Metallurgist, Vol. 52, Nos.

11–12, 2008

PRODUCTION AND USAGE OF POWDERED

ALKALI METAL SILICATE HYDRATES

A. S. Brykov and V. I. Korneev UDC 661.8:537.868

We discuss general issues relating to production and usage of soluble powdered hydrated alkali metal
silicates, which are widely used as binding and alkalinizing agents in various areas of modern industry.
Key words: hydrosilicate powders, use of hydrated silicate powders, silicate module, liquid glass, spray drying.

As is well known, alkali metal (sodium and potassium) silicates are widely used in the production of various struc-
tural and composite materials, as well as detergents, dyes, and glues [1]. Sodium liquid glass – an aqueous solution of sodium
silicates with various degrees of polymerization and with SiO2-to-Na2O molar ratios (moduli) of 1 to –4 – is more frequent-
ly used domestically. The widespread use of liquid sodium glass is explained by ease of production and the low cost and
accessibility of the raw material. Potassium liquid glasses are much more rarely used (in the production of silicate dyes
and finishing materials) than sodium liquid glasses.
Sodium liquid glass is produced by dissolving anhydrous alkali silicate (bulk silicate produced by alloying silica
with sodium carbonate or sodium sulfate) in an autoclave. Use of bulk silicate in various composite materials is limited due
to the low dissolution rate of bulk silicate in water [2].
Sodium silicates are also domestically produced in the form of crystalline sodium metasilicate hydrates. For exam-
ple, sodium metasilicate nonahydrate (general formula Na2O·SiO2·9H2O) is produced in Russia by crystallization from low-
modulus aqueous silicate solutions. Nonahydrate metasilicate has a low melting point, which makes it difficult to transport
and store. It is primarily used in detergent production.
Unlike low-modulus silicates, silicates with modulus greater than 1 are unable to crystallize out of their own solu-
tions. In other countries, higher-modulus solid silicate hydrates are produced by drying solutions of the corresponding silicates
in spray towers to a final hydrate content of 10–20% [1]. This process leads to amorphous powders (hereinafter referred to
as hydrosilicate powders or HSPs).
Thus, modern HSP production processes call for dissolution of bulk silicate in an autoclave, with the resultant solu-
tion (liquid glass) being dried to the desired final moisture content in a tower.
Several other processes for production of amorphous alkali silicate hydrates with modulus greater than 1 are also
described in the literature – steam hydration of ground bulk silicate [3], salt fractionation of hydrated silicate forms from
aqueous solutions of univalent metals in water-miscible organic solvents [4], and drying of aqueous solutions of alkali sili-
cates in a suspended layer of inert bodies [5]. A process for microwave drying of liquid glass has recently been patented [6].
Not all foreign manufacturers of liquid glass also produce solid silicate hydrates. There is a European HSP manu-
facturer, Akzo-PQ Silica VOF (Netherlands), which produces sodium silicate hydrates in powdered or granule form under
the trade name Britesil. This firm produces a very broad range of powders, e.g., Britesil H20 (powder with modulus 2),
HS265 (modulus 2.65), HS330 (modulus 3.3). These powders have hydrate moisture contents of 16–20%, and a very narrow
particle size distribution. Eighty percent of the particles in the powders have sizes between 63 μm and 250 μm, with no pow-
der fraction. Both the granules and the powder are highly porous and have good mechanical strength which enables the HSP

St. Petersburg State Technological Institute, 26 Moskovskii Prospekt, 190013 St. Petersburg, Russia. Translated
from Metallurg, No. 11, pp. 82–85, November, 2008. Original article submitted October 29, 2008.

648 0026-0894/08/1112-0648 ©2008 Springer Science+Business Media, Inc.

TABLE 1. Physical and Chemical Characteristics of Monasil Brand Sodium Silicate Hydrates Produced by the Volkhov
Chemical Plant

Statistic Standard values

Powder grade H22 H28

External appearance White granulated powder
SiO2 mass % 53–58 52–64
Na2O mass % 24–29 20–24
Silicate modulus 1.9–2.5 2.5–3.1
Losses during calcination, mass % 13–23 12–28
Dissolution time, min 2–15 5–30

