Polish Journal of Chemical Technology, 10, 3, 13 — 20,

Pol.2008,
J. Chem.
10.2478/v10026-008-0030-6
Tech., Vol. 10, No. 3, 2008 13

Manufacturing of phosphoric acid from hydroxyapatite, contained in the

ashes of the incinerated meat-bone wastes
Kinga Krupa-¯uczek, Zygmunt Kowalski, Zbigniew Wzorek
Cracow University of Technology; Institute of Chemistry and Inorganic Technology, ul. Warszawska 24, 31-155 Kraków,
Poland, e-mail: [email protected]

The results of the investigations concerning phosphoric acid manufacturing, by the extraction method, from
the ashes containing hydroxyapatite, obtained through the thermal treatment of bone sludge have been
presented. The incinerated bone sludge with ~16% P content and the minimal amount of impurities can
be an alternative source for phosphoric acid production. The process consists in two stages. In the 1st stage,
reaction of hydroxyapatite with phosphoric acid resulting in monocalcium phosphate formation in the
solution obtained is carried out. The tests revealed that overall hydroxyapatite dissolution in phosphoric acid
takes place when the concentration is 37% H3PO4. In the 2nd stage monocalcium phosphate is converted into
calcium sulphate using concentrated sulphuric acid at the recommended temperature of 95°C. The prin-
ciples of the technological idea of the process of phosphoric acid manufacturing from HA-containing ashes,
obtained by bone wastes incineration, as well as a preliminary economic analysis for the production of
10 000 t/year of food-grade phosphoric acid have been developed.

Keywords: meat waste, hydroxyapatite, phosphoric acid.

INTRODUCTION lysate” and bone sludge. Chemical composition of sludge,

obtained from different sorts of bone, does not differ much
About 18mln t/year of meat wastes, containing phospho-
(Table 1)5.
rus compound, are generated by the meat industry in the
European Union countries. That sort of waste can be an Table 1. Chemical composition of bone sludge
alternative source of phosphorus, while the amount of natu-
ral phosphate rock is in continuous depletion1 – 5. According
to the „cleaner technology” rules, more considerations has
been given to the substitution of natural raw materials for
wastes and for preventing the waste release in the environ-
ment1, 2.
Practical processing of meat industry wastes is regulated The phosphorus content (~ 14 %) is at the level of that
by the European Union law5, 6. According to the law, the in phosphate rocks. The tested bone sludge (a mixture
wastes are divided into categories depending on the risk of 1 : 1 : 1 by weight), composed of pig legs, pig bones and ox
infectious disease. The wastes such as meat-bone crushes and bones contained pieces from a few to dozens cm in large.
all kind of animal parts that may generate potential risk of The composition (wt.%) of the sludge was: H2O ~ 7.0;
CJD disease belong to the 1st category of high risk5, 6. organic matter ~ 16.1 (in wet mass), ~ 17.3 (in dry);
The only possible method, enabling neutralisation of these fat = 3.0; protein = 14.3; phosphorus P ~ 13.1 (in wet
wastes, is thermal treatment at temperatures higher than mass), ~ 14.1 (in dry); CaO ~ 35.7 (in wet mass), 38.4 (in
850°C. The wastes of the 2nd category are by-products de- dry)5. The combustion energy determined using the calorim-
rived from animals (droppings, enteron content), sludge from eter KL-12Mn (Precyzja-Bit Company) was 7.9 MJ/kg (in
slaughterhouse sewage utilisation, and animal products con- comparison, the heat of coal combustion is 20.66MJ/kg)5, 11.
taining veterinarian medicines. The wastes of this category The X-ray diffraction analysis (XRD) of the sludge was
have to be utilised in incinerating plants, too. Bone sludge performed with the Philips X'Pert diffractometer equipped
(protein-free and fat-free bones) – skin, hoofs, horns, pigs with the graphite monochromator PW 1752/00 and anode
bristle, feathers, blood recovered from other than ruminant copper. The result obtained revealed that hydroxyapatite,
animals, parts of the animals suitable for consumption, and (HA), was the only crystalline phase in bone sludge (Figure
those, though discarded by the people, estimated as no caus- 1). The thermogravimetric analysis in air, (TGA), using the
ing danger of a disease transfer from animal to human being simultaneously recorded DTA-DTG system SDT 2960 TA
belong to the 3rd category of wastes. They can be utilised Instruments, presented in Figure 2, demonstrates three steps
thermally or processed into biogas or compost. of bone sludge decomposition, while the temperature is in-
In the paper, the results concerning the extraction of phos- creasing. The combustion of the organic matter is performed
phoric acid from the ashes obtained by thermal processing up to ~ 600°C. The fourth endothermic effect around 800°C
of bone sludge have been presented. is likely to be associated with CaCO3 decomposition.
The bone sludge was incinerated in a stationary chamber
oven at 600 and 950°C for 3 hours in air atmosphere5, 12.
EXPERIMENTAL PART
Phosphorus and calcium concentration, in the ashes ob-
Bone tissue, beside the meat tissue, is the main constituent tained, were analysed according to standards10, 13. The chemi-
of the wastes generated by slaughterhouses5, 7. The bones, cal composition of the ashes is summarised in Table 2. The
after initial preparation, removing metallic pieces, and crush- XRD patterns of the ashes, presented in Figure 4, indicate
ing, are subjected to hydrolysis8, 9, yielding „protein hydro- that hydroxyapatite is the only crystalline phase in the ashes.
14 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008

