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Procedia Engineering 46 (2012) 255 265

1st International Symposium on Innovation and Technology in the Phosphate Industry

[SYMPHOS 2011]

Manufacture of Aluminium Fluoride of High Density and Anhydrous

Hydrofluoric Acid from Fluosilicic Acid
Alain Drevetona,*
AD Process Strategies Sarl, Rue Chaponnire 9, CH-1201 Geneva, Switzerland

Abstract
New process technologies are disclosed to manufacture aluminium fluoride of high density and anhydrous hydrofluoric acid starting from
fluosilicic acid as raw material which is obtained during acidulation of phosphate rock in the manufacture of phosphatic fertilizers. An
overview of the relevant process technologies used commercially to consume this fluosilicic acid is provided in this paper. The new
process technologies which shall be implemented to satisfy market demand in fluorochemicals (production of aluminium fluoride of high
density from fluosilicic acid and production of anhydrous hydrofluoric acid from fluosilicic acid) and overcome some technical issues as
well are described.

2012
2012 The
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PublishedbybyElsevier
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peer-review
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Committee of
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CC BY-NC-ND
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Keywords: aluminium fluoride, hydrofluoric acid, fluorine technology, fluosilicic acid, fluorochemical, silicon tetrafluoride, sodium silicofluoride,
suplphate of potassium, sodium sulphate

Nomenclature
AHF
ATH
DCP
FSA
FSA1G
FSA2G
FSA3G
HBD
HFC
KSF
LBD
MGSF
MOP
PA
PR
SA
SAC

Anhydrous hydrofluoric acid

Alumina trihydrate, aluminium hydroxide
Dicalcium phosphate
Fluosilicic acid, fluorsilicic acid
FSA-based technology of the first generation
FSA-based technology of the second generation
FSA-based technology of the third generation
High bulk density, HD-AlF3
Hydrofluorocarbon
Potassium silicofluoride, Potassium fluosilicate
Low bulk density, LD-AlF3
Magnesium silicofluoride, Magnesium fluosilicate
Muriate of Potassium, KCl
Phosphric acid
Phosphate rock, Rock
Sulphuric acid
Sulphuric acid concentration

* Corresponding author. Tel.:+00 41 22 548 1249; fax:+00 41 22 545 7512.

E-mail address: a.dreveton@adpro-stg.com

1877-7058 2012 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of the Scientific Committee of SYMPHOS 2011
Open access under CC BY-NC-ND license. doi:10.1016/j.proeng.2012.09.471

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Alain Dreveton / Procedia Engineering 46 (2012) 255 265

SSA
SSF
SOP
STF
Symbols
MMT

Sodium sulphate anhydrous

Sodium silicofluoride, Sodium fluosilicate
Sulphate of Potassium
Silicon tetrafluoride
Million metric tons

1. Fluorine raw material resources

Fluorochemicals are essentially produced from raw material fluorspar (Acid Grade Fluorspar: CaF2 > 97%). A small
amount only (about 5%) is produced from phosphate rock, an alternative raw material containing fluorine for production of:

Fluosilicic acid
Fluosilicates
Cryolite
Aluminium fluoride
Silicon tetrafluoride

1.1. Uses of Fluosilicic acid

Fluosilicic acid is used as water fluoridation agent of drinking water to prevent tooth decay in US, Canada, South Africa
and Australia mainly. The US production of fluosilicic acid in 2010 estimated and reported by USGS (Miller, 2010) is
68000 tons (FSA as 100% H2SiF6) mostly used for water fluoridation and manufacture of silicon tetrafluoride (STF = SiF4)
up to 20000 tons being a raw material for polysilicon produced by MEMC, an intermediate to high purity silicon for solar
and chips applications. In this process, MEMC claimed that the capital cost of this process is reduced by 50 % compared to
classical Siemens process and electric consumption for purification reduced by 20 folds. Other uses of FSA are in the
tanning of animal skins, in ceramic and glass etching, in technical paints, in oil well acidizing, preservative of wood,
hardening of masonry, remover of mould, remover of rust and stain in textiles, cleaning and sterilizing agent in industry,
and in electro-refining of lead, etc. Very minor quantities of FSA are produced also from fluorspar processing.
Table 1: Uses of fluosilicic acid
COUNTRY

COMPANY

FLUOROCHEMICAL
PRODUCT

YEARLY CAPACITY
(TON)

US

4 Companies (Plants) Reporting

FSA

<< 68000

US

PCS Phosphate Co.

