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This article comes from Weixin Official Accounts: Earth Knowledge Bureau (ID: diqiuzhishiju), text: Wang Guanlong without thorns, proofreading: Gu Hanying/editor: chestnut

In 1869, Russian scientist Mendeleev published this early periodic table of elements. The format is not the same as it is now. We will find that there is one less "helium" in it, which is an extremely rare element in the earth's atmosphere and was not on the table at that time.

Mendeleev Museum in St. Petersburg

Original manuscript of the periodic table

(Photo: Wiki) ►

Mendeleev wrote in his first edition of his chemistry textbook Principles of Chemistry

first published the periodic table of elements.

(Periodic table diagram of elements in Principles of Chemistry: aip.org) ▼

The year before 1869, French and English astronomers observing the emission spectrum of the chromosphere of the Sun discovered this new element from the Sun and named it Helium (Greek: λ η ος), which means Helios in Greek.

Spectral lines of helium (Figure: wiki) ▼

Helium was first discovered on Earth in 1881 by Italian physicist Luigi Palmieri while analyzing magma from Vesuvius.

In 1895, Scottish chemist William Ramsay first isolated helium from yttrium uranium. Humans can finally observe and study this rare element directly.

Most helium on Earth is the result of radioactive decay

Helium is therefore abundant in uranium and thorium minerals

(William Ramsey and the Clevisite diagram of purified helium: wiki) ▼

Until today, only 48.4 billion m3 of helium resources have been discovered on Earth, and China is a very helium deficient country.

Helium is the second smallest element in the periodic table after hydrogen. It is also the direct product of hydrogen thermonuclear fusion, so there is no shortage of helium on the sun, and there is also the possibility of "helium flash" in later years.

And helium is also located in the rightmost column of the periodic table, and "neon argon krypton xenon radon" belong to the inert gas. Due to its low density and inability to form various compounds such as water like hydrogen, helium as an elemental gas can easily escape out of the atmosphere, and over time, helium on Earth becomes less and less.

Helium is low in air and easy to escape.

The world's exploitable helium resources mainly come from natural gas

So helium is a scarce, non-renewable resource.

(Color and spectrum of some rare gas discharges: wiki) ▼

In addition to its density and inertness, helium is the element with the lowest known melting point and boiling point, and has unique physical and chemical properties such as low solubility and high thermal conductivity.

These properties make helium widely used in various fields of industry.

Helium is a very light inert gas, not as flammable and explosive as hydrogen, so it is very suitable for filling balloons and airships. It is also commonly used to detect whether there is gas leakage in pipelines, containers and equipment.

Helium is used for much more than that.

(Two-chamber helium leak detector diagram: wiki) ▼

In some special welding applications, inert helium is used as a shielding gas to prevent the molten metal from reacting with oxygen in the air, known as helium shielded welding.

tungsten inert gas welding

(Photo: wiki) ►

Helium's ultra-low melting point allows it to remain liquid at extremely low temperatures, so liquid helium is an important cooling medium widely used to cool superconducting magnets, nuclear magnetic resonance instruments and laser equipment.

In advanced manufacturing, helium is also used in liquid fuel rockets, manned deep submersibles, fourth generation nuclear reactors, semiconductor manufacturing, quantum computers, precision analytical instruments, and nuclear magnetic resonance.

Given such a wide range of uses,

Helium is actually a national security, high-tech industry development

Strategic noble gas, known as "gold gas"

(Liquid helium is used to cool superconducting magnets in modern MRI scanners.)

Helium has become an indispensable emerging strategic resource. The global demand for helium in 2021 is estimated to be 204 million m3 (2.04×108m3) and is growing at an annual rate of about 5%.

Although according to the latest exploration results, the global helium resources have great potential for exploitation, but this is actually a segmented and highly technical market, resource development is seriously insufficient, and overall supply is still in short supply.

Liquid helium cooling is required in many sophisticated studies

But there are very few countries in the world that can produce helium

(Photo: news.harvard.edu) ▼

Moreover, this limited helium is highly concentrated in a few countries.

At present, the world's industrial helium is basically extracted from natural gas containing helium, so helium production and natural gas are highly correlated. According to the data of the United States Geological Survey, by the end of 2021, the total helium resources in the world are about 48.4 billion m3 (484×108m3), among which the United States, Qatar, Algeria and Russia account for 87% in total.

