Market Research, Global Market for Germanium and Germanium Products

By Andrei Besedin

The research report is focused on analysis of the world germanium market and the germanium product market. The report provides details on the markets, outlines market forecasts. The markets analysed from the 5 Forces Porter framework. 
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1) Get detailed understanding of germanium market and germanium product market
2) Be prepared for an important relevant meeting and conference quickly
3) Get the most detailed and profound research information on worldwide germanium market and germanium product market. The report - the most detailed research report on the market focused on gernamium and germanium product market with more than 200 pages of research text, extensive numerical and graphical information
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6) Identify market direction. The report has details on major producers as well as details by producing country.
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• Language: English
• Publisher: Andrei Besedin
• Release date: Dec 29, 2017

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industries.

CHAPTER 1.      GENERAL REVIEW OF THE INDUSTRY.

1.1.      HISTORIC, PRESENT AND ESTIMATED CORRELATION OF GLOBAL GERMANIUM DEMAND AND SUPPLY.

GENERAL DATA ABOUT GERMANIUM (GE)

Germanium is a chemical element with symbol Ge and atomic number 32. It is a lustrous, hard, grayish-white metalloid in the carbon group, chemically similar to its group neighbors tin and silicon. Purified germanium (Ge 99.9999%) is a semiconductor, with an appearance most similar to elemental silicon. Like silicon, germanium naturally reacts and forms complexes with oxygen in nature. But, unlike silicon, it is too reactive and is found in the Earth crust only in compounds.

Due to its low content in the crust of Earth and geochemical resemblance to a number of wide-spread elements, Germanium demonstrates limited ability to produce the minerals of its own, penetrating to the crystalline grid of other minerals. That is why native germanium minerals occur very seldom. Almost all of them are sulfosalts: germanite Cu2 (Cu, Fe, Ge, Zn)2 (S, As)4 (6 - 10% Ge), argyrodite Ag8GeS6 (3,6 - 7% Ge), canfeldite Ag8 (Sn, Ge) S6 (up to 2% Ge), and other rare minerals (ultrabasite, ranerite, franckeite).

At room temperature germanium is proof against the action of air, water, alkali solutions, low-concentration hydrochloric and vitriol acids. At the same time it is easily soluble in aqua regia and alkali solution of hydrogen peroxide. It is slowly oxidized by azotic acid.

GERMANIUM PRODUCTION.

The main mass of Germanium is dispersed in the crust of Earth in a great number of rocks and minerals. For instance, in some sphalerites its concentration is several kg per ton. In enargites it is up to 5 kg/t, in pyrargyrite it is up to 10 kg/t, in sulvanite and franckeite its concentration is up to 1 kg/t, hundreds and dozens of g/t in other sulfides and silicates. Germanium occurs in the deposits of many minerals, in iron ores, in some oxide minerals (chromite, magnetite, rutile, etc.) in granites, diabases and basalts. Besides, germanium is present in almost all silicates, in certain fields of coal and oil.

There is a substantial amount of Ge in zinc, lead, copper-zinc ores (as isomorphic impurities) and minerals (in the form of intergrowth of Ge-minerals in concentrating minerals). Such dispersion of Ge is explained by the fact that it can behave both like chalcophilic, lithophilic and siderophile element.

In industry germanium is mainly obtained from the side products of non-ferrous ores products (zinc blende, zinc-copper-lead polymetal concentrates. As a raw they also use ash from coal combustion (the method is typical of Russia and China), gasifiers dust and coke plants waste. The cost of germanium is a driven power for its production from by-products and waste of other industries. The share of Ge recovered from scrap has already reached 30–40 % and will keep on growing stimulated by the Waste Electrical and Electronic Equipment Directive (WEEE Directive).

THE MAIN STAGES OF PRODUCING GE AND GE CONTAINING PRODUCTS.

They take germanium containing sulfide zinc or lead ores or coals, in which germanium is present within the range from thousandths to hundredths of a percent, to successively receive: Ge concentrate (from 5 to 30 % Ge), germanium tetrachloride (GeCl4), its oxide, poly and monocrystals. The by-products of this technological chain include goods of various applications.

Figure 1.1. The main stages of general production of Ge and Ge containing products¹.

GeCl4 is used as a component for production of glass in optical fiber equipment (fiber optic communication line). GeO2 with the purity of up to 99,999% is used in catalysts for polymerization of PET plastics (Poly Ethylene Terephalate resins). BGO (Bi14Ge3O12) is applied in the production of crystals for scintillation detectors of high-energy photons. Poly and monocrystal windows and lens, produced from Ge monocrystals grown by Czochralski method, are applied in night infrared imaging.