STF

< 28000

EU (BE)

Prayon

SSF/PSF

18000 / 3000

EU (HU)

Bige Holdings

Cryolite

<<

EU (PL)

TARNOBRZEG Ltd.

Cryolite

<<

EU (SE)

Alufluor

LD-AlF3

23000

CN

Several Producers

LD-AlF3

Small

CN

Wengfu

AHF

20000

IN

Alufluoride

LD-AlF3

5000

IN

Hindalco

LD-AlF3

3000

CN

Several Plants

SSF/PSF/MGSF
/NH4F

--

CN

Yunnan Three Circles Chemical Industry Co.

SSF/PSF

--

JO

JPMC

LD-AlF3

20000

ID

PT Petrokimia Gresik

LD-AlF3

12000

RU

Phosagro /Ammophos

LD-AlF3 / SSF

23000

BY

JSC Gomel Chem. Plant

Cryolite / LD-AlF3

5000/5000

LT

Eurochem / Lifosa

LD-AlF3

17000

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Aluminium fluoride is still the major product out of FSA with a production < 100000 tons / annum against about
800000 tons / annum mainly produced from fluorspar reported by (Reynolds, 2010) . See Table 2 below. 
Table 2: World and China aluminium fluoride (AlF3) production and consumption per year (x 1000 tons)

STF could grow significantly as its added value is higher than manufacturing AlF3 / AHF making projects even more
attractive. Already five projects have been implemented in Asia (approx. 70000 tons / annum STF) using the fluorspar
process although it makes more sense to start from FSA.
Presently there is a supply shortage of FSA for water fluoridation in US and Canada and prices of FSA have risen
significantly.

1.2. Fluorspar resources

China is dominating largely the fluorspar industry (59% of world fluorspar production) (Will, 2010)) and China is
starting to face sourcing problems at present. China has changed its policy with tighter rules. Consequently fluorspar prices
are rising. Europe has included fluorspar in a list of 14 minerals classified as critical. A raw material is labelled critical
when the risks for supply shortage and their impacts on the economy are higher compared with most of the other raw
materials

a)

(b)
Fig. 1 : World production of fluorspar (a) 5.1 million tons (Will, 2010) and (b) 5.4 million tons (Miller, 2010). Reserves of fluorspar are reserves
that are economical to extract and recover according to USGS (Miller, 2010) are also reported.

According to (ResearchInChina, 2010), the fluorspar reserves in China (2009) reached 21 million tons, providing 9.3%
of the worlds total, ranking at the third position, while the fluorite output recorded three million tons in the same year,
contributing 58.8% to the worlds total, topping the global list. According to statistics of year 2009, the ratio of fluorite

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Alain Dreveton / Procedia Engineering 46 (2012) 255 265

reserves to output in China was not more than seven, indicating that the fluorite resource in China is likely to run out within
seven years provided that the recoverable reserves of fluorite will fail to increase.
China is deficient in fluorite resource and demand is growing for fluorite year after year at significant pace. In 2009, the
apparent consumption of fluorite in China reached 2.8 million tons, up 8.2% from a year earlier; and the figure in H1 2010
hit 1.93 million metric tons (MMT). Concerning the consumption of fluorite, China ranks first around the globe, but lags far
behind the developed countries in term of downstream consumption. A case to this is fluorine chemical industry, the
demand of fluorite is 30% less in China than opposed to nearly 60% in developed countries.


Fig. 2 : Map of fluorspar reserves in China (HeQing, 2005, p. 5)

(a)

(b)
Fig. 3: World HF production capacity is about 2 million tons in 2009 (a) and Fluorine Industry Segments: fluorocarbon production is the largest HF
segment followed by aluminium fluoride production (Will, 2010)

As long as fluorspar was cheap, there was no need for an alternative source of fluorine like FSA. Presently the price of
fluorspar is about USD 350.-/ton FOB compared to FSA 100% that can be produced very cheaply, by operating a single
absorber. The theoretical price of FSA would be USD 600.-/ton if fluorine F contained in FSA is assumed at the same value
of F contained in fluorspar. At this price, it makes any business for fluorine attractive and it is adding appreciable value to
the phosphate business. Especially for aluminium fluoride that is a bulk chemical, easily transportable requiring large