Countries with large helium resources are basically natural gas giants ▼

The production pattern of helium is basically the same. The United States and Qatar account for 80% of the world's production, Algeria and Russia account for 14%, and a small amount comes from Australia and Poland. Compared to them, helium production in the Asia-Pacific region is negligible.

! Horizontal screen-schematic diagram of global helium reservoir distribution and production capacity pattern (2022) ▼

Among them, the United States is the undisputed first in terms of resources and output. The United States has been developing and utilizing helium since the beginning of the last century. Until 2012, the U.S. helium supply was close to 80 percent of the world's.

However, the old United States produces more and uses more. After all, this gas is mostly used for high-end manufacturing. American enterprises are originally large users of helium, so that the strategic reserves of helium in the United States are almost exhausted. From 2012 to 2020, helium supply in the United States decreased by 40 percent from 133 million m3 to 83 million m3. By 2021, U.S. helium supply will further decline to 77 million m3.

The helium production of Qatar has increased rapidly in ten years, reaching 51 million m3 (0.51×108m3) in 2021, far ahead of Algeria 14 million m3 and Russia 9 million m3 in the second echelon.

Qatar is a big natural gas producer and has the support of American equipment

There is a natural advantage in the production of helium ▼

Countries outside these four giants are constrained by insufficient proven reserves on the one hand and technology on the other, because helium purification is very difficult and involves a series of complex technologies, which do not include the equipment and specifications required for storage, transportation and use.

Since recoverable helium is usually mixed with natural gas, it is necessary to extract "crude helium" from natural gas first through mass separation and other technologies, and then refine crude helium. Take AMGAS gas field in Lenexa, Kansas, USA as an example, its daily natural gas output since August 2022 is about 2832m3, from which 14.16m3 helium can be extracted.

Two professors at the University of Kansas found evidence

Helium in natural gas was first discovered

(Photo: wiki) ►

At present, there are two main ways to extract helium: direct helium extraction from natural gas and flash helium extraction from liquefied natural gas (LNG-BOG). The latter has higher efficiency and great development potential, but it has high requirements for the scale and extraction technology of raw gas, and "direct helium extraction from natural gas" is the only industrial method to obtain helium at present.

But China's natural gas fields are low in helium.

Direct extraction costs are extremely high

To achieve independent production, we must rely on LNG-BOG for the time being.

This technical route can be divided into "cryogenic method" and "non-cryogenic method."

Cryogenic method is the most economical and effective, and it is also the best scheme for helium liquefaction and transportation. The main principle is to purify qualified natural gas through refrigeration and cryogenic rectification to obtain primary crude helium (here,"one" sounds), and further enrich to obtain crude helium with concentration of 30%-80%. The impurity gas in crude helium is removed under low pressure and low temperature environment by cryogenic adsorption or cryogenic condensation and freezing method, and then high-purity helium is liquefied by helium liquefier.

Schematic Diagram of Natural Gas Helium Recovery Process ▼

Cryogenic process is also called cryogenic rectification process

Separation of gases by differences in boiling points of different gases ▼

This cryogenic method seemed easy, but it was actually very difficult. In principle, as long as the temperature is lowered enough, helium will be liquefied, but as mentioned above, helium is the element with the lowest liquefaction temperature, so its liquefaction method is very special, and it must undergo complex multi-stage liquefaction. Simply put, it cools itself. The technical requirements are high.

In recent years, the "non-low temperature method", that is, the "normal temperature method" to extract helium, has been successfully developed, which requires the membrane method! The operation mode is mainly multi-stage membrane method, multi-stage pressure swing adsorption, or membrane method + multi-stage pressure swing adsorption. However, the power consumption of this set of operations is too high and the process is complex, so it is not suitable for large-scale helium extraction.

Membrane Technology for Extracting Helium from Natural Gas

(Photo: uq.edu.au) ▼

To sum up, helium is widely used in modern industry, but its reserves and production capacity are highly concentrated, and the technical threshold for purification and liquefaction is also very high, which will inevitably lead to short supply.

China is short of helium, what should we do? And the contradiction between supply and demand is the most tense in our country. At present, China is already one of the largest helium consumers in the world, but it relies heavily on imports. In recent years, its dependence on foreign countries has reached more than 95%.

With the development of scientific research, medical technology and high-tech industry in China, the demand for high-purity helium is increasing.

