about the potential impacts of acidizing. The study’s findings could prove to be be a major boon to other states and nations that are seeking a responsible approach to the rapid expansion of fracking and acidizing. [Emphasis added]
Halliburton Introduces Technology to Control Fracture Face Damage and Help Improve Production from Unconventional Reservoirs Press Release by Halliburton, September 25, 2006, Business Wire
Halliburton’s (NYSE:HAL) Production Optimization Division has added a breakthrough technology to its suite of stimulation products, GasPerm 1000(SM) service. GasPerm 1000 service helps improve production from unconventional reservoirs including tight gas, shales and coalbed methane. Based on a newly developed microemulsion surfactant, the service helps remove water drawn into the formation during the fracturing process. Removing the water can improve permeability to gas at the fracture face and help increase gas production. In addition, GasPerm 1000 service represents a safety and environmental advancement, replacing methanol in many applications. “Halliburton has focused our top researchers on developing technology to help operators achieve better results from unconventional reservoirs and GasPerm 1000 service is the initial result of this research,” said Jim Prestidge, vice president within the Production Optimization Division. “The characteristics of unconventional reservoirs pose unique challenges, particularly in the area of controlling fracture face damage. GasPerm 1000 service technology was developed to help achieve maximum production following a fracturing treatment and with the focus on environmental sustainability, our constant guiding principle as we develop new chemicals.” …
In Canada, coalbed methane production is growing extremely fast. Production from gas shales, such as the Barnett formation, has shown exponential growth in the past five years. Fracturing will continue to play a major role in coaxing production from these reservoirs.
In the fracturing process, water can be drawn (imbibed) into the
formation from the fluid used to create the fracture. The water drawn
into the pore spaces is held there by capillary pressure and surface
tension and can block gases from flowing into the wellbore. Commonly
called “water block,” this process is especially pronounced in
unconventional gas reservoirs where the lower permeability results in increased capillary pressure. GasPerm 1000 service has been shown to enable the imbibed liquids to be expelled from the rock matrix and fracture system, thereby enabling improved gas production.
From both an environmental and safety perspective, GasPerm 1000(tm) additive can be used in place of methanol. When run as an additive at field use concentration, the GasPerm 1000 additive reduces flammability risk as compared to methanol at concentrations typically used for water block treatment applications. A comparison test performed in an ultra-low perm tight gas sand formation from the Rockies demonstrated that under comparable conditions, the formulation containing GasPerm 1000 additive outperformed a conventional methanol-based formulation. GasPerm 1000 additive is compatible with both acidic and basic fluid systems and is used as an acidizing additive or fracturing fluid additive. [Emphasis added]