Endangered helium: bursting the myth

8/10/2019 Endangered helium: bursting the myth

1/532 www.tcetoday.com december 2013/ january 2014

tce ENDANGERED ELEMENTS

E n d a n g e r e d

h e l i u m : b u r s t i n g t h e m y t h

Contrary to recent reports, we are not about to runout of helium any time soon, say Richard Clarke ,

William Nuttall , and Bartek Glowacki


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CAREERS tceENDANGERED ELEMENTS

Since 2000 there have beenthree helium crises whenthe supply chain has become

bottlenecked, and we are inone right now. But let us beclear. These are short-termshortages caused by upstreammarket disturbances, notlong-term problems.

The Earth just cannot hold on to itshelium. If it could, the noble gasmight comprise more than 10%of the atmosphere and we would not be writing about a helium supply problem.For nearly a century chemical engineering

has enabled helium to underpin ourincreasingly technological world. A new UShelium law may have averted a crisis, butthere is still much to be done if heliums vital role is to continue.

Although helium is being generatedunderground as uranium and thorium atomsdecay, practically all of the Earths helium 99.997% to be precise 1 has escaped intospace through a peculiar mechanism calledion outflow. Most of what remains is in theatmosphere 2. The 3.8bn t of helium in the air would keep helium users going indefinitely.But at a concentration of just 5.2 ppm,meeting the worlds helium needs of30,000 t/y from the air would require a fleetof gas plants as big and as energetic as powerstations.

Instead, we must make do with the 8m t theUS Geological Survey estimates is buried inthe Earths crust. That substantial resourcehas supplied the world with abundanthelium. It is a story that started in 1903, at adud natural gas well in Dexter, Kansas. Thedisappointed townspeople called it windgas; it had a composition of 72% nitrogen,

some methane, and 1.84% helium. And thatmight have been the end of the matter, had itnot been for two unrelated events. The first was that helium was also foundto occur in many other natural gas wells inKansas (though nothing like as much as was

later found in the giant, but now declining,Hugoton-Panhandle field). The second eventoccurred in 1914, early in the First World War, when first the British, and later the Americans, became convinced that Zeppelins were being filled with helium (in fact, Germanairships were lifted by hydrogen right up untilthe Hindenburg disaster of 1937).

From the 1920s onwards an all-out USnational programme, for a long time led bychemical engineer Clifford Seibel, soughtto find helium-bearing gas fields andco-produce the helium for strategic purposes.

As a lift gas, helium played a vital role in theSecond World War, filling airships that wereused to guard the Atlantic convoys. As new applications emerged in the 1950s,helium purity was much improved throughthe use of activated carbon; when cooledby liquid nitrogen all gases except heliumand neon are adsorbed. From the HeliumConservation Act of 1925 until the HeliumPrivatisation Act of 1996 (HPA) the USgovernment dominated the helium market,and for half a century the US was the solesource of helium overseas.

Helium refiner

Helium refiner

Refinedhelium

Refinedhelium

Crudehelium

1600 psi

1600 psi

670 psi

610 psi

Number of wells(@670 psi)

CrudeheliumCrude

helium

Crudehelium

Crude heliumcompression

Naturalgas

Naturalgas

Nitrogen

Nitrogen

Nitrogenrejection

Natural gasliquids (NGLs)

NGLs

NGLs

Sales gas

Sales gas

Salesgas

Crude heliumrecovery plant

Crude heliumrecovery plant

MM

M

M

M

Length is~400 milesTX, OK, KS

US BLM pipeline

Cliffside storage field

Nativegas

Injectedgas

Nativegas

Heliumenrichmentunit

(4)(9)(12)

Mixedgas

Crude helium meter

Native gas: 1.8% He, 25% N 2, 73 % Hydrocarbons

Injected gas: 55% He, 41% N 2,


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To meet the needs of the Apollo spaceprogramme and Cold War defence, theFederal agency responsible, the Bureauof Mines, now the Bureau of LandManagement (BLM), built up a huge

strategic stockpile of helium in Texas but,in doing so, incurred a US treasury debtof US$1.4bn. Two decades later, manyquestioned the need for a governmentstockpile of helium, and Congress waspersuaded to pass the HPA. By October2013 the HPA was obsolete: the debt hadbeen paid, yet a third of the stockpile stillremained. Just in time, the Helium Stewardship Act (HSA) became law on 2 October 2013.It enables the BLM to carry on producinghelium from the Cliffside helium reservelocated near Amarillo, Texas. For now, onethird of the worlds helium supply originatesfrom that reserve and the new Act requirespart of the output to be auctioned.