Figure 1. X-ray diffraction pattern, (XRD), of bone sludge Figure 3. XRD of the ash obtained through bone sludge
incineration in the stationary chamber oven at
950°C

Figure 2. DTA-DTG curves of bone sludge TGA analysis in the air

The morphology of the ashes obtained was investigated by Table 2. Chemical composition of the ashes obtained by
the scanning electron microscopy method (SEM), using the incineration of bone sludge in the stationary cham-
S-4700 Hitachi, equipped with the EDS analyzer5. It has ber oven at temperatures of 600°C and 950°C5
been found (Figure 4) that the ash resulted from bone sludge
incineration at the temperature of 950°C in the stationary
chamber oven in air atmosphere is of homogeneous struc-
ture. The oval-shaped grains of the crystallites of about 0.5
– 1.0 μm large can be seen in the picture. The absence of
agglomerates indicates the lack of agglutination. The white
shades, shown in the picture, may indicate the melted areas rity and lack of heavy metals, facilitates its processing when
of the sample resulted from overheating. That may indicate it is used as a source of phosphorus5, 12. The incinerated
that the incineration temperature was too high. bone sludge can be used for food-grade phosphoric acid
The tests on incineration indicated that the ash obtained production.
was almost pure hydroxyapatite. The homogenous chemical
composition and the chemical properties, especially its pu-
 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008 15

PHOSPHORIC ACID MANUFACTURING

Phosphoric acid was obtained by the extraction of H3PO4 from
hydroxyapatite with the concentrated sulphuric acid14 – 16.
2Ca5(PO4)3OH +10H2SO4 + 18H2O =
6 H3PO4 + 10 CaSO4 · 2H2O (1)
The process was carried out in two stages. In the 1st stage
hydroxyapatite was treated with phosphoric acid to obtain a
solution of monocalcium phosphate Ca(H2PO4)2. In the 2nd
stage calcium sulphate was precipitated using sulphuric acid5, 16.
The goal the first part of the investigations was to determine
the amount of phosphoric acid sufficient for the total disso-
lution of the hydroxyapatite at 75°C. The reaction was car-
ried out for 4h in a glass reactor equipped with the heating
jacket, reflux condenser, and a mechanical stirrer5. The re-
Figure 4. Microphotograph of the surface of the ash, ob- sults are shown in Table 3.
tained by bone sludge incineration at 950°C in the Table 3 demonstrates that the lowest phosphoric acid
air concentration sufficient for the total dissolution of
Ca5(PO4)3OH is 27.5% H3PO4, and that does not depend
on the ratio of Ca5(PO4)3OH /H3PO4. However, while the

Table 3. Results on hydroxyapatite dissolution in phosphoric acid of different H3PO4 concentration