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259

amounts and competitive sources of fluorine. At the time of writing this paper, some Acid Grade Fluorspar from China
reached USD 500.-/ton back to pre-recession highs.
phosphate rock resources
The world population is expected to reach 9 billion of inhabitants in 50 years and productions / capacities are forecasted
to increase by more than 50% maybe 70%. In the near future, fluosilicic acid uses will probably increase bearing in mind
that environmental regulations are more stringent, technical hurdles for the technology are now resolved, technical expertise
is available, communication between the industrial sectors concerned is improving constantly.
The phosphate rock reserves are assumed to be sufficient for more than a century; other base reserves less attractive will
be considered at the end of the century only. (See below Fig. 4 Hubbert peak for phosphorus)
Table 3: Phosphate rock production and reserves according to USGS (Jasinski, 2011)

According to International Fertilizer Association (IFA, 2009), the world production of phosphate rock in 2009 was 162
million tons phosphate rock (49.7 million tons as P2O5) and the world production of phosphoric acid was 33.6 million tons
expressed as P2O5 (48.6 million tons expressed as H3PO4)

Assuming that phosphate rock contains 2 to 5% fluorine (average approx. 3% F) an amount of 4.8 million tons of
fluorine is available which is about twice the amount of F present in fluorspar. (Fluorspars are up to 48% F).

Fig. 4: Peak of phosphate rock [Hubbert peak] (Kauwenbergh, 2010)

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Alain Dreveton / Procedia Engineering 46 (2012) 255 265

Assuming a recovery rate of 35% as a minimum as per data below (EFMA, 2000, p. 24) for dihydrate (DH) & Hemihydrate (HH) Phosphoric Acid processes: an amount of 1.7 million tons F could be recovered (2.0 million tons FSA 100%)
corresponding to 1.4 million tons AHF about 70% of world production.
For higher accuracy of this assessment, the production of FSA should be defined for each production plant and calculated
as a function of the rock used and technology used for manufacturing phosphoric acid if exact production is not known.
Table 4: Typical distribution of F in dihydrate and hemihydrate PA (phosphoric acid) processes

Acid
Gypsum
Reactor off gas
Flash cooler vapour
Concentrator vapour

Dihydrate process (%)

Hemihydrate process (%)

15
43
5
3
35

12
50
8
30
-

As shown above (Table 1) fuosilicic acid finds its main application in the manufacture of low bulk density (LBD)
aluminium fluoride being a large volume chemical which is mostly produced from fluorspar as high bulk density (HBD)
aluminium fluoride. From fluosilicic acid a small amount only is produced. Aluminium fluoride is essentially used as a flux
for smelting aluminium by volumetric addition to the cells of aluminium smelters in order to regenerate the cryolite bath.
HBD aluminium fluoride is the preferred material due to its high density and good fluidity and none of this high density
material is produced at present from FSA via intermediate HF which process is available, feasible and proven at this time.
Hereinafter are disclosed new process technologies for manufacturing anhydrous hydrofluoric acid (AHF) from
fluosilicic acid (FSA) which AHF can be converted into (HBD) aluminium fluoride. This aluminium fluoride technology
often referred to as the Dry/FSA Process which is a gas phase process using a fluidized bed reactor. An opportunity to invest
in profitable projects does exist really. Additionally the manufacture of various downstream products of fluorine:
refrigerants, fluoropolymers, etc and downstream products of silicon: silicon metal, silicon tetrafluoride, silicas may offer
further interesting opportunities.
2. FSA-based Fluorine technologies
2.1. LBD-Aluminium fluoride from FSA [FSA1G]
FSA1G: FSA-based technology of the first generation (1G) is the: wet FSA process for production of AlF3 from FSA.
This process has also an equivalent process of first generation starting with fluorspar which is the old wet HF/fluorspar
process for production of aluminium fluoride and cryolite which is today totally abandoned.
The first process known for manufacturing (LBD) aluminium fluoride from fluosilicic acid was patented by ChemieLinz, Austria (Weinrotter, 1963) about 50 years ago and many plants were built based on this technology or comparable
technologies.
Chemistry:
H2SiF6 + Al2O3.3H2O  2 AlF3 + 3 SiO2 + 4H2O

[1]

This process uses the direct neutralization of the fluosilicic acid with alumina hydroxide carried out in a stirred reactor. It
is often referred to as the Wet/FSA Process . Although this technology tends to be abandoned due to the low density and
low fluidity (flowability) of the product, the high capital cost of the plant and its environmental issues resolved partially
only as neutralization of mother liquors may still be required, further developments of this process would revive this
technology being still accepted by few players only. Improvements are available from us for material of construction and
cost-effective design, improved crystallisation process, product granulation, etc.
This process requires very pure FSA. Quality of the FSA is often a limitation to use this process.

