Promising New Sources of Helium

by Dr. John Barclay, Emerald Energy NW, LLC, jabarclay@comcast.net and Raymond Hobbs, United Helium, Inc., rh@unitedhelium.com

1. Background
Helium is the second most abundant element in the universe after hydrogen. It is a colorless, odorless, non-toxic, inert, monoatomic gas. At standard conditions 288.7K (60°F) and 0.1013 MPa, helium has a density (0.1688 kg/m3) that is less than all other elements except hydrogen (0.0850 kg/m3). It is classified as a noble gas in the periodic table and its most common isotope is 2He4, indicating the helium atom has a nucleus containing two protons and two neutrons. Liquid helium’s boiling temperature at 0.1013 MPa is 4.22K (-452°F). It is the only element that remains liquid upon cooling unless it is pressurized to about 2.5 MPa (~25 atmospheres) and cooled to 0.95K. It is much lighter than air and once released into the Earth’s atmosphere, it has sufficient energy to escape into space, resulting in a concentration in the Earth’s atmosphere of only 5.2 parts per million by volume. Helium was first detected in the sun in 1868, but it was not isolated and characterized as helium on Earth until 1895 by William Ramsay, a Scottish chemist, and independently in the same year by two Swedish chemists, Per Cleve and Abraham Langlet. Helium was among several gases called “permanent” gases because they did not liquefy by isenthalpic expansion from high pressures when starting the expansion near room temperature (the inversion temperature of helium is about 50K at 0.1013 MPa—different references cite slightly different values). As a result of numerous cryogenic technology improvements and better understanding of the thermodynamics of gases in the late 19th and early 20th centuries by several amazing low temperature scientists, helium was first liquefied and retained in milliliter quantities by Dutch physicist H. K. Onnes at the University of Leiden in 1908. Helium has numerous incredibly interesting properties that are well beyond the scope of this short article. Good references to read for more details are cited in this article [1, 2, 3, 4, 5].

2. Helium Applications

Helium has many uses because of its unique physical properties (small atom, extreme mobility, low boiling point, low density, low solubility, high thermal conductivity and completely inert). Some of those uses include the following:

• A refrigerant to provide the lowest cryogen temperatures attainable for low temperature research
• A refrigerant used in superconducting magnets and medical systems such as MRI scanners
• Purging and pressurizing fluid in aerospace applications
• Shield gas for inert gas arc welding and other forms of protective atmospheres in furnaces
• Leak detection, especially in high-pressure piping systems
• Coolant for high temperature gas-cooled nuclear reactors
• Buoyant gas for balloons and other lighter-than-air activities
• Mixed with oxygen to provide a safe breathing gas for deep-sea divers
• Excellent carrier gas in gas chromatography

The US Department of Interior through the US Geological Survey regularly reports on US helium production and demand (Figure 1). The demand for helium is steadily growing, especially for liquid helium for applied superconducting applications using low-temperature superconductors.

