ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 6, pp. 893 ! 895.

+ Pleiades Publishing, Inc., 2006.

Original Russian Text + E.M. Shvarts, R.G. Belousova, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 6, pp. 905!907.

INORGANIC SYNTHESIS
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
AND INDUSTRIAL INORGANIC CHEMISTRY

Synthesis of Zinc and Copper Borates

in a Single Technological Cycle
E. M. Shvarts and R. G. Belousova
Institute of Inorganic Chemistry, Riga Technical University, Salaspils, Latvia

Received December 21, 2005

-
. . .
Abstract A zero-waste technology was developed for obtaining in a single technological cycle four valuable

. . . [ ]
products: combustion retarder Zn3B10O18 14H2O, microfertilizer 2ZnO 3B2O3 7H2O, copper borate
3CuO 2B2O3 nH2O mNa2SO4, and wood antiseptic Mebor.
DOI: 10.1134/S107042720606005X

Many zinc borates are known. Among them are the low yield. The authors of [5] developed a method
various hydrates 2ZnO . 3B2O3 . nH2O (n 7.5, 7, 5, for synthesizing zinc borate Zn3 . B10O18 . 14H2O
4, 3.233.7) [1]. Most of them are obtained from zinc in a 80 3 94% yield.
sulfate, sodium tetraborate, zinc carbonate, zinc oxide
As for copper borates, their amorphous {2CuO .
or hydroxide, and boric acid under various condi-
B2O3 . H2O and 3CuO . 2B2O3 . nH2O (n 1, 2, 4, 5)
tions. The hydrate containing 3.233.7 molecules of
[6]}, crystalline {bandylite CuB(OH)4Cl [7] and
crystallization water, obtained from zinc chloride,
henmilite [Ca2Cu(OH)4B(OH)4]2 [8]} minerals, and
sodium tetraborate, and sodium hydroxide on heating
synthetic borates {Na6Cu2[B16O24(OH)10] . 12H2O
[2], is the most important. Zinc borate 2ZnO . 3B2O3 .
[9], K5HCu4O[B20O32(OH)8] . 32H2O [10], and
(3.233.7)H2O is widely used under the brand name
Cu(NH3)4B4O7 . 6H2O [11]} are known.
[Firebrake] as a synergetic additive to halogen-con-

taining antipyrenes and antimony oxides to protect
polyvinyl chloride, polyesters, polyolefines, and rigid
polyurethanes against fire.
In 1993, zinc borates, 4ZnO . B2O3 . H2O and
4ZnO . B2O3, were obtained by the reaction of zinc
oxide or its corresponding salt with boric acid or with
its salts in water at high temperature. It was also sug-
gested to use these borates as fire retarding and smoke
suppressing additives to organic polymers [3]. Also,
a borate Zn3 . B10O18 . 14H2O (3-5-14) is known.
It was first synthesized by Putnin’ and Jevin’sh [4]
but failed to find application in industry because of
ÄÄÄÄÄÄÄÄÄÄ
Synthesis of Zn3 . B10O18 . 14H2O yields a mother
liquor containing (g l!1): B(III) ~10 and Zn(II) 4.22.
The goal of our study was to develop methods that
involve utilization of the forming wastewater. We
achieved this by developing a zero-waste cycle that
simultaneously yielded four valuable products: Zn3 .
B10O18 . 14H2O ([Pyroteran]), dizinc hexaborate hep-
tahydrate 2ZnO . 3B2O3 . 7H2O (2-3-7) (BZn), cop-
per borate 3CuO . 2B2O3 . nH2O . mNa2SO4 (BCu),
and wood antiseptic [Mebor.] An example of a zero-
waste cycle for joint synthesis of 3-5-14, 2-3-7 zinc
borates and copper borate is presented in the scheme.

Scheme for synthesis of zinc and copper borates in a single cycle.