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261

Fig. 5: Flowsheet LBD-Aluminium fluoride from FSA. Wet FSA-based Process of first generation [FSA1G]

Plants (usual name) built with this technology: JPMC, Alufluor, Lifosa, Ammophos, Alcoa, Luzhai, Guixi, Dayukou,
Wengfu, Achinsk, Pchiney Salindres, Lubon, DMCC, Alufluoride, Navin, Hindalco, SPIC, PT Petrokimia Gresik, AlQaim,
Gomel, Trepca.
2.2. HBD-Aluminium Fluoride from FSA and AHF from FSA [FSA2G]

FSA2G: FSA-based technologies of the second generation (2G) known also as HF from FSA or dry process for AlF3
from FSA or fumed silica process by the fluorine route.
A process for manufacturing AHF from fluosilicic acid was disclosed first by Tennessee Corp., USA (Oakley, 1962)
(Houston, 1962) maybe 50 years ago and further disclosed by Wellmann-Lord (Kelley & al., 1971), etc and more lately by
(Flemmert, 1974) of Nynaes Petroleum, Sweden, and (Zawadzki, 1977) Lubon Works, Poland, the latter operated a small
pilot plant for manufacturing diluted HF. In 2008 Wengfu, China commissioned a first commercial plant for AHF with the
technology of Buss Chemtech AG, Switzerland based on know-how from Lubon Works.
Chemistry:
H2SiF6.SiF4(aq) + H2SO4 2 SiF4 + 2 HF(aq) + H2SO4
5 SiF4 + 2 H2O 2 H2SiF6 .SiF4 (aq) + SiO2 (s)
Al2O3.3H2O Al2O3 + 3 H2O
Al2O3 + 6 HF 2 AlF3 + 3 H2O

[2]
[3]
[4]
[5]

The process is based on the decomposition of FSA by mixing strong fluosilicic acid with strong sulphuric in a stirred
reactor and separating silicon tetrafluoride gas using sulphuric acid as dehydrating agent and extracting the anhydrous
hydrofluoric acid into separation columns as per the principle shown on the flowsheet below. The evaporation can be
realized with a single stage or two stages. Presently AD Process Strategies Sarl proposes an improved process of this
technology to suit the water balance of the phosphoric acid (PA) plants, di-hydrate (DH) PA Process and especially hemihydrate (HH) PA process being not suitable to receive large amount of water at its goal is to produce strong phosphoric acid
directly. Sulphuric acid containing water that is generated from this HF plant has to be re-circulated to the phosphoric acid
plant. The sulphuric acid usage or recirculation which is normally 30 ton/ton AHF as 100% H2SO4 can be reduced to 15
ton/ton. Water contained in the acid recirculated is reduced from more than 10 ton/ton AHF down to 5 ton/ton.
The technology of second generation is proven, resolves environmental issues and is very profitable as raw material costs
are low (low cost of fluorine, no cost for sulphur or sulphuric acid at all), the capital cost is reasonable. Moreover this
technology is promising as it open markets to HBD aluminium fluoride and anhydrous hydrofluoric acid, both being large
volume chemicals.

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Alain Dreveton / Procedia Engineering 46 (2012) 255 265

This process is less sensitive to impurities contained in the FSA due the provision of AHF purification unit in the
process.

Fig. 6: Simplified flowsheet AHF from FSA [FSA2G]

Fig. 7: Flowsheet HBD-Aluminium Fluoride from AHF [FSA2G]

An optional process is a process with hydrolysis of STF in the gas phase under high temperature to produce silica, Fumed
silica as per the Nynaes process or silica as per the Reed process. Silicon tetrafluoride (STF) can be produced from this
process as well.
Plants (usual name) built with this technology: Lubon, Grace, Wengfu for AHF