Figure 1: Chart of helium use in the US as reported by the US Geological Survey

 3. Sources and Production of Helium

On a galactic scale, in addition to the huge formation of helium in the Big Bang, large quantities of helium are continuously produced by nuclear fusion of protons (hydrogen nuclei) in stars such as our sun. There are two sources of terrestrial helium [6]: (1) the primordial helium derived from sources deep within the Earth; and (2) the product of radioactive decay of uranium and thorium elements in the Earth’s crust that emit alpha particles (He++ ions). The emitted helium ions capture electrons from surrounding materials to make stable helium gas that accumulates with other gases in geological structures. Because helium is about five parts per million by volume of the Earth’s atmosphere, it was considered to be a very rare gas. In 1903 in Dexter KS a new gas well emitted a large flow of gas that wouldn’t burn [7]. The gas was analyzed by University of Kansas professors H. P. Cady and D. F. McFarland, who confirmed that its composition was about 72% nitrogen, 15% methane, traces of other light hydrocarbons and several other inert gases that included 1.84% helium [8]. Helium was also found in the gas from numerous other wells in the central US, which indicated helium was not as rare as originally thought. Using isotopic ratios, it has been determined that most of the helium in the gas fields is from radioactive decay. However, because there were few industrial applications for helium in 1906, nothing much happened as a result of this discovery until World War I, when observation and barrage balloons began to be used. Highly buoyant helium in air was preferred over even more buoyant hydrogen in air because helium was non-flammable and diffused through balloon materials slower than hydrogen. The US Navy and Army, the US Bureau of Mines and the US Geological Survey within the Department of Interior investigated numerous geological structures in Kansas, Oklahoma, Texas, eastern New Mexico and Pennsylvania with new natural gas wells to determine the extent of the helium reserves in the US. The investigation, published by the US Geological Survey in 1921, indicated that the US had significant quantities of helium that could be extracted from natural gas [9]. To capture the strategic helium being extracted from natural gas, the US government established the Federal Helium Reserve in large underground caverns near Amarillo TX in 1925. Several subsequent acts of Congress over the last 90 years made the helium market much more controlled than other industrial gas commodities. Additional analysis and surveys by the US Bureau of Mines and private entities to measure the helium content in most US gas wells indicate that as of 2005, the majority of natural gas reservoirs with significant concentration of helium are in the reservoirs listed in Table 1 [10].

 Table 1: US natural gas reserves with a significant concentration of helium

Pipelines from extraction plants in these areas transported the crude helium (nominally 50-80% He) to the National Helium Reserve near the southern tip of the Hugoton reservoir in Amarillo. Additional promising and underdeveloped geological formations with significant amounts of helium not on the list in Table 1 are known in eastern Arizona [11], New Mexico [4], and Utah and Colorado. Two interesting attributes of the helium-containing gas mixtures in some of these undeveloped regions are: 1) there are helium concentrations as high as 9 mole percent; and 2) the major components are carbon dioxide or nitrogen [12] rather than methane. For example, the plant recently started up by Air Products in Doe Canyon CO [13] separates and purifies CO2 and He gas mixtures. At this plant Air Products processes the CO2 for Kinder Morgan, which distributes the CO2 to its customers in Texas for enhanced oil recovery while Air Products liquefies and sells liquid helium (LHe) or regasified compressed helium to its industrial gas customers. United Helium, Inc. is a privately held company based in Phoenix AZ whose CEO is Ray Hobbs. It was created in 2013 by the principals of Mesquite Energy Partners (MEP) to commercialize helium extraction from large acreages of undeveloped lease holdings in eastern Arizona in the Holbrook Basin and nearby areas (see Figures 2 and 3). United Helium’s corporate mission is to begin to produce helium from its leasehold holdings of approximately 33,000 acres in the Holbrook Basin of Apache County AZ. United Helium obtained working interest assignments from MEP in exchange for equity and other considerations. The leaseholds are on State of Arizona and private land, which are grouped into two geographic areas, Holbrook North and Holbrook Central. The Holbrook North lease assignments were completed on June 20, 2013. Negotiations for the Holbrook Central lease between MEP and HNZ Potash, LLC were completed August 30, 2013, and assignment to United Helium was completed on September 6, 2013.

One of United Helium’s principals and its chief geologist, Gordon LeBlanc, Jr., had drilled three wells in the Holbrook Basin almost a decade ago, when the value of helium was much less than today. High-pressure gas with about 90% N2 and 8% He was found, but the gas had no oil and only traces of methane, so the wells were shut in. In early 2014 United Helium re-opened these wells and tested pressures, flows and composition from several zones at different depths. The composition of two samples in the zones was determined by two reputable analytical labs. One sample indicated ~28% CO2, ~60% N2, ~3% CH4, small amounts of other gases, and 4.8 mole percent He. The second sample has similar gases but with a few percent less CO2 and N2 and 9.3% He. With these very encouraging results, United Helium is working to develop these geological structures and bring a new supply of helium into the market.