As anyone who purchases helium knows,

operational. Crude helium from QatarsLNG plants is purified and liquefied inthe worlds largest liquefier built by AirLiquide. Hundreds of 40,000 l cryogenicISO-containers are used to ship liquidhelium all over the world, and increasingly

to Asia, where there is great demand forhelium in high-tech industries. The verypure liquid is decanted or compressed intrans-fill facilities (see Figure 2 3) through which the needs of both liquid and gasusers are met. This is a delicate balancingact and it is here that gas for party balloonsis bottled, whether from recycled helium orfrom incoming gas that might otherwise goto waste. Unconventional sources of helium arebeginning to make an impact on the supplyside too. In several US states there is small-

scale helium production from reserves thatare predominately nitrogen 4. There thedrilling target is helium as there is little or nofuel value in the well gas. During the comingdecade Russia expects to open up hugenatural gas fields in Siberia that contain upto 0.58% helium 5. Helium extraction andstorage is a priority for Gazprom. Otherpotential sources include Irans South Parsfield, Indias geothermal wells 2; Arizonas StJohns CO 2 field; Shells Pearl gas-to-liquidsproject in Qatar; the Mount Kitty field incentral Australia and even Italy where itsnatural gas grid contains up to 0.1% heliumthat can be traced to gas imported from Algeria6. In Colorado, another CO 2 reserve atDoe Canyon is expected to start producinghelium by 2015. Nevertheless, the globalhelium supply situation will remain quitechallenging over the next few years.

not just for balloonsPerhaps stimulated by its apparentabundance, helium has become anessential, but mostly unseen, componentof modern technology ranging from welding, to leak detection, rockets and

semiconductor fabrication. Much of it(29%) is used in cryogenics (see Figure 3) and 75% of that is used to cool magneticresonance imaging (MRI) machines.

In the UK, the upper Thames Valley nearOxford is a hotspot for cryogenics such is thediversity and extent of helium-using scienceand industry there. The Siemens MRI factoryalone produces 30% of the superconductingniobium-titanium (Nb-Ti) magnets used inMRI machines found in hospitals aroundthe world. Engineers there focus on waysto minimise each machines helium use.Helium demand persists, however, becausethe MRI market is growing strongly, such isthe diagnostic capability of these machines. Helium re-condensers, such as theGifford-McMahon and pulsed-tubemachines, operate at -269C. They ensure

Crudehelium~70%

Conventional heliumproduction (US BLM)

Helium productionfrom LNG processes

Radioactivedecay

Gaseous heliumdirect sales

Liquid helium distributedto end users

Purificationsteps

Regionaldelivery

Recovery(balloon gas)

Release intoatmosphere

after use

Enrichment

Wholesale transportation(tube trailers)

Wholesale transportation(liquid containers)

Purificationsteps

Otherconventional andunconventional

heliumproduction

Heliumliquefaction

Radioactive decayreleased into air

Helium vented duringnatural gas extraction,

LNG production orgas burning

Rawhelium

(4055%)BLM

reserve

Endusers

Heliumreserve

base

Atmosphere

Transfillfacilities

Grade Agaseoushelium

Liquidhelium

Figure 2: The upstream helium market, showing how helium sources connect to end-users(Cai et al 3 )

Perhaps stimulated by itsapparent abundance, heliumhas become an essential, but

mostly unseen, componentof modern technology ranging from welding, toleak detection, rockets andsemiconductor fabrication.

