A 1.

3 : 144
BULLETIN OF

US.DEPARTMENT OFAGRICULTURE
No. 144

Contribution from the Bureau of Soils, Milton Whitney,

IAChief.
N
December 24, 1914. IND was 8251 )
LIBRARY
THE MANUFACTURE OF ACID PHOSPHATE.
By Wu. H. Waggaman, Scientist in Fertilizer Investigatiorg. 7 1915
INTRODUCTION .

The acid -phosphate industry in the United States has grown to

enormous proportions. In spite of the fact that numerous other
forms of phosphatic fertilizer have been proposed or patented from
time to time, and the application of raw ground -rock phosphates
directly to the field has been recommended by some agronomists
and agricultural chemists, the annual production of superphosphate
continues to increase There is little doubt, therefore, that this
material will continue to be the basis of most of our commercial
fertilizers.
While the general procedure followed in making acid phosphate
is a familiar one, many of those engaged in the production of this
material have but little knowledge of the chemistry involved and are
unfamiliar with numerous details of its manufacture, which are of
great economic importance. Competition has become so keen in
the fertilizer industry during the last few years that in order to make
a reasonable profit the manufacturer can no longer afford to carry on
his business in the loose way formerly so prevalent, but must practice
the most modern scientific methods and exercise the closest supervi
sion over every detail of his factory processes. It is believed that
the preparation of this bulletin is justified by the information it will
furnish the fertilizer manufacturers ; but it is intended primarily to
give the progressive farmer a clearer knowledge of that compound
which is the basis of fertilizers, in order that he may more intelligently
buy and handle his fertilizer and determine for himself its true
value. Such knowledge, it is believed, should tend greatly to clarify
prevailing ideas concerning the value of factory and of home-mixed
fertilizers, and to throw light on the attendant question of inordinate
profits alleged to be made by manufacturers. This paper describes
1 Brogdon, J. S. , Manufacture of Acid Phosphate. Amer. Fertilizer, 39 (5) , pp. 25–29 (1913).
NOTE . - Describes the manufacture of acid phosphate from phosphate rock, detailing the chemical and
mechanical changes involved . Of interest to fertilizer manufacturers generally.
58869°/14 -1
2 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .
>

the whole process, including the preparation of the raw materials

used, the methods of manufacture with the chemical reactions
involved, the equipment of the modern factory, the disposal of
obnoxious gases , the methods of drying, storing, and disintegrating
the superphosphate, and the cost and disposal of the finished product.
RAW MATERIALS .

The raw materials used in the manufacture of acid phosphate are

bone, guano, apatite, phosphate rock, and sulphuric acid.
Before the discovery of the vast deposits of phosphorites or natural
phosphate rock in this country bone was one of the farmer's chief
sources of phosphoric acid .' The bones were either steamed, charred,
or burned and applied directly to the field, or after grinding were
made into acid phosphate by treating with an approximately equal
weight of sulphuric acid.
Ground bone, however, has considerable agricultural value with
out being acidulated, and besides, the cost of the phosphoric acid
contained therein is so much greater than that contained in phosphate
rock that it is obviously not economical to use the former material
in the manufacture of acid phosphate. The amount of this substance
now derived from bone is therefore relatively small.
Guano is another substance which has been extensively used in
the manufacture of acid phosphate. This material consists essen
tially of the excrements of birds and sometimes of bats, and at one
time was found in large quantities. There are two types of guano
deposits : (1 ) The unleached deposits which are usually found in
caves or other sheltered places where the droppings have been pro
tected from the leaching effect of percolating water. Such a deposit
not only contains phosphoric acid in a readily available form , but
also carries considerable quantities of nitrogen , the fertilizer constit
uent commanding the highest price. (2) That which has been
leached of its more soluble constituents by exposure to the weather.
It contains practically no nitrogen and its phosphoric-acid content,
though usually high, is relatively insoluble. Deposits of guano have
been eagerly sought, and accessible and valuable ones are now rather
scarce. Only those containing high percentages of nitrogen, or situ
ated in regions having excellent transportation facilities, are able to
.compete with other and cheaper sources of phosphate .
At one time apatite was largely used in the manufacture of acid
phosphate. This mineral is very widely distributed, and occurs in
rocks of various kinds and ages. It is most common , however, in
rocks of the metamorphic crystalline variety, such as limestone,
gneiss, mica, schist, beds of iron ore, etc. There are two main vari
eties of apatite, namely, chlor -apatite (Cacica, P ,0z) and fluor
 THE MANUFACTURE OF ACID PHOSPHATE , 3