Semi-conducting properties of germanium are applied in electric devices and solar inverters, as well as Si-Ge compounds. To some extent it is applied in the production of luminous colors, metallurgy and medicine.

Thus, there are several germanium markets: its dioxide of various purity for various applications, tetrachloride, zone-refined polycrystalline ingots, monocrystals, optical blanks and substrates.

PRODUCTION OF GE DURING SULFIDE ORES CONVERSION.

A wide-spread method of germanium production is based on simultaneous extraction of germanium from sulfide zinc, lead-zinc and sometimes copper-inc ores. During hydrometallurgy method of zinc ore production, Ge remains in dump leaching cakes of zinc calcine. During the production of lead, Ge is simultaneously received from sublimates during slag fuming. During the production of copper, Ge is extracted from the dust of mine and reverberatory melting, dust of converters and sublimates during slag fuming.

For example, during oxidizing roasting, germanium is oxidized to GeO2, which reacts with the oxides of the calcine and concentrate, producing germanites and silicon germanites, and remains in the calcine. The latter is leached with sulfuric acid and Ge is dissolved. After solution neutralization, germanium remains in the cake, which is subjected to waeltz - reduction roasting. Waeltz oxide (in which germanium may be contained with indium, thallium, cadmium, etc) is subjected again to acid leaching and then treated with CaO (MgO) to precipitate and concentrate germanium.

PRODUCTION OF GE DURING COAL COMBUSTION.

During industrial coals combustion their mineral components are distributed between slag, remaining in the combustion chamber, and fly ash (ash carryover), carried along by the combustion gases. Practically all germanium (from 70 to 95% depending on the combustion mode) contained in coal turns into gaseous germanium monoxide and then, as long as the combustion product cools down, it condensates on fly-ash in the form of GeO2, germanites and silicon germanites. The principal amount of Ge precipitates on the particles of ash, which should be caught, to the maximal extent possible, in filters and electrical filters. In any case, the concentrates are further treated with hydrochloric acid or chlorine, followed by distilling off germanium tetrachloride from hydrochloric acid solutions and its refining distillation, GeCl4 hydrolysis for production of GeO2 and GeO2 hydrogen reduction, if it is necessary to obtain metal Ge. The obtained Ge globule is subjected to zone refining.

GLOBAL GERMANIUM PRODUCTION.

Rare earth elements including germanium belong to the types of mineral raw having strategic importance for the industrialized nations of the world community.

In 1990 the total resources of germanium as a chemical element contained in zinc deposits were assessed at 120 thousand tons, and in coals at 4.5 thousand tons. Semi-industrial production of Germanium dioxide was started by Eagle-Picher (the USA) approximately in 1941, and in 1948 the production of GeO2 in the world reached 460 kg. After that the production of Ge in the world was ever growing.

The ups and downs of hopes on the growth of mono germanium production in 1995-2000 were related to the projects of global satellite telephone communication like Iridium, Inmarsart or ISO Global. They envisaged launching to the orbit a great number of satellites with strong on-board power. Thus, for instance, one PAS-5 satellite constructed by Hughes Space and Communication Co. to this end required 15 thousand GaAs double-layer batteries with the efficiency of 21.6% on Ge substrate with the diameter of 100 mm. It was calculated that the first stage of implementation of Iridium project would require 18 tons of Ge monocrystals of perfect structure. While they were expecting orders, the producers started collecting material, which prompted the growth of prices on the market, which is in fact rather small. Iridium system was launched in 2001, but in a limited scope. Currently, the growth of this sector is supported by the development of satellite television and high-speed Internet.

GLOBAL GERMANIUM MARKET.

The global germanium market is extremely dynamic and changing. The supplies of germanium largely depend on zinc mining industry, while the demand in the mineral varies depending on changes in the branches of industry and its final consumption.

China is a recognized leader in germanium production and consumption. There are several big companies producing germanium raw on its territory:

Yunnan Chihong Zn & Ge Co., up to 40 tons a year

China Germanium Co., Ltd., up to 40 tons a year

Tongli Germanium Co., Ltd., up to 10 tons a year

In China there are ore fields, at which the production of germanium is possible. The fields are mainly located in:

brown coal mines near Lincang, Yunnan Province;

coal mines near Xilinhaote, Inner MongoliaProvince.

The total amount of the reserves is 3500 tons and the potential reserves are 9600 tons. The deposits of Germanium in the Yunnan province make up 33.77% of all reserves in China.

Today, most of the Chinese germanium and its products are exported to the USA, Germany and Japan. America is a major exporting market of the Chinese germanium. 60% of germanium varieties exported from China consists of germanium dioxide. Most of it is exported to Japan. In 2011-2013 polycrystal zone-refined germanium was playing a substantial part in the export structure. Yet, its role diminished during the last years giving way to other varieties of germanium.