retail prices have seen annual double-digitpercentage rises for nearly ten years. Yetsome scientists, notably Nobel LaureateRobert Richardson, have argued that todaysprices are not high enough to preserve vitalsupplies for research. This is why the HSA has

a provision to hold back a part of the heliumstockpile for government and research use inthe 2020s. Even though the HSA is now in place thereneeds to be a reality check. The Cliffside fieldhas been producing flat out since the HPAcame into effect in 1998 and the reservoirpressure is falling. New compressorsare required to keep the crude heliumenrichment unit operational (see Figure 1).Other production measures may be neededto allay concerns about water flooding thereserve. Output from Cliffside is expected to

decline steeply until around 2020, after whichthe remaining reserves will be allocated bythe US government.

where next?If Cliffside and the Hugoton-Panhandle fieldshave had their heyday, where will tomorrowshelium come from? Significant reserves arebeing produced in Wyoming and there ismuch activity outside the US. Since the mid-1990s it has been clear that low-grade heliumsources can be produced from natural gas when it is liquefied in an LNG plant. Heliumrefineries attached to such plants in Algeria

(Arzew started up in 1995), Qatar and atDarwin in Australia will together produce asmuch helium as Cliffside once did.

The Ras Laffan 2 helium plant is now fully


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CAREERS tceENDANGERED ELEMENTS

Figure 3: The many global uses of heliumMagnetic resonance imaging 21%(other cryogenic applications including physics research 8%)

Pressurisation and purging including rockets 11%

Welding 17% Leak detection 5%

Controlled atmospheres including diving 6%

Semiconductors, optic fibres (heat transfer) 14%

Analysis including chromatography 5%

Party balloons 8% Weather balloons 5%

(source: bit.ly/LGYh8J)

that the liquid helium bath in a modernMRI machine needs only be filled onceevery 510 years. As leak rates fall, it is thehelium inventory (per machine) that coulddominate demand.

Since 2000 there have been three helium

crises when the supply chain has becomebottlenecked, and we are in one right now.But let us be clear. These are short-termshortages caused by upstream marketdisturbances, not long-term problems.Partly these disruptions can be traced backto the HPAs pricing mechanism and theBLMs large market share. This, some argue,has dissuaded helium refiners from enteringor staying in the market.

The world will not run short of helium formany decades to come, but neverthelessnow is the time to start to address the

serious long-term problems that will hithelium supply when the world eventuallymoves away from fossil fuels. There is also the shale gas effect . Shalegas contains virtually no helium. As morenatural gas has come into the market, US gasprices have fallen to a point recently where ithas not been economic to develop new shalegas wells. A side-effect of these low pricesis that some conventional gas productionhas become uneconomic. This is what hashappened at the Keyes field in Oklahoma.In the 1960s the Keyes plant was one of themost important helium sources in the world.Now production has stopped. Of course, theUS may start exporting LNG but whetherthis will bring more helium to the marketremains an open question, even if naturalgas prices rise again.

wasted opportunity A fact that surprises many helium usersis that about half of all helium moleculesunearthed during natural gas productionnever make it to the market. This is called venting. There are two main reasons for this.Firstly, helium is nearly always co-produced

with natural gas, so the requirements ofthe 1,000-times-bigger natural gas industrytakes precedence. Secondly, if the heliumconcentration in natural gas is low itmay not be economical to recover it. InQatar the concentration is around 0.04%,but historically 0.3% was considered thebreakeven point. In the LNG process most ofthe heavy components (ethane, propane etc)are removed and the methane is condensed.The main condenser has a purge line toprevent inert gas blanketing, and it is thisstream, sometimes rich in helium, that isthen purified and liquefied for export.

In future, large-scale processes such asair CO2 capture may be developed. Possiblythey could be adapted to economicallyco-extract atmospheric helium in industrialquantities. Willem Keesom, who in 1926

21%

17%

6%

5%

14%

11%


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succeeded in freezing helium, mooted suchan idea in his 1942 treatise about helium 7.