To summarize the potential of United Helium’s current Arizona leasehold for helium production, the leases encompass some of the world’s richest helium deposits, with concentration levels up to 9%. The leases lay between the DBK Field to the north (refer to the caption of Figure 2 from S. Rauzi and L. Fellows), which has an estimated 4 billion standard cubic feet of recoverable helium assuming 4.5% concentration, and the St. Johns Dome to the south. The Concho Dome complex is a large geological feature in these leasehold areas that is prospective for commercial quantities of helium, natural gas and oil. Stratigraphic mineral test wells have been previously drilled in the Concho Dome complex and have encountered significant shows of oil, natural gas and helium. The Manuel Seep Field and Little Colorado structures are located within the Concho Dome complex and have not been drilled to sufficient depths to test for helium, oil and natural gas. The much higher structure, the Navajo Anticline Field, was initially drilled in 1960, with indications the structure has helium and nitrogen gas. However, the Navajo Anticline was not developed at that time due to various “land swap” dealings among the State of Arizona, private owners and the Navajo Nation. United Helium leaseholds include part of this field.

Unit operations to purify methane gas mixtures from large gas fields where the raw gas flow rates collected from numerous wells are tens to hundreds of MMscfd are well known [14], especially for methane gas mixtures where the primary purpose of a plant is purification of methane to meet pipeline injection specifications [15]. The removal of nitrogen to increase energy content of natural gas at a nitrogen rejection unit is a good example [16]. Recovery of crude-grade helium with 50-80% He concentration is a valuable byproduct at Shute Creek that is sold to one of the industrial gas companies such as Praxair to further purify and liquefy it for their industrial gas customers.

However, at individual gas wells, where flow rates may only be 2-3 MMscfd, different purification techniques must be used to be cost effective. A good example is removal of bulk concentrations of CO2 where direct-contact amine absorption columns with separate amine regeneration and process gas drying modules work very well and are cost effective at large scale, but pressure swing adsorption techniques are superior at plants with small flow rates. Because of helium’s very low liquefaction temperature and its very low solubility in other cryogens such as liquefied natural gas (LNG) and liquid nitrogen (LN2), cryogenic separation is an effective technique to concentrate the helium after components that will freeze out (H2O, CO2, C4 and hydrocarbons) are removed from the helium-containing process gas. The first LNG plant in the US was a project for helium recovery from natural gas in 1917. Both Linde cycle and Claude cycle refrigerators were used for this gaseous helium recovery project. Liquid helium was first produced in the US in 1946 by Sam Collins at MIT, using several innovative coiled-fin tube heat exchangers and two reciprocating isentropic expanders to pre-cool compressed helium below its inversion temperature such that a final J-T isenthalpic expander produced liquid helium [17]. Derivatives of this successful liquefier were commercialized by A. D. Little, Chart Industries, and since 1999 are globally made and sold by Linde.

Emerald Energy NW, LLC (EENW), was formed three years ago by John Barclay as an energy technology and technical services company whose primary mission is to create small-scale LNG/compressed natural gas (CNG) and LH2/CH2 supply and end-use infrastructure for strategic customers. The EENW team has many years of first-hand knowledge of all aspects of optimized smaller-scale LNG plants and refueling stations; purification of multiple complex gas mixtures; and innovative li-quefaction of cryogens such as LNG, LH2 and LHe. EENW emphasizes development of innovative and proprietary advanced technology such as cryogenic purification, continuous adsorption purification, small-scale active magnetic and gas regenerative refrigerators and liquefiers that are cost effective and efficient. EENW has developed a very effective and inexpensive plant design for United Helium that purifies and liquefies raw gas mixtures at nominally 100 psia with flow rates of 2-3 MMscfd with high concentrations of nitrogen and carbon dioxide and ~5% helium. The end product at each small-scale plant is liquid grade-A helium (99.996% pure) that can be readily delivered to customers in cryogenic tankers designed to transport LHe over the road.