893
894 SHVARTS, BELOUSOVA

Results of analyses of zinc and copper borates

ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ ³ Composition, wt % ³ X-ray diffraction patterns
Main
³ ÃÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄ
A
Borate
components
³ ³ found ³ calculated ³ D, ³ Intensity, %
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄ
. .
3ZnO 5B2O3 14H2O ³ ZnO ³ 29.30 ³ 29.91 ³ 9.591 ³ 100
³ B2O3 ³ 40.82 ³ 41.21 ³ 6.689 ³ 100
³ ³ ³ ³ ³
. .
H2O 30.58 29.88 2.935 80
2ZnO 3B2O3 7H2O ³ ZnO ³ 32.66 ³ 32.70 ³ 6.79 ³ 100
³ B2O3 ³ 41.60 ³ 41.98 ³ 3.36 ³ 80
³ ³ ³ ³ ³
. . .
H2O 25.65 25.35 3.02 80
3CuO 2B2O3 nH2O mNa2SO4 ³ CuO ³ 39.90 ³ ³ ³
³ B2O3 ³ 26.60 ³ ³ ³
³ Na2SO4 ³ 10.30 ³ ³ ³
³ H2O ³ 21.30 ³ ³ ³
³ ZnO ³ 2.50 ³ ³ ³
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄ

The 3-5-14 zinc borate was obtained by reacting
zinc sulfate solutions and a solution containing borax
and boric acid under heating, with stirring of the re-
action mixture and isolation of a crystalline 3-5-14
zinc borate from mother liquor no. 1 by filtration.
Mother liquor no. 1 was used to obtain a 2-3-7 zinc
borate. To mother liquor no. 1 we added calculated
amounts of borax and zinc sulfate (both dry). After
the reaction mixture was heated and stirred, crystalline
zinc borate was filtered off. The remaining mother
liquor no. 2 was used to synthesize copper borate.
Copper borate was obtained by addition of cal-
culated amounts of copper sulfate and sodium hydrox-
ide. Mother liquor no. 3, obtained upon separation
of copper borate, corresponds in composition to
the known wood preservative [Mebor.]
The 3-5-14 zinc borate can be used as nontoxic
fire-retarding additive to lacquers, paints, and polymer
materials, and as a constituent of fireproofing formula-
tions for impregnation of wood. It is effective even in
the absence of antimony halides and oxides [12].
The 2-3-7 zinc borate and copper borate can be used
as microfertilizers for a presowing seed treatment of
vegetables, flax, sugar beet, and other cultures [13].
EXPERIMENTAL
Trizinc decaborate tetradecahydrate Zn3 . B10O18 .
14H2O. Borax Na2B4O7 . 10H2O (38.1 g) and boric
acid (61.8 g) were dissolved in 800 ml of distilled
water, and zinc sulfate ZnSO4 . 7H2O (28.8 g), in
200 ml. Both solutions were poured into a 2-l flask
and heated to 30 3 40oC under mechanical agitation to
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
complete crystallization of amorphous precipitate
(~6 h).
The crystalline precipitate was filtered off, washed
with 100 ml of warm water, and dried in air to give
26.5 g of 3-5-14 zinc borate (in 94% yield), iden-
tified by X-ray analysis. This is a white crystalline
substance in the form of very fine needles. The results
of the analysis are listed in the table.
Dizinc hexaborate heptahydrate Zn2 . B6O11 .
7H2O. After separation of 3-5-14 zinc borate, mother
liquor no. 1 contains 4.22 g l!1 Zn(II) and 10.03 g l!1
B(III). The mother liquor was heated in a 2-l round-
bottomed flask to 50 360oC, and then 39.45 g zinc
sulfate was dissolved in it. After that, 78.48 g of
borax was added and agitation was continued until
an amorphous precipitate was formed. The precip-
itate crystallized in 4 h under heating and stirring.
The crystals were filtered off, washed with warm
water (50 ml), and dried in air. The 2-3-7 zinc borate
(49.28 g) was obtained in 96% yield, identified by
chemical analysis (see table).
Copper borate. Mother liquor no. 2, containing
Zn(II) (2.27 g l!1) and B(III) (11.62 g l!1), was used to
obtain copper borate. Copper sulfate CuSO4 . 5H2O
(88.73 g) was dissolved in 140 ml of distilled water
under heating, and 42 g of NaOH was dissolved in
72 ml of distilled water. A copper sulfate solution
was added to mother liquor no. 2, placed in a 2-l
round-bottomed flask and agitated with a mechanical
stirrer. A NaOH solution was added in small portions
under agitation, the temperature was raised to 80oC,
and the solution was stirred for 4 h. The resulting
Vol. 79 No. 6 2006
 SYNTHESIS OF ZINC AND COPPER BORATES IN A SINGLE TECHNOLOGICAL CYCLE 895