He believed that helium reserves willbecome critical in a future that is not toofar remote. Cryogenic air separation (ASU)technology provides one such route, and

companies like Ukraines Iceblick havedeveloped processes that purify the ASUpurge gases krypton, xenon, neon andhelium. The main challenge is that even ina large ASU that produces, say, 1,000 t/d ofoxygen the helium output would be just1 m3/h. Today, in at least one ASU whereneon is a by-product, helium is alsoproduced. In practice, a crude helium-neon mixture would be compressed and transported toa central rare gas refinery. Richard Clarkeand Roger Clare 2 estimate that Grade A

(99.996%) helium could be produced by ASUs for around US$42,500/t (US$200/thousand ft 3), similar to todays wholesaleprice. But even if every large over-the-fence ASU project recovered helium, thecumulative total volume produced over a20-year period would only amount to 1 or2% of current helium demand. However,the trend towards super-sized ASUs mightenable the nascent oxy-fuel combustionindustry to develop. In that case, heliumfrom air may one day produce ~3,000 t/y ofhelium. As the conventional US helium reservesdiminish this decade, and in all likelihoodthe US starts importing helium, it is criticalthat the best helium recovery technologiesare brought into production in the naturalgas industry. Helium that is not separatedand stored at source is not preserved. Atthe same time dominant users, like theMRI industry, will continue their quest tobecome virtually helium independent.

Many researchers are now focussing onnew materials that work at higher cryogenictemperatures, on processes that use lesshelium and on designs with less helium

inventory. General Electric8

has beeninvestigating ways to significantly reduce thehelium inventory of MRI magnets becauseNb-Ti is still the superconductor of choicefor MRI. It is cheap, malleable and effective. Another approach being explored atthe University of Cambridge is to useliquid hydrogen-cooled superconductorssuch as MgB 2 for combined power andhydrogen delivery to cities 9. If a pressurisedhelium loop is used to transfer heat froma superconductor environment to a liquidhydrogen bath, then indirectly-cooledhydrogen technologies could break intothe medical market as well 10. The OpenUniversity is currently researching pathwaysto a future hydrogen economy includingthose in which cryogenic liquid hydrogenenters the market as a substitute for

liquid helium.In other industries (such as

semiconductor and optic fibre manufacture)helium is often used just once and then vented to atmosphere. There is a realchallenge to develop cost-effective recycling

systems where the recovered helium purityis consistently good enough to expose tohigh value production streams. For now,though, the constant purity of liquid heliumusually trumps recycling. It is by no means clear which way thehelium story will develop. Today, thereare strong supply-side and demand-sidechanges taking place. Ultimately, heliumfrom natural gas may be just a steppingstone towards an age where sustainablehelium will come from the air. Meanwhilethe medical imaging industry, in response

to supply shocks and increasing price, isreducing its dependence on helium eventhough global helium production continuesto climb, as new and unconventional heliumsources come to market. tce

Richard Clarke, FIChemE ([email protected]) is a consultant andwriter on helium supply and cryogenicprocess engineering; William Nuttall is professor of energy at the OpenUniversity; Bartek Glowacki is professorof energy and materials science at the

Department of Materials Science andMetallurgy, University of Cambridge

further reading1. http://bit.ly/1aCEOlb2. The Future of Helium as a NaturalResource , Nuttall, WJ, Clarke, RH, andGlowacki, BA, (Eds), Routledge, 20123. http://bit.ly/16YVB4N4. http://bit.ly/1cjPTuc5. http://bit.ly/1bzLy666. http://bit.ly/1fyTCXs

7. Keesom, WH, Helium , Elsevier, 19428. http://bit.ly/1irT5LD9. www.msm.cam.ac.uk/ascg10. http://bit.ly/1cUI12q

As the conventional UShelium reserves diminishthis decade, and in all

likelihood the US startsimporting helium, it iscritical that the best heliumrecovery technologies arebrought into production inthe natural gas industry.Helium that is not separatedand stored at source is notpreserved.

Chemical Engineering MattersThe topics discussed in this article refer to thefollowing lines on the vistas of IChemEs technicalstrategy document Chemical Engineering Matters :

EnergyLine 1

Health and wellbeingLines 4, 1112, 1617, 27

Visit www.icheme.org/vistas1 to discover wherethis article and your own activities t into the myriadof grand challenges facing chemical engineers
http://www.msm.cam.ac.uk/ascghttp://www.msm.cam.ac.uk/ascg

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Endangered helium: bursting the myth