Since 2017, China's helium imports have remained above 20 million m3 (2000×104m3) for a long time. In 2018, the import volume reached 23.11 million m3 (2311×104m3), accounting for about 14.4% of the global helium production and 98.51% of its dependence on foreign countries. (2018 Annual global production of 160 million cubic meters)

2014-2021 China helium production and import trend chart ▼

Since there are only a few major helium producers in the world, China has little choice in importing helium, mainly from Qatar, the United States and Australia, and a small amount from Russia.

At the enterprise level, our helium imports mainly come from the "six major" foreign investors, including Linde, Air Liquide, Air Chemical, Iwaya Industry Co., Ltd., Dayang Nitric Acid Co., Ltd. and Wujiang Messer, which account for 82% of the total imports.

▼

After 2020, due to production, shipping, tariffs and other reasons, imports from the United States will decrease rapidly, directly restricting China's helium imports.

As an alternative, helium from Qatar made up for the gap in the United States. In 2021, Qatar exported 16.84 million m3 helium to China, accounting for 82%.

China's dependence on helium in Qatar can be said to be very serious

However, the price of helium in Qatar is on the high side, and the technology and equipment actually come from the United States. If the United States wants to, it can also block the road of Qatar.

Moreover, in addition to the helium gas source, the manufacturers of helium liquefiers and liquid helium tanks are basically American enterprises. In order to monopolize the gas source and lack their own production capacity, they have restricted their supply to China for a long time. These factors all lead to China's easy "neck jam" in helium.

In May this year, China's independent research and development of liquid helium tanks entered mass production for the first time

In order to cope with the problem of helium deficiency, China is strengthening exploration work and technological research to improve helium production and extraction efficiency.

Since 2003, the geological survey agency of the Ministry of Natural Resources has been investigating helium resources in various places.

The large superimposed basins and intracontinental rift basins in central and western China are the main enrichment areas of helium resources in China. According to preliminary prediction, the prospective helium resources in Sichuan, Ordos, Tarim, Qaidam and Fenwei basins may reach more than 8 billion m3 (80×108m3). These are the main exploration areas for China's rapid realization of productivity.

Helium in China is mostly from the same source as oil and gas, and there are deep gas reservoirs.

This makes it difficult and costly to exploit helium resources in China

(Helium Distribution Map of China's Oil and Gas Bearing Basins) ▼

In terms of technology, at present, our technology of extracting crude helium from natural gas, refining crude helium and storing and transporting gas helium has been relatively mature. However, the technology of large-scale helium liquefaction and liquid helium storage is still in the research stage.

Although the homemade helium liquefier has been successfully developed, there is still room for improvement in performance and reliability. Moreover, the liquid helium storage tank has not been localized, stuck in the structural design and insulation materials, it will take time to fully produce independently.

Large Cryogenic Refrigeration System in Liquid Helium to Superfluid Helium Temperature Range

Successfully developed in 2021 to achieve national production of complete machine system

(80L / h helium liquefier diagram: ipc.cas.cn) ▼

To alleviate the helium shortage problem, in addition to open source, you can also throttle. To put it bluntly, it is to save money, improve recycling and reuse rates, reduce waste, or develop alternatives to helium, which can also reduce the demand for helium and reduce dependence on foreign countries a little bit.

As for finding more helium sources overseas, in view of the dual concentration of resources and technology, efforts should be made, but mainly depend on the production capacity and attitude of other countries.

China's helium is not self-sufficient yet

Seeking multi-channel helium import is also a solution to ensure the safety of helium resources

(Natural gas deep processing technology device for helium production on Heilongjiang barge)

Of course, some people may think that the sun is not all helium, can you get a little down, this should be no less technically difficult than controllable nuclear fusion, with this ability, basically nothing is lacking.

Although China's helium shortage problem is very serious, there are always more ways than difficulties. Since 2018, the degree of dependence on foreign countries has been decreasing. It should be expected to realize stable and sustainable supply of helium.

References:

1. "China's Helium Shortage: Causes and Implications" - Teng et al., Energy Policy, 2018.

2. "Helium: A Squeaky Voice for China's Development" - Liu, S., Energy Science & Technology, 2019.

3. "Analysis of China's Helium Supply and Demand Situation" - Zhang et al., Journal of Natural Gas Science and Engineering, 2020.

4. "China's Helium Shortage and Strategies for Sustainable Supply" - Li et al., Resources, Conservation and Recycling, 2021.

5. Tang Jinrong, Zhang Yuxuan, Zhou Junlin, et al. Global Helium Industry Chain Analysis and China's Countermeasures [J] . Geological Bulletin, 2023, 42 (1): 1-13

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