Table 1.2. Global production of the natural* germanium across the countries of the world in 2013-2014, in tons².

The general analysis of the germanium market in China shows that in 2014 the total amount of natural Ge was just 110 tons (without its secondary conversion) including 31.4 tons or 28.5% for domestic consumption. The amount of export is 78.6 tons or 71.5%. The experts of Asian Metal agency predict that in the future, in 2015, the export of germanium from China is going to rise by 5.4% and reach 82.8 tons. As far as inner consumption is concerned, its level is going to increase by 5.1% and reach 33 tons in 2015 and 44.6 tons in 2020.³

Though the USA is rich in germanium reserves, its production output is extremely low, and the country mainly depends on import. In spite of rich germanium reserves, the level of American germanium production makes up ~2.6% of global amount due to limited development of local fields.

In the USA the sulfide zinc ores and by-product germanium concentrate is produced at 3 mines. This is Red Dog Mine, Alaska, the biggest zinc mine in the world, Gordonsville in Tennessee and Pend-Orielle in Vermont. In 2004 Economic Geology published data on the content of Ge in the ores of Red Dog Mine, which is 106 g/t. It means that 8 thousand tons of Ge is produced.

As a strategically important material, germanium was included in the list of the USA National Defense Strategy (NDS): in 1984 in the amount of 30 thousand tons of zone-refined ingots, in 1987 - 146 thousand kg and in 1991 - 68198 kg. Every year NDS sells, via the Defense Supply Agency, part of its germanium reserves, about 4000-8000 kg a year, at the open market, on the tender basis. These sales are not only a good price indicator for the market participants, but are also an important factor of global prices formation.

The general level of germanium consumption (not production) in the EU countries is assessed at 26.6 tons in 2014 and it is predicted to increase with the average growth rates of 2.5% till the level of 31.03 tons in 2020. Among the principal consumers of germanium in Europe there is France with 22.76%, Germany with 18.71% and England with 14.4%. In its turn Russia occupies the 4th position with 9.7% or 2 577 kg of Ge. Yet, the Russian market of germanium consumption ranks 1st in the EU in terms of growth: the level of consumption grows with the average rate of 3.3% up to the level o 3.2 tons in 2020.

In Russia all industrial reserves are concentrated in three principal regions: Maritime Territory, Sakhalin and Chita regions.

The largest explored reserves of Ge in the coals of Russia include:

Pavlovskoye Field (MaritimeTerritory) - the content of Ge is 300 g/t,

Tarbagatay (Buryatia) - 72 g/t,

Novikovskoye (Sakhalin) -200-350 g/t,

Shkotovskoye (MaritimeTerritory) has extremely high content of Ge, but the reserves are located on the depth of 500m under Peter the GreatBay in the Sea of Japan.

Practically all natural germanium in Russia is produced from Pavlovskoye Field. The other deposits of germanium are currently not developed or their use is low.⁴

The USSR developed two technologies of germanium production: from over-resin waters of coke plants and the ashes of Ge-containing coals. In the first variant, they make use of the property of tannin to connect even the smallest amounts of germanium. The first domestic GeО2 was developed in 1941.

After that they started using the second method. The chain of Ge production was geographically dispersed. The coal produced at Novikovskoye and Tarbagatay fields was burnt at Chita TPP-2, where the ash was caught. Then it was moved to the Urals, to Mednogorsk Copper and Sulphur Combined Works or to Uzbekistan to Angren Chemical and Metallurgy Works, where the enriched concentrate was produced, which was processed at Germanium state enterprise in Krasnoyarsk (from 1961 through 1998, Krasnoyarsk Plant of Non-Ferrous Metals) or at Zaporozhie Titan and Magnesium Combined Works. These enterprises produced zone-refined germanium-, its dioxide, mono and polycrystals of optical blanks, etc. After the collapse of the USSR there was no production of germanium from 1994 to 2001.

In Russia there are two major germanium producers: OJSC Germanium and Germanium & Applications LLC. As far as OJSC Germanium is concerned, the company makes part of 5 biggest enterprises in the world. It produces secondary germanium, processes waste and purchases raw all over the world (for instance, it buys scrap, mineral waste in Finland)⁵… The market experts assessed the level of secondary germanium production at ~7.5-8 tons in 2013. Thus, practically all natural raw in Russia is produced by Germanium & Applications LLC, which uses the ores of Pavlovskoye Field (up to 2.5-3 tons in 2013)⁶.

The export from the RF is carried out only by two companies: OJSC Germanium and Germanium &