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263

2.3. HBD-Aluminium Fluoride and AHF from fluosilicates (from SSF or FSA) [FSA3G]
FSA3G: FSA-based technology of the third generation. This is the advanced process for stand-alone plants providing
many alternatives for not recycling water and sulphuric acid to the phosphoric acid plant and alternatives for reusing the
material streams available inside the process cycle.
When diluted sulphuric acid stream is not returned to the phosphoric acid plant or can not be re-circulated due to
technical reasons or not and in particularly in the process of second generation mentioned above, AD Process Strategies Sarl
proposes a new technology for stand-alone HF plants. The proposed process uses a fluosilicate as an intermediate (solid)
raw material, which is transportable not like FSA and reaction of this fluosilicate with strong sulphuric acid. The silicon
tetrafluoride and hydrofluoric acid so obtained are treated as per the state of art technique in a similar manner as mentioned
above for the technology of second generation using absorption / desorption of HF in sulphuric acid. The diluted sulphuric
acid stream resulting from this process can be pre-concentrated and recycled to the phosphoric acid plant or used in
production of fertilizers like single superphosphate (SSP), dicalcium phosphate DCP, ammonium sulphate (AS), etc or
concentrated and recycled to the HF reaction or purified for sale.

Fig. 8 : Block diagram for HFD Aluminium fluoride and AHF from SSF or FSA [FSA3G]. (in dark blue: main process cycle, in light blue: optional
process units). [Operation units: R-Reactor, S- Separator, A- Absorber, C- Crystallizer,..]

Water balance for the various technologies

FSA1G

Wastewater to be neutralised or recycled in cooling tower water loop.

FSA2G

30 to 15 tons sulphuric acid and 10 to 5 tons of water in spent acid per ton HF produced (or per 45 tons of
PA produced expressed as P2O5) to be recycled.

FSA3G

5 to 0 tons of sulphuric acid and 5 to 0 tons of water in spent acid per ton HF produced to be recycled.

Chemistry: The process uses the chemical reaction of sulphuric acid / sodium fluosilicate in opposite direction under
different conditions, in aqueous medium and low temperature (step 1) and in anhydrous medium and high temperature (step
2):

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Alain Dreveton / Procedia Engineering 46 (2012) 255 265

Step-1: Production of sodium fluosilicate (SFS) or silicofluoride (SSF) by one of these chemical reactions: (reaction 2 is
the usual process to manufacture SSF)
H2SiF6(aq) + Na2SO4(s) Na2SiF6(s) + H2SO4(aq)
H2SiF6(aq) + 2 NaCl(s) Na2SiF6(s) + 2 HCl(aq)

[6a]
[6b]

Step-2: Decomposition of SSF by Sulphuric Acid and recycle of SiF4 creating a loop to generate additional FSA and
SSF. (This reaction was tested; yield is not critical as the salt is recycled or can be purified as required)
Na2SiF6(s) + H2SO4 2 HF(g) + SiF4(g) + Na2SO4(s)
3 SiF4 + 2 H2O 2 H2SiF6(aq.) + SiO2(s)

[7]
[8]

Step-3: The aluminum fluoride is produced between reaction of HF with alumina trihydrate in a fluidized bed reactor.
This process is the same as for the fluorspar process or FSA process of second generation [FSA2G])
Al2O3.3H2O Al2O3 + 3 H2O
Al2O3 + 6 HF 2 AlF3 + 3 H2O

[4]
[5]

Step-4: Pre-concentration of sulphuric acid (A pilot unit is operating since more than 10 years concentrating sulphuric
acid up to 85% in presence of fluorine) and recycle of this acid to the process or reused by other consumers.
Plants built with this technology: First prefeasibility study is underway. Acceptance for this technology of third
generation is higher than for the technology of second generation.
Use of Potassium fluosilicate (PSF) instead of SSF for this Process still needs to be investigated. It provides the
advantage of producing directly sulphate of potassium (SOP) which is a large volume fertilizer.
3. Extra- productions using third FSA generation technology [FSA3G]
Many alternatives are potentially available to use the materials present in streams internally recycled in this process that
will definitely improve the benefits and economics of projects.
3.1. Production of Dicalcium Phosphate (DCP)
Production of DCP from HCl (and optionally from sulphuric acid and sodium chloride or sea water) for production of
DCP (feed grade) as a production unit or as neutralization unit with separation of solids and recycling for production of
DCP (fertilizer grade).
Dicalcium Phosphate dihydrate CaHPO4.2H2O, is produced by a wet process according to the following steps:
[9]
Ca3(PO4)2 + 4 HCl Ca(H2PO4)2 + 2 CaCl2
[10
Ca(H2PO4)2 + Ca(OH)2 2 CaHPO4.2H2O + 2 H2O
- Reaction of phosphate rock with hydrochloric acid, main raw materials, from which a monocalcium phosphate liquor is
obtained.
Purification of the remaining solution by means of the removal of the inert matters and undesirable compounds.
Production of dicalcium phosphate by means of calcium salts precipitation and product filtration.
Drying of dicalcium phosphate at moderate temperature to keep its two water
molecules.
3.2. Production of Sulphate of Potassium (SOP)