16 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008

clear solution obtained was left to stay, after a few hours tite dissolution in phosphoric acid a set of experiments was
secondary hydroxyapatite started to precipitate. A similar carried out according to the second order rotatable design in
effect was observed when phosphoric acid, containing 30% three factors Z1, Z2, Z3 (Tables 5 and 6). The choice of the
H3PO4, was used. Further dissolution was carried out for 2 limiting concentrations of H3PO4 for the experiment was
and 4h at 75°C, while the weight ratio of the solid/liquid was based on phase diagram of H2O – P2O5 – CaO 14, so that
1/15, 1/11 and the concentration of the acid was 10; 20; 25; calcium sulphate was hydrated to the solid phase of the final
27.5; and 30 % H3PO4 (Table 4). In the case of the 2-hour product.
reaction with 10% H3PO4, the dissolution of Ca5(PO4)3OH The tests on hydroxyapatite dissolution in phosphoric acid
was not completed. Also, the concentration of 20 and 25% at different concentrations revealed that overall dissolution,
H3PO4 was not sufficient for the total hydroxyapatite disso- without secondary precipitation, takes place only when the
lution, additionally, the system reached some rate of over- acid concentration was 37% H3PO4. In the acid of 24%
saturation and a secondary precipitate of CaHPO4.2H2O H3PO4 the hydroxyapatite was dissolving incongruently. In
was formed5. Total hydroxyapatite dissolution was achieved the acid of 50 and 59% of H3PO4 the secondary precipitate
in the acid of 27.5% H3PO4 within 17 minutes. was formed.
Table 4 demonstrates that time is not significant for the The aim of the second stage of the experiments was to
hydroxyapatite dissolution under the investigated conditions. determine the most preferable for calcium sulphate precipi-
To evaluate the optimal parameters (concentration, tem- tation conditions. In the experiment, the concentration of
perature, weight ratio of liquid/solid phases) of hydroxyapa- phosphoric acid, (37% H3PO4) was maintained constant,
while the temperature and sulphuric acid concentrations were
Table 4. The rate of hydroxyapatite dissolution in phos-
phoric acid obtained for the lowest (1 : 11) and
variable parameters. First, hydroxyapatite was dissolved in
highest (1 : 15) ratio of the solid/liquid phase. phosphoric acid (37% H3PO4) solution at the temperatures
Dissolution time 2 hours [°C] of 75, 80, 85, 90, 95. The molar ratio of Ca5(PO4)3OH
to H3PO4 was 1 : 47.4 ( by weight, 8g : 100g). Afterwards,
calcium sulphate precipitation from the obtained solution
was carried out by sulphuric acid (concentration: 15 – 60%
H2SO4) addition. The amount of H2SO4, taken for the pre-
cipitation, was equivalent to the amount of calcium intro-
duced with Ca5(PO4)3OH. The introduction of H2SO4 into
the solution, containing Ca(H2PO4)2, resulted in white pre-
cipitate formation. The hot precipitate was filtered off imme-
diately. In the obtained phosphoric acid phosphorus and
calcium and ions were analyzed (Table 7). The precipitate

Table 5. Parameters of the designed experiments

Table 6. Matrix of the experiment designed

 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008 17

was subjected to X-ray diffraction and for water and phos- The ciagram of the technological idea of phosphoric acid
phorus content analysis. production from hydroxyapatite obtained by bone wastes
The data in Table 7 indicate that when the concentration incineration is shown in Figure 6. Part of the phosphoric
of the sulphuric acid is increasing, introduced for calcium acid, recycled from the filtration section, part of the mixture
sulphate precipitation, calcium concentration in the obtained of phosphoric acid with calcium sulphate, recycled before
phosphoric acid is decreasing, but sulphate-ion concentra- calcium phosphate was filtered off, and the suspension of
tion is increasing. The X-ray diffraction analysis (Figure 5) hydroxyapatite in water are directed to the reactor equipped
of the precipitates obtained in the process of phosphoric acid with the heating jacket. After the hydroxyapatite was dis-
formation identified gypsum in the precipitate obtained at 85 solved, sulphuric acid, diluted with the washings from the
– 95°C, while in the precipitate obtained at 75 – 80°C, hemi- filtration section, was added. The suspension, containing
hydrate CaSO4.0.5H2O was additionally found5. calcium and phosphoric acid, is filtered off with the use of
Table 7. Result of analysis of phosphoric acid obtained from hydroxyapatite at different temperature
18 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008

Figure 5. XRD of the precipitate obtained in the process of H3PO4 formation at temperature of 95 (A) and 75°C (B).
Concentration of sulphuric acid used was 50 – 60% H2SO4

the filter-press. Part of the phosphoric acid obtained has In Table 8 the parameters of the phosphoric acid manu-
been recycled to the reactor, the rest is directed to the con- facturing from apatite in Wizow Chemical Works plant in
centrating section. The concentrated phosphoric acid (75% comparison to the manufacturing (to be made) from hy-
H3PO4 ~ 54 P2O5) can be commercialized or used for the droxyapatite, derived from bone wastes has been presented.
production of phosphoric acid salts by the company. The The assessed cost of the phosphoric acid (100% H3PO4)
vapours from the reaction and from the acid concentrating production from hydroxyapatite is ~$500/t. The current
section are condensed. The condensate is used in the filtra- cost of the commercial food-grade phosphoric acid is on the
tion section for phosphogypsum washing. The level of $1200. A comparison of these two numbers indi-
phosphogypsum is temporarily stored and then sold. cates that the expected profit of phosphoric acid production
from the incinerated bone wastes could be high5.
Table 8. Parameters of phosphoric acid technology carried out in ZCH Wizow plant in comparison to the manufacturing (to
be made) from hydroxyapatite, derived from bone wastes [17]
 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008 19