apatite (CaFCa P2012) . The latter variety is by far the most com
3

mon , but there are intermediate compounds containing both chlorine

and fluorine. Pure fluor-apatite contains 42.3 per cent phosphoric
acid (P203), but it is seldom found in a pure condition . The occur
rence of apatite associated with magnetite in northern New York 1
has long been known, but attempts to separate the apatite commer
cially have proved unsuccessful.
In Norway and Canada , however, there are large deposits of apa
tite which were at one time extensively worked, but the discovery
of cheaper and more accessible sources of phosphoric acid (particu
larly in the United States) has caused a serious curtailment in the
mining of this mineral .
The main objections to apatite as a source of phosphoric acid are,
first, the expense of mining and picking the rock and, second, the
large percentage of fluorine, which yields obnoxious gases when the
rock is treated with sulphuric acid . The superphosphate now man
ufactured from apatite is but aa small percentage of the total material
marketed .
The vast bulk of acid phosphate produced both in this country
and abroad is made from the amorphous phosphates of lime, of which
there are enormous deposits in the States of Florida, Tennessee, Utah,
Idaho, Wyoming, and Montana, and in northern Africa, and smaller
deposits in the States of South Carolina, Arkansas , and Kentucky in
this country, and in France, Germany, England, and Belgium .
Ocean and Pleasant Islands of the Gilbert group, as well as some
of the Society Islands in the southern Pacific and Christmas Island
in the Indian Ocean, contain large quantities of very high grade
phosphate rock ; in fact, these phosphates are as rich as any amor
phous phosphates known. It is only in recent years , however, that
the deposits have been developed to any extent, and owing to the
lack of harbors the rock must be loaded at sea, which makes their
exploitation somewhat difficult.
The character of the American deposits, the methods of mining
and preparing the rock for the market, the cost of production , annual
output, and other details of this industry have been described in
2
bulletins of this department, and so need not be repeated here.
In Table I is given a list of the more important phosphatic sub
stances (with their approximate composition) used in the manu
facture of acid phosphate .
1 Blake, W. P. , Trans. Am. Inst . Min. Engrs., 21, pp. 157-160 (1892-93).
3

2 Buls. 41, 69, 76, and 81, Bureau of Soils, U.S. Dept. Agr .; Bul . 14, U. S. Dept. Agr. ( 1913) .
4 BULLETIN 144 , U. S. DEPARTMENT OF AGRICULTURE .

TABLE I. — Composition of phosphatic materials used in the manufacture of acid phosphate.

alumi
Oxide
Silica
insol

iron
(Fe2O3
and
Nitrogen

),num
of
or

A).( l2O3
S(). iO2
Phosphatic Location ,

uble
material .

(N).
P.ct. P.ct. P.ct. P.ct. P.ct. P.ct. P.ct.
Bone ash . 4.06 3.01 5.28 35.38 76. 65
Fat-extracted 4.14 3.60 5.24 21. 68 46.50
bone .
Bone or animal 1.12 2.00 0.37 1.00 8.00 31.99 73. 10
charcoal .
Apatite :
High grade... Canada . 3.67 .70 3.10 4.13 38.60 88. 20
Lower grade . ..do .. 8.92 1.03 3.04 8. 05 34. 42 78. 65
A patite ( high Norway .. 3.62 1.37 2.62 . 29 39.44 86.10
grade ) .
Bat guano . Porto Rico . 8.35 1.59 7.57 16.52
Guano in crusts .. West Indies .45 5.88 24.36 53.18
Phospho -guano . Mexico ... .40 1.14 39.70 86.66
Phosphorite:
High grade... Somme, France . .79 1.39 9.17 35. 59 77.69
Lower grade. .do . 8.55 4.07 6.95 29.10 63.53
Do .. Liege, Belgium . 16.14 2.39 5.00 7.07 27.20 62. 15
Coprolites. Cambridge , 9.00 2.30 34.00 77.70
Eng .
Do.. Suffolk , Eng . Not det. 9.00 6.00 10.00 23. 63 54.00
Phosphate nod- Russia . Not det. 5.00 6.98 12. 23 32.82 75.00
ules.
Do ... South Carolina .. 4 to 12 1 to 4 2 to 8 11 to 25 25 to 28 57 to 64
Hard rock phos- Florida .. 4.13 3.00 4.40 3.63 36.39 83.14
phate.
Land pobble ..... do . 5 to 10 1 to 4 O to 3 2 to 5 30 to 34 69 to 78
phosphate.
Brown rock phos- Tennessee .. 2.5 to 10 3 to 8 0 to 5 0 to 10 30 to 38 69 to 87
phate .
Blue rock phos- ..... do .. 2.5 to 70 2.5 to 7 O to 3 0 to 2 27 to 32 62 to 73
phate.
White rock phos ..do . 2 to 7.5 1.5 to 3.5 32 to 38 73 to 87
phate.
Black rock phos- Arkansas. 15 to 40 2.5 to 9.5 23 to 28 53 to 64
phate.
Brown rock phos- | Kentucky .. 2 to 5 2.5 to 5 30 to 35 69 to 80
phate.
politic black Utah , Idaho , etc. 1.8 to 10 07 to 1.6 1.8 to 1.35 3.8 to 13,6 27 to 36.5 62 to 83
phosphate.
White phosphate Ocean Islands... Not det . 42 1.0 4.91 38.73 84. 65

