Profitable uses for Anhydrite from the Production of Hydrofluoric Acid

1 Introduction

The raw materials for producing hydrofluoric acid on an industrial scale are fluorspar and
sulphuric acid. For every ton of hydrofluoric acid yielded by this reaction, about 3.6 tons of
anhydrite is produced. In 1992 for instance, hydrofluoric acid plants produced some 3 to 4
million tons of anhydrite, which corresponds to a few percents of the world production of
CaSO4. 2H2O.

In contrast to the hydrofluoric acid, which was always the primary product, anhydrite was
regarded as a nuisance by-product during the initial decades of hydrofluoric acid produc-
tion. The idea was to get rid of it at the lowest possible cost. Two main methods were em-
ployed, and still are in many countries:
- Dumping on waste tips
- pumping, in slurry form, into lakes, rivers, oceans

As plants grew larger and people started to become aware of ecological problems, disposal
of the anhydrite became increasingly difficult and costly. With this in mind, producers of
hydrofluoric acid began investigating the possibility of using the anhydrite as raw material
for other industries instead of discarding it.

It is now possible to treat the anhydrite, yielded from BCT's hydrofluoric acid plants, to ob-
tain a marketable, competitive product for a number of other uses. As a matter of fact, the
technical requirements for these uses are a good deal easier to meet than those specified,
say, for by-products and waste materials from the phosphate industry.

After the anhydrite leaving the rotary kiln has been neutralised with quicklime, it is ground
to the required fineness. Additional chemical or mechanical treatment is necessary for
some uses. The saleable anhydrite is then shipped in tank cars.

As a result of the steady improvement of the hydrofluoric acid production process, synthetic
anhydrite has now become a sought-after raw material. It is an excellent additive in the
manufacture of cement and is also in high demand for the production of flooring materials
and prefabricated construction elements.

2. Anhydrite from BCT's Hydrofluoric Acid Plants

Natural and synthetic anhydrite have different crystal structures. Unlike the coarse-grained
natural material, the synthetic anhydrite, obtained from the production of hydrofluoric acid,
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consists of very small primary crystals agglomerated so as to form secondary particles

with high specific surface area.

Another important advantage of the synthetic anhydrite obtained from continuously operat-
ing plants, and one that is highly appreciated by users, is its unchanging chemical compo-
sition. The composition of natural anhydrite, on the other hand, differs from one deposit to
another.

The anhydrite leaves the rotary kiln at a temperature of 250° C. Residual sulphuric acid is
then neutralised with lime, after which the anhydrite is crushed.

The crushed anhydrite is pulverised in order to obtain a material that will set. For certain
uses additives are added during the grinding operations, e.g. to accelerate setting.

Properties of the synthetic, neutralised anhydrite:

Appearance: white, slightly beige powder
Density: 2.96 g/cm3
Bulk density after pulverising: 1 .3 kg/l
Melting point: 1450° C
Typical analysis: 97 - 98 % CaSO4
1 - 1 .5 % CaF2
0.5 - 1 .0 % CaO

3 Possible Uses for Synthetic Anhydrite

3.1 General Comments

Synthetic anhydrite is chemically related to gypsum, but unlike gypsum it is anhydrous.

The two substances also differ in crystal structure. Building plaster generally crystallises
out in the form of needles that nest together with large cavities in between, while anhydrite
crystals are cuboidal with large-area contact and few cavities. This produces the high
strength found, for instance in anhydrite flooring.

3.2 Anhydrite as building material for floors and prefabricated elements

Flooring material is produced by mixing pulverised anhydrite containing an accelerator (i.e.

anhydrite binder) with sand in a proportion of about 1: 2.5 by volume and adding water to
obtain a pumpable mix. Piston pumps are used to move the floating on the floors.

More recently applicators have begun producing a more liquid mix from the chemical an-
hydrite. Because the liquid is self-levelling, screeding is eliminated.
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The high volume stability of anhydrite floors makes it possible to lay large areas with no
joints and without any fear of cracks developing. The floors also dry and harden rapidly
(can be walked on after two days) and have high strength, good insulating properties
against heat and sound, a smooth finish, and resistance to attack by oil and solvents.
Anhydrite floors can also be laid using prefabricated tiles. A great deal of laying time and
labour can be saved by casting floor heating tubes into these tiles or applying special sur-
facing materials right at the factory. And, if even better strength properties are desired,
special resins can be added to the mix.

German standards DIN 4208 classifies anhydrite binders in three quality grades with the
designation AB 50, AB 125 and AB 200. The different strength levels specified for the
three grades are determined by grinding fineness and by the type and amount of additives
used.

Minimum strength in kg/cm2

at an age of
7 days 28 days
28 days
Grade desig- Flexural ten- Compressive Flexural ten- Compressive
nation sile strength strength sile strength strength
AB 50 7 (15) 25 (50) 15 (35) 50 (150)
AB 125 15 (30) 65 (150) 25 (50) 125 (250)
AB 200 20 (40) 100 (200) 40 (80) 200 (400)

Only the highest grade, AB 200, is used for flooring. It can be produced without difficulty
from hydrofluoric acid based anhydrite.

3.3 Uses in the cement industry

In contrast to its use as anhydrite binder, synthetic anhydrite is added to cement mainly to
retard the setting of Portland cements and blast slag cements.

Application of synthetic anhydrite in the cement industry:

Purpose
Percentage of CaS04
(referred to raw material
Prior to burn 0.5 - 1 % Alkali binder
Ground into clinker 3 - 8 % setting retarder
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Tests have shown that hydrofluoric acid based anhydrite helps to produce cement of uni-
form quality because its chemical composition is so uniform.