to maintain its particle size distribution during transportation and storage. The high rate of dissolution in water for these HSPs
is particularly noteworthy.
Sodium HSPs manufactured by Henkel KGaA (Germany) are known under the trade name Portil. The American
firm PQ (Philadelphia Quartz), the Czech firm Silchem (trade name Susil), the Indian firm Navtara & Company (trade name
Portex), and several others also produce hydrosilicate powders.
In Russia, the Volkhov Chemical Plant (Leningrad Oblast) has been producing silicate hydrates under the trade name
Monasil since 2004 [7]. The specifications for Monasil powders are listed in the table below.
Spray drying does not have a substantial impact on the polymer composition of the silicate solution. Like the initial
liquid glass, the solid silicate hydrates contain anions consisting of one or more silicon/oxygen tetrahedrons bound by an oxy-
gen bridge. The alkali cations electrostatically bound to the anions are surrounded by hydrate shells consisting of water
molecules. This weakens the bonds between the alkali cations and the anion framework, generally making the silicate hydrate
highly soluble. Some of the sodium ions substitute for protons, which makes the silicate structure loose. The colloidal silica
particles in the system and the anhydrous solution form a vitreous mass that retains the structure of the solution [1, 8].
The dissolution of sodium silicate hydrates in water has been studied in detail and described in [3, 9].
Long-term practical experience in various foreign countries indicates that amorphous solid silicates of alkali metals
(primarily sodium) with moduli between 1 and –3.5 are indispensable in many promising industrial applications. Unlike bulk
silicate, HSP has a fairly high dissolution rate in water, even at ordinary temperatures, and aqueous HSP solutions have bind-
ing qualities similar to those of liquid glass.
In many foreign countries, HSPs are widely used in the production of various materials (see Fig. 1), and a relatively
small assortment of powders with various moduli is capable of meeting an extremely wide variety of requirements.
Most construction materials and composites have optimum properties that can be achieved using sodium HSPs with
moduli of 2–3.5, since this range corresponds to the optimum combination of binding properties and resistance to water and
chemical corrosion.
In recent years, dry composites containing all required ingredients and ready for use have come to be more impor-
tant domestically. The ease with which such composites can be used (all that is required is mixing with water) makes them
very attractive for users. For this reason, HSPs may be of interest to Russian manufacturers of structural dry mixes, detergent
powders, and drilling fluid concentrates.
The shipping costs for HSPs and for dry mixtures based on HSPs are much lower than those for shipment of liquid
glass; in addition, delivery of the latter to the northern portion of the country, where significant quantities of liquid glass are
used for drilling oil and gas wells, is somewhat of a problem.
If necessary, HSPs can easily be used to prepare liquid glass of the desired modulus and concentration immediately
at the site of use. Silicate hydrates are used as accelerant admixtures in cement compounds to significantly increase concrete

649
 Production Production
of dry building of detergents Water
paints and cleaners treatment

Production
Production
of dry compounds
of dry concentrates
Sodium and potassium hydroaluminosilicates for fabrication of
for preparation of
acid-resistant and
drilling muds
refractory materials

Production Preparation Admixture for Preparation

of welding of structural concrete mixes of liquid glass
electrodes sealants and shotcrete

Fig. 1. Applications of granulated alkali metal silicate hydrates.

setting speeds [10]. Moreover, the alkaline silicates react with the Ca(OH)2 formed during hydration of the clinker minerals
and convert it into calcium silicate hydrate, thereby providing a noticeable reduction in porosity and permeability of the set
cement, and improving its surface wear resistance. In significant amounts, alkali silicate admixtures will reduce the final
strength of the set cement; however, some data indicate that the strength of the set cement during the early phases of the hard-
ening process is somewhat higher than that of control samples [11].
HSPs are recommended for use as a cement admixture for burial of toxic waste and radwaste in a cement
matrix [11]. In this case, the silicates not only accelerate setting and acquisition of strength during the early phase, but also,
most importantly, reduce the mobility and leachability of hazardous materials from the cement matrix, preventing them from
entering the groundwater. Thus, the highly alkaline conditions created by HSP cause most heavy-metal ions to precipitate out
in the form of insoluble hydroxides.
Acid-resistant cements find use as binders for application of individual chemically resistant materials for protecting
the housings of chemical apparatus, as well as for preparation of acid-resistant mortars and concretes capable of resisting
most mineral and organic acids [1].
Acid-resistant quartz silicon fluoride cement, which is a mixture of finely ground quartz sand and sodium hexafluo-
rosilicate, has come into widespread practical use. Acid-resistant set cement is obtained by dissolving this mixture into liquid
glass [12].
The cement mortar hardens and is converted into acid-resistant set cement when the alkali silicate reacts with the
sodium hexafluorosilicate.
Powdered sodium or potassium hydrate can be used to enable production of dry acid-resistant compounds that are
ready for use upon mixing with water [13, 14]. The strength and acid resistance of the resulting set cement is no worse than
that of standard acid-resistant cement dissolved in liquid glass.
Like liquid glass, HSP is also used as a binder in heat-resistant cements, which also include refractory fillers and a
hardener [15]. Sodium fluorosilicate is generally used as a hardener, while various refractory minerals are used as fillers.
Dry acid-resistant and refractory compounds based on HSPs are useful for shotcrete lining of various process sur-
faces. This involves accelerating a dry composite in a shotcrete system nozzle, where the dry composite is mixed with water
and compressed air is used to discharge the mixture onto the surface being treated [13, 15].
In the traditional processes for preparation of various mortars, glues, and compounds, the dry ingredients are mixed
with liquid glass, which is a dense, viscous liquid, and this causes certain practical difficulties: for example, it is difficult to
obtain the homogeneous mixture required in order to obtain a final product of acceptable quality. In this respect, use of HSPs
may turn out to provide improved manufacturability.
It should nevertheless be remembered that replacement of liquid glass with powder will require detailed process
engineering and will turn out to be impossible in many cases. This is especially true in those cases where liquid glass is used