Figure 6. Diagram of the technological idea of phosphoric acid production from hydroxyapatite obtained by bone wastes
incineration

CONCLUSION enabled an assessment of the cost of around ~ $500 /t. In

comparison to the current cost of the commercial food-grade
The results that led to the elaboration of phosphoric acid
phosphoric acid (~ $1200 /t) the expected profit could be
production method from the ashes obtained through the
high.
incineration of bone wastes from meat industry have been
presented. The ash is a valuable alternative source for food-
grade phosphoric acid production. It is characterised by high LITERATURE CITED
phosphorus concentration (the level of 16% P) and traces of 1. Kowalski, Z. (1998). Czystsza produkcja jako strategia
impurities. ochrony œrodowiska naturalnego. Biuletyn nr 3. Kraków, Polska:
On the basis of the research, carried out on the laboratory Komitet In¿ynierii Œrodowiska PAN.
scale, the technological parameters of two-stage phosphoric 2. Kowalski, Z. & Kulczycka J. (2004). Cleaner production
acid processing from hydroxyapatite obtained through the as a basic element for the sustainable development strategy.
P. J. Chem. Technology 6, 4, 35 – 40.
incineration of bone wastes have been evaluated. In the 1st
3. Steen, I. (1998) Phosphorus availability in the 21st cen-
stage hydroxyapatite is dissolved in phosphoric acid to yield tury: Management of non-renewable resources, Phosphorus
mono-calcium phosphate in solution. The overall hydroxya- and Potassium, 217, 25 – 31.
patite dissolution takes place in phosphoric acid with the 4. Phosphates, August 1997. European Chemical Industry
37% H3PO4 content. In the 2nd stage calcium phosphate is Council and C.E.E.P.
converted into calcium sulphate using concentrated sulphu- 5. Krupa-¯uczek, K. (2007). Receiving phosphoric acid from
ric acid. bone sludge from meat industry. Unpublished doctor`s thesis,
A preliminary economic analysis of the production of Cracow University of Technology, Poland.
10 000 t/year of food-grade phosphoric acid (100% H3PO4)
20 Pol. J. Chem. Tech., Vol. 10, No. 3, 2008

6. Regulation (EC) No 1774/2002 of the European Parlia-

ment and of the Council of 3 October 2002 laying down
health rules concerning animal by-products not intended
for human consumption, Official Journal of the European
Communities, No L 273, 10.10.2002.
7. Pezacki, W. (1991). Przetwarzanie surowców rzeŸnych.
Wp³yw na œrodowisko przyrodnicze. Warszawa, PWN.
8. Konopka, M., Kowalski Z., Fela K., Cholewa J.,
Bajcer T. & Klamecki G. (2006). Charakterystyka nisko-
temperaturowego procesu otrzymywania protein na bazie
tkanki miêsno-kostnej z zastosowaniem wybranych enzymów.
Recyklace Odpadù X. VŠB Ostrava, Czech Republic,
03.11.2006, 311 – 316.
9. Minczewski, J. & Marczenko, Z. (1965). Chemia
analityczna. Warszawa, PWN.
10. Polish Standard. (1988). Chemical fertilizer. Labora-
tory test of phosphate content. PN-88/C-87015.
11. Wandrasz, A.J. & Wandrasz, A.Z. (2005). Badanie
sk³adu elementarnego i w³aœciwoœci kalorycznych produktów
zwierzêcych. Paliwa z odpadów, t.5. Gliwice, Wyd. Helion.
12. Kowalski, Z., Wzorek, Z., Krupa-¯uczek, K. & Sobczak,
A. (2007) Mo¿liwoœci otrzymywania hydroksyapatytu poprzez
kalcynacjê pó³produktów kostnych z przemys³u miêsnego.
In¿ynieria Stomatologiczna – Biomateria³y, Tom 4, nr 1, 7 – 11.
13. Polish Standard (1997) Fodder. Phosphate of fodder.
PN-R-64803.
14. Praca zbiorowa. (1958) Technologia zwi¹zków
fosforowych. Warszawa, PWT.
15. Górecki, H. (1980) Bezodpadowe metody przetwarzania
mineralnych surowców fosforowych. Wydawnictwo Politechniki
Wroc³awskiej, Wroc³aw.
16. Becker, P. (1983) Phosphates and Phosphoric Acid,
Raw materials, Technology and Economics of the Wet proc-
ess, Marcel Dekker Inc., New York.
17. Unpublished information material of „Wizów” estab-
lishment.