 4. Helium Supply Business
The global and US helium markets are inter-related more than perhaps is desirable now that there is a scarcity of helium, especially LHe in the US. An interesting analysis of the global supply/demand market for helium published in 2005 has been updated in an insightful book with chapters on relevant topics on helium written by experts recently published entitled “The Future of Helium as a Natural Resource” [18, 19].
There have been an increasing number of articles over the last few years in the US expressing concern over the shortage of helium; the artificial market being caused by the low price of helium being sold by BLM at the Federal Helium Reserve under mandate from Congress; the high price of LHe if one can get it at all (the highest price I have personally heard is $19/liter or ~$72/gallon) but some people mention prices higher than that. (As a point of reference, LNG commercially sells for about $1.25/LNG gallon and hydrogen sells for about $10/kg excluding excise taxes.) The new helium extraction plants in Wyoming and Colorado will increase the US supply of helium, but because almost half of the helium used and/or exported in recent years could deplete the Federal Helium Reserve in a few more years, there is a major concern for adequate future US supplies, especially, because over half of the helium is used as gas in situations where the helium is lost into the atmosphere.

 5. Summary and Recommendations
This short article was intended to give a few promising observations about US helium supply and use. First, the US should consider helium as an important sustainable resource with limited amounts produced by radioactive decay; second, all liquid helium users should use helium recovery and re-liquefaction systems; third, the production of LNG from the paradigm shift occurring in cleaner, less expensive, domestic LNG/CNG fuels in the transportation sector of the US should be strongly leveraged by requiring any LNG liquefaction plant to invest the small incremental cost to recover He from sources with less than 0.1% helium content; and fourth, professional societies such as the CSA, APS, ACS, ASME and AIChE should continue to organize members for helium groups.

References

1. W. E. Keller; Helium 3 and Helium 4; Plenum, NY 1969
2. S. W. Van Sciver; Helium Cryogenics; 2nd ed.; Springer, 2011
3. K. R. Atkins; Liquid Helium: Cambridge Univ. Press; 1959
4. R. F. Barron; Cryogenic Systems; 2nd ed.; Oxford Univ. Press; 1985
5. J. Wilks; The properties of liquid and solid helium; Oxford Univ. Press; 1987
6. J. E. Spencer; Arizona Bureau of Geology and Mineral Technology Field notes; Vol. 13, page 15; 1983
7. http://www.acs.org/content/acs/en/education/whatischemistry National Historic Chemical Landmarks; American Chemical Society; 2000
8. H. P. Cady and D. F. McFarland; Science, 24, 611, 1906, “Helium in Natural Gas”
9. G. Sherburne Rogers, U.S. Geological Survey Professional Paper 121, “Helium-Bearing Natural Gas”; Government Printing Office, Washington, D.C., 1921
10. R. F. Broadhead; New Mexico Geology; Vol. 27, No. 4, 2005; “Helium in New Mexico—geologic distribution, resource demand, and exploration possibilities”
11. S. L. Rauzi and L. D. Fellows; Arizona Geology; Vol. 33, No. 4, 2003; “Arizona has Helium”
12. S. L. Rauzi; Arizona Geological Survey, Report 03-05, October 2003; “Review of Helium Production and Potential in Arizona”
13. M. Bomgardner; cen.acs.org; November 4, 2013; “More Helium on the Way by 2015”
14. A. H. Younger, Natural Gas Processing Principles & Technology, Chem. Eng. Graduate Lectures, U. of Calgary, 1989
15. Engineering Data Book, Vols. I & II; Gas Processors Suppliers Association
16. The Exxon Mobil plant at Shute Creek, WY
17. S. C. Collins; Rev. Sci. Instr. 18, 157 (1947); “A Helium Cryostat”. (J. L. Smith wrote a great article on 50 years of LHe at MIT)
18. Z. Cai, R. Clarke, N. Ward, W. J. Nuttall, and B. A. Glowacki; Cambridge University; Zhiming Cai MPhil topic (2005); “Modeling Helium Markets”
19. The Future of Helium as a Natural Resource: edited by W. J. Nuttall, R. H. Clarke, and B. A. Glowacki; Routledge Publishing

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