Limestone and clay, the raw material, are reduced to nut size and then subjected to a
grinding / drying operation. Prior to the burn, the raw meal is granulated with anhydrite (to
bind alkalis during the burn). The granules are then burned in a directly fired rotary kiln at
1'450° C to produce clinker. To make the clinker capable of reaction it has to be pulver-
ised.

After 3 - 8 % anhydrite has been added as a setting retarder, pulverisation takes place in
ball mills. The product is high- quality cement.

3.3.1 Action of anhydrite added as alkali binder prior to the burn

The alkalis present in the raw meal (0.5 - 0.6 % Na2O, 0.5 - 2 % K2O) vaporise at a tem-
perature as low as about 800° C. If the vapours condense on coolers, or even worse on
the electrostatic filters, breakdowns and pollution are likely.

SO3 from CaSO4 in the raw meal promotes the formation of relatively non-volatile alkali
sulphates, thus keeping the alkalis in the clinker.
1 ) 2SO2 + O2 2SO3
2 ) SO3 + K2O K2SO4
3 ) SO3 + CaO CaSO4
4 ) SO3 + Na2O Na2SO4

At the same time, water in the kiln gas aids the formation of volatile hydroxides. This helps
to keep the harmful alkalis in the gaseous phase.

This means that the addition of 0.5 - 1 % anhydrite (no water of crystallisation) before the
raw meal is burned makes it possible to reduce the internal concentration of alkalis to the
desired level.

The residual fluorspar content in the anhydrite presents no obstacles to its use as an alkali
binder in the kiln. It has been demonstrated that the fluorspar does not decompose. All of it
leaves the kiln system in solid form, either as CaF2 in the kiln dusts or in the residual
clinker melt.

3.3.2 Action of synthetic anhydrite used as setting retarder

Because fine-ground cement has high specific surface area, it allows the water to start
hydration of the clinker phase without delay.
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If the cement contains no source of sulphate such as anhydrite, extremely rapid hydration
would cause the mix to stiffen too fast and become difficult to work with. The sulphate
added slows down stiffening by reacting with the clinker phase. This reaction starts as
soon as the pulverised anhydrite is dissolved. It produces a complex compound that acts
as a protective layer, thus preventing excessively rapid hydration.

The higher the alumina content or the fineness of the clinker, the higher the alkali content
of the cement, or the higher the mixing temperature, the more sulphate a cement needs.
Anywhere from 3 to 8 % anhydrite is added to the cement during grinding, depending on
the particular conditions.

The residual fluorspar in the anhydrite has no effect on the cement's properties as long as
the cement contains no more than 1 % CaF2. Because only 3 to 8 % anhydrite is added
and it contains no more than 2 % fluorspar, the fluorspar content of the cement is normally
far below 1 %.

3.4 Production of sulphuric acid and cement clinker

All known processes are based on the Müller-Kühne reactions; anhydrite and additives,
that promote the formation of cement clinker, are fired in rotary kilns to produce SO2 gas
and cement clinker. The SO2-laden gases are then processed to yield 98 % sulphuric acid.
When the cement clinker is pulverised and mixed with additional anhydrite, the result is a
high-grade cement.

Although this process is already being used successfully in South Africa, Japan. USA and
some EEC countries, the relatively low capacities prevent it from being an economical
proposition for making use of the anhydrite, produced by hydrofluoric acid plants.

3.5 Other uses for synthetic anhydrite

3.5.1 Agriculture and related uses

Anhydrite is used in agriculture for drying out wet land, gardens, golf courses, etc. This
application has been very successful in the USA

3.5.2 Plastics industry

Synthetic anhydrite is used as a filler in the compounding of plastics.

3.5.3 Plaster from synthetic anhydrite

The properties of synthetic anhydrite also make it a desirable binder for interior plasters.
Synthetic anhydrite has extremely low shrinkage and swelling values. As a result, plasters
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made from it can be applied to large areas in any desired thickness. Because no stresses
are created, no cracks will develop. Besides absence of cracking, plasters made from an-
hydrite have a number of other positive features; high strength, ability to "breath", ease of
handling and application, good frost resistance, high thermal resistance, low consumption
and rapid drying.

The following mixing ratios yield excellent hard plasters from anhydrite:

Mixing ratio (by volume) for various types

Synthetic Sand
anhy-
Lime drite
Single-layer plas-
3 1 12
ter
Undercoat plaster 3 1 12

Final coat plaster 3 2 3

3.5.4 Production of porous bricks

Basically, porous bricks are similar to expanded concrete. They are porous, correspond-
ingly light and will float, but will not soak up water because the pores are closed and can
be worked easily with woodworking tools.

Porous bricks are made by adding an expanding agent to the anhydrite binder that dou-
bles or triples the volume of the mix. Otherwise the production process is identical to that
used for prefabricated flooring tiles.

Porous bricks are used primarily for insulation purposes.

3.5.5 Hydration of synthetic anhydrite

Synthetic anhydrite can be hydrated with water to form hemihydrate or dihydrate. This
process is used today in countries like Japan that have no deposits of hemi- or dihydrates
worth exploiting.

Either hemihydrate or dihydrate can be produced, depending on the particular application,

by adding the necessary stoichiometric quantity of water.

Hemihydrate can also be obtained by reacting appropriate quantities of anhydrite and wa-
ter-dispensing dihydrate with each other.
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There are two different hydration processes. One employs elevated temperatures (in the
order of 100° C) and normal pressure. With this process, it is possible to hydrate the hy-
drofluoric acid based anhydrite just as it comes out of the rotary kiln and convert it to
granulate form. The anhydrite leaving the kiln at a temperature of 300° C is sprayed with
the hydration water, which quickly cools it to 100° C as part of the water evaporates.

The other possibility is to hydrate at ambient temperature. In this case the moistened an-
hydrite is subjected to a pressure of 300 bar for several hours.