650
as a precipitating or coagulating agent. However, HSPs can always be used within the framework of the initial process, i.e.,
initially prepare the liquid glass from powder, and then use it as before.
The foreign and domestic oil industries have each developed a broad spectrum of effective and environmentally safe
alkali-silicate-based (liquid glass and bulk silicate) drilling fluids and drilling fluid reagents [16]. Drilling fluids are used for
lubrication of drill bits during oil production, for removal of drill cuttings, and for borehole conditioning.
Attempts are currently under way to produce dry drilling-fluid concentrates using liquid glass or ground bulk sili-
cate. In the first case, a mixture of solid ingredients (e.g., sapropel) and liquid glass is dried, and the resulting solid material
is ground up (or molded into briquettes) [17]. In the latter case, the resulting concentrates are only suitable for use in hot,
high-pressure boreholes where the bulk silicate can dissolve rapidly.
Studies performed at ATEKO and NIO Burenie companies and the Gubkin Russian State University of Oil and Gas
HSPs enable drilling concentrates to be produced in dry composite form convenient for shipment and readily soluble at the
usage site or in the well itself (either a hot or a cold well) [18].
In foreign countries, HSPs are widely used in the production of dry detergents and cleaners (both household prod-
ucts and industrial products) due to their high dissolution rate and the fact that they produce an alkaline environment in the
detergent solution (as is required for removal of oil, fat, and protein stains). Moreover, silicate anions inhibit corrosion of
metal surfaces and act as a water softener.
The widespread use of HSPs for this purpose is due to the fact that modern foreign technology for dry detergent pro-
duction enables the manufacturer to maximize the effective use of dry ingredients [19].
Akzo-PQ recommends that such dry mixtures have HSP concentrations of 10–20%. In addition to HSPs, such com-
pounds may also contain surfactants, alkalinizing agents, enzymes, stabilizers, fillers, etc.

REFERENCES

1. V. I. Korneev and V. V. Danilov, Soluble and Liquid Glass [in Russian], Stroiizdat, St. Petersburg (1996).
2. B. D. Toturbiev, Construction Materials Based on Sodium Silicate Composites [in Russian], Stroiizdat, Moscow
(1988).
3. P. N. Grigor’ev and M. A. Matveev, Soluble Glass [in Russian], Promstroyizdat, Moscow (1956).
4. R. Iler, The Chemistry of Silica, Wiley, New York (1965) [Russian translation: Mir, Moscow (1982), 416 pp.].
5. Patent 1680625 SU, C 04 B 33/32, Method for Production of Alkali Silicate Hydrate Powders, published September
30, 1991.
6. Patent 2134247 RU, C 04 B 12/04, C 01 B 33/32, Method for Production of Sodium or Potassium Silicate Hydrate
Powders, published August 10, 1999.
7. A. S. Brykov, V. V. Shapsikov, and T. V. Artem’ev, “Sodium silicate hydrate: A new product from OOO Vitakhim
and the Volkhov Chemical Plant,” Constr. Mater., No. 3, pp. 45–47 (2006).
8. L. S. Dent Glasser and C. K. Lee, J. Appl. Chem. Biotechnol, 21, 127–133 (1971).
9. V. I. Korneev, V. V. Danilov, A. Yu. Silin, and A. P. Sizonenko, Zh. Prikl. Khim., 61, No. 4, 831–835 (1990).
10. Patent 4402749 US, C 04 B 007/35, Cementitious Composition with Early High Strength Development and Methods
for Controlling Setting Rate, published September 9, 1983.
11. J. Larosa-Tompson, P. Gill, B. E. Scheetz, and M. R. Silsbee, Proc. 10th Int. Congr. on the Chemistry of Cement,
Gothenburg, 1997, Vol. 3.3.
12. M. I. Subbotkin and Yu. S. Kuritsyna, in: Acid-Resistant Concrete and Mortar Based on Liquid Glass (M. A. Mat-
veev, ed.), Stroiizdat, Moscow (1967).
13. Patent 4227932 US, C 04 B 10/4, Single Component Potassium Silicate Cement for Dry Gunning, published October
14, 1980.
14. E. Yu. Aleshunina, A. S. Brykov, V. V. Danilov, and V. I. Korneev, “Acid-proof formulation based on hydrated sodium
silicate powder,” Zh. Prikl. Khim., 73, No. 10, 1612–1615 (2000).

651
15. Patent 4780142 US, C 04 B 012/04, Hard Setting Refractory Composition, published October 25, 1988.
16. Patent 1792420 SU, C 09 K 7/02, Reagent for Treatment of Water-Based Drilling Fluid and a Production Method
for Said Reagent, published January 30, 1993.
17. Patent 2051944 RU, C 09 K 7/00, Method for Production of Drilling Concentrate, published January 10, 1996.
18. A. S. Brykov and V. I. Korneev, “Sodium silicate hydrate powders in oil and gas production,” in: Abstr. of Papers
from the Appl. Scie. Conf. on Chemistry for the Russian Fuel and Energy Complex [in Russian], St. Petersburg, p. 80
(2000).
19. Z. I. Bukhshtab, A. P. Mel’nik, and V. M. Kovalev, Technology of Synthetic Detergents [in Russian], Legpromizdat,
Moscow (1988).

652