blue precipitate was filtered off from a hot solution,
washed with 100 ml of warm 1% boric acid, and dried
in air to give the product (75.6 g) in 96.5% yield.
The composition of the product is listed in the table.
Copper borate is a blue finely dispersed amorphous
powder with admixture of sodium sulfate, whose con-
tent depends on its concentration in mother liquor
no. 2. The product has the formula 3CuO . 2B2O3 .
nH2O . mNa2SO4. In this case, the ZnO content can
be disregarded. The product is insoluble in water.
fertilizers for presowing seed treatment of vegetable
cultures and flax.
REFERENCES
1. Supplement to Mellor’s Comprehensive Treatise on
3
Inorganic and Theoretical Chemistry, New York:
Longman, 1980, vol. 5, part A, pp. 577 578.
2. US Patent 100 526.
3. PCT Int. Appl. WIPO Pat. 9 310 045.
4. Putnin’, Ya.K. and Ievin’sh, A.F., Nauch. Trudy

3
Precipitation of zinc and copper borates in a com- Len. Gos. Univ., 1958, Ser. 22, Khim. Facul’t., VI,
mon process yields mother liquor no. 3. It contains pp. 69 71.
(wt %): 0.002 CuO, 1.77 B2O3, and 5.75 Na2SO4 and 5. LV Patent 10 101.

3
can be used as a preservative for plywood and lumber. 6. Boiko, B.F., Khimiya boratov (Borate Chemistry),
Riga: Akad. Nauk Latv. SSR, 1953, pp. 105 115.

3
CONCLUSIONS 7. Palache, Ch. and Fostag, W.T., Am. Mineral., 1938,
vol. 23, no. 2, pp. 85 90.

3
(1) Zinc and copper borates, 3ZnO . 5B2O3 . 14H2O, 8. Nokai, J., Okada, H., and Masutomi, K., Am. Mineral.,
2ZnO . 3B2O3 . 7H2O, and 3CuO . 2B2O3 . nH2O . 1986, vol. 11, nos. 9/10, pp. 1234 1238.

3
mNa2SO4, were obtained by the reaction of the cor- 9. Behm, H., Acta Crystallogr., 1983, vol. 39, no. 1,
responding sulfates and borax in the presence of boric pp. 20 22.

acid or sodium hydroxide in a single technological
cycle.
(2) The mother liquors obtained, which are satu-
rated solutions of boric acid, are used for further
synthesis of zinc borates.
(3) The borates obtained can be used as a fire-re-
tarding and smoke-suppressing additives and a micro-
3
10. Heller, G., Z. Naturforsch., 1985, vol. 406, no. 4,
pp. 462 466.
11. Adams, R.M., Boron, Metallo-Boron Compounds and
Borates, New York: Wiley, 1964.
3
12. Shvarts, E.M. and Belousova, R.G., Latv. Kimijas
Zurnals, 2002, no. 3, pp. 271 275.
3
13. Stramkale, V., Kondratovics, U., Vikmane, M., et al.,
Proc. in Agronomy, 2000, no. 2, pp. 61 65.

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