Production of SOP by the double salt decomposition, Glaserite process. In this process sodium sulphate is reacted with
potassium chloride to yield potassium sulphate. This reaction occurs in two steps as follows:
[11]
4 Na2SO4 + 6 KCl = Na2SO4.3K2SO4 + 6 NaCl

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265

2 KCl + Na2SO4.3K2SO4 = 2 NaCl + 4 K2SO4

[12]
This process route is cheaper than the Mannheim process (thermal oven process) and it makes sense if the sulphate is
available and cheap.
3.3. Production of Silicon Tetrafluoride (STF)
STF product of reactions [2] [7] is dried, purified and compressed into pressure cylinders for transportation to the
polysilicon plant, if required or better polysilicon plant is built at site.
3.4. Production of Sodium Sulphate (SSF)
Sodium sulphate product of reaction [7] can be purified using a crystallization process to obtain the quality required for
the final applications of SSA in detergents, paper, glass, etc
3.5. Production of Silica
Byproduct silica can be used in the defluorination process of phosphoric acid or defluorination process of sulphuric acid,
production of water glass, production of precipitated silica, production of zeolites, production of cements or used as soils
conditioners.
4. Conclusion
Fluorine chemistry is basically a good solution for adding value to the phosphate downstream products.
No doubt, economics are good as raw materials are available almost free of charge. It is only a matter to discuss how
good are the economics? What are the best options to be selected?
Presently as the costs of raw materials are escalating, environmental issues are every day of bigger concern, expertise is
accessible, technologies are affordable in cost-effective manner and from us particularly, barriers between the various
industrial sectors are not anymore a brake (between fluorine industry and other industrial sectors such as fertilizers,
aluminium, cement, solar and polysilicon, etc), then great opportunities for cooperation are in front of us. Hoping in future
cooperation.
These new fluorine technologies are real innovations for the fertilizer industry and surely they will be implemented
progressively. More and more projects are under study and hopefully some projects might be realized in the near future.
References
[1] EFMA. (2000). Production of phosphoric acid, Best available techniques for pollution prevention and control in the European fertilizer industry,
booklet No. 4 of 8.
[2] Flemmert, G. L. (1974). US3969485 Process for converting silicon-and-fluorine-containing waste gases into silicon dioxide and hydrgen fluoride.
[3] HeQing. (2005). The situation and development of resource of fluorspar in China. Some thinking of fluorspar industry by CFIC. Fluorspar 2005.
[4] Houston, T. T. (1962). US 3218125 Process of producing hydrgen fluoride from fluosilicic acid in a two-stage procedure. Tennessee Corp.
[5] IFA. (2009). http://www.fertilizer.org/ifa/HomePage/STATISTICS/Production-and-trade.
[6] Jasinski, S. M. (2011). Phosphate rock, U.S. Geological Survey, Mineral Commodity Summaries, January 2011.
[7] Kauwenbergh, S. V. (2010). World phosphate rock reserves and resources. Center for Strategic and International Studies, September 22, 2010. IFDC.
[8] Kelley, C., & al., A. G. (1971). U 3758674 Process for producing anhydrous HF. Wellman Power-Gas Inc.
[9] Miller, M. (2010). Fluorspar. USGS.
[10] Miller, M. (2010). Fluorspar, U.S. Geological Survey, Mineral Commodity Summaries, December 2010. USGS.
[11] Oakley, L. C. (1962). US3218124 rocess of producing hydrogen fluoride a s a dry gas from clear fluosilicic acid-containing solutions. Tennessee
Corp.
[12] ResearchInChina. (2010). Fluorspar report annoucement on ResearchInChina Website. ResearchInChina.
[13] Reynolds, M. (2010). Aluminium Fluoride (AlF3) - A market striving towards equilibrium. Aluminium International Today , January,] February.
[14] Weinrotter, F. (1963). Fluoride of aluminium as by-product of superphosphate manufacture. ISMA Technical Conference. Helsinki, Finland, 3-5
September 1963: IFA.
[15] Will, R. (2010). China and the shift in the fluorochemical value chain. Fluorspar 2010.
[16] Zawadzki, B. (1977). US4062930 Method of production of anhydrous hydrogen fluoride.