1 Known to the trade as bono phosphate of lime, b . p . l .

The sulphuric acid used in the manufacture of acid phosphate is

the ordinary " chamber acid.” It ranges in specific gravity from
1.5 to 1.6 at 60° F. and contains from 60 to 70 per cent of sulphuric
acid. The fertilizer trade, however, is accustomed to expressing
the strength of " chamber acid ” in Baumé degrees (°B) . The
manufacturer should have conversion tables at hand showing the
specific gravity and percentage of acid corresponding to each degree
registered by the Baumé hydrometer. Part of such a table approved
and adopted by the Manufacturing Chemists Association of the
United States is given in Table II.
 THE MANUFACTURE OF ACID PHOSPHATE , 5

TABLE II. — Specific gravities and their equivalents in Baumé degrees of sulphuric acid of
various strengths.

Per cent Per cent Per cent

B. Sp . gr. ° B. Sp. gr. ° B. Sp. gr.
H2S04 . H2S04 . H2SO ,

0 1.0000 0.00 25 1. 2083 28. 28 49 1.5104 60.75

1 1.0069 1.02 26 1.2185 29.53 50 1.5263 62. 18
2 1.0140 2. 08 27 1. 2288 30. 79 51 1.5426 63.66
3 1.0211 3. 13 28 1.2393 32.05 52 1.5591 65. 13
4 1.0284 4.21 29 1. 2500 33.33 53 1.5761 66.63
5 1.0357 5. 28 30 1.2609 34.63 54 1.5934 68. 13
6 1.0432 6.37 31 1. 2719 35.93 55 1.6111 69.65
7 1.0507 7.45 32 1. 2832 37. 26 56 1.6292 71. 17
8 1.0584 8.55 33 1. 2946 38.58 57 1.6477 72. 75
9 1.0662 9. 66 34 1.3063 39.92 58 1.6667 74.36
10 1.0741 10.77 35 1.3182 41. 27 59 1. 6860 75. 99
11 1.0821 11.89 36 1.3303 42. 63 60 1.7059 77.67
12 1.0902 13.01 37 1.3426 43.99 61 1. 7262 79. 43
13 1.0985 14. 13 38 1.3551 45.35 62 1. 7470 81.30
14 1. 1069 15. 25 39 1.3679 46. 72 63 1. 7683 83. 34
15 1. 1154 16. 38 40 1.3810 48. 10 64 1. 7901 85. 66
16 1. 1240 17.53 41 1.3942 49. 47 641 1. 7957 86.33
17 1. 1328 18. 71 42 1.4078 50.87 64.3 1.8012 87.04
18 1. 1417 19.89 43 1.4216 52. 26 643 1. 8068 87.81
19 1. 1508 21.07 44 1. 4356 53. 66 65 1.8125 88.65
20 1. 1600 22. 25 45 1.4500 55.07 651 1.8182 89.55
21 1. 1694 23.43 46 1. 4646 56. 48 655 1.8239 90.60
22 1. 1789 24.61 47 1. 4796 57.90 652 1. 8297 91.80
23 1.1885 25. 81 48 1.4948 59.32 66 1.8354 93. 19
24 1. 1983 27.03

THEORETICAL BASIS FOR THE MANUFACTURE OF ACID PHOSPHATES.

The process of making acid phosphate was devised in order to

change the phosphoric acid contained in the substances just enumer
ated into a more soluble or " available " condition.
The phosphates of lime, as found in nature are highly basic com
pounds or solid solutions offering considerable resistance to the sol
vent influence of percolating meteoric or soil waters . The less basic
phosphates (those containing less lime, iron, alumina, or magnesia)
are more soluble in water. Therefore, in order to bring about the
desired change, an acid stronger than phosphoric acid is added in
sufficient quantity to combine with a portion of the lime, producing
a phosphate less basic and , consequently, more soluble. The reagent
which has been found best suited for this purpose is sulphuric acid ,
not only because of its cheapness but because calcium sulphate, one
of the products of the reaction, takes up the excess of water present
in the acid phosphate to form gypsum . The final product, there
fore, if properly made, is dry and can be readily mixed with other
ingredients to make a complete fertilizer.
The main purpose sought to be accomplished in the factory treat
ment of phosphate rock is to prepare a product in which the phos
phoric acid will be water soluble, so far as this can be accomplished,
with due regard to the physical properties of the product essential
to its ready mixing and handling. While it is a matter of no great
difficulty to determine by a chemical analysis just what constitu
ents are in a given phosphate rock and in what proportions, it is not
1 Bul. 41 , Bureau of Soils, U. S Dept. Agr . ( 1907) .
6 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .
known just how these constituents are chemically united. It is gen
erally assumed that the phosphoric acid is combined with the lime
in a hypothetical compound - tricalcium phosphate (known to the
trade as bone phosphate of lime, b . p. 1.) , represented by the formula
Ca, (PO3) 2, and that this compound, when treated with sulphuric acid
(H,SO,) and water (H,0) in the right proportions, is converted into
a mixture of gypsum (CaSO, 2H ,0 ) and monocalcium phosphate
[Ca ( H ,PO2)2]. Both gypsum and monocalcium phosphate are per
fectly definite, well-known compounds. The former is but slightly
soluble, the latter readily soluble in water. As a matter of fact, in
the reaction cited above, it is probable that dicalcium phosphate
[Ca (HPO ),] is formed as well. Both these calcium phosphates are
decomposed by water, so that a solution of monocalcium phosphate,
if diluted, will precipitate dicalcium phosphate and if the dilution
be carried further, a phosphate even more basic than the tricalcium
phosphate is formed. Obviously, the more basic the calcium phos
phate, the less soluble it is in water. It is equally obvious that when
incorporated in the soils, the soil water, while dissolving and dis
tributing the phosphate, is at the same time decomposing it into
less soluble forms. Assuming now, as we may do for convenience,
that the reaction takes place in the mixing as outlined above, it may
be represented thus:
Tricalcium phosphate or pure phosphate rock . Sulphuric acid. Water.
Ca ( PO4) 2 + 2H2SO4 + 411,0
1 molecule, weight 310 . 2 molecules, 4 molecules,
weight 196 . weight 72.
Gypsum . Monocalcium phosphate or superphosphate.
2 ( CaSO, 2H,0 ) + Сан ,( PO4) .
2 molecules, weight 344 . 1 molecule, weight 234 .
The above equation means that in order to change completely 310
parts of tricalcium phosphate or pure phosphate rock into acid
phosphate, 196 parts of pure sulphuric acid are required , or 1 ton of
phosphate rock requires 0.63 ton of sulphuric acid. Factory practice
and long experience in the manufacture of acid phosphate have
shown, however, that much better results are obtained by employing
sulphuric acid containing from 30.35 to 37.82 per cent of water
( chamber acid ” ). A part of the water contained in this acid is
evaporated by the heat of the chemical reactions taking place, and a a

part is taken up by the calcium sulphate formed to produce gypsum ,

as shown in the above equation .
IMPURITIES IN PHOSPHATE ROCK.

Besides calcium phosphate the phosphates of commerce always

contain varying quantities of impurities, such as organic matter,
silica or silicates, calcium fluoride, oxides or phosphates of iron and
1 Vide, Bul. 41, Bureau of Soils, U. S. Dept. Agr., pp. 22-25 ( 1907).
 THE MANUFACTURE OF ACID PHOSPHATE . 7

aluminum , and carbonates of lime or magnesia. All of these impuri

ties take up or are acted upon directly or indirectly by sulphuric acid,
the bases being converted into sulphates and the fluorides, carbonates,
and organic matter being decomposed with the evolution of gases.
It is very important that the manufacturer should be acquainted
with the effect that these impurities and the compounds produced
therefrom will have upon his acid phosphate, and he should be able to
calculate from the analysis of his raw material what quantity and
strength of sulphuric acid is required to satisfy these impurities.
The action of the sulphuric acid upon the various foreign substances
found in natural phosphates of lime, and the effect of these impurities
on the finished product are discussed below in some detail.
ORGANIC MATTER .

Practically all phosphates, with the exception of apatite, are of

animal origin and therefore contain a certain amount of organic
matter. When present in any quantity organic matter usually
imparts a dark color to the phosphate. The presence of very small
quantities can be detected by the putrid odor emitted on crushing or
grinding the rock. The phosphates of our western States, as well as
some of the Tennessee rock, contain considerable quantities of organic
matter, while most of the Florida phosphates are very low in this
material.
The methods now employed in drying phosphate, either by calcining
it on ricks of wood or putting it through a rotary drier, burns out or
destroys a part of the organic matter ; the remainder is carbonized by
sulphuric acid with the evolution of volatile or gaseous products.
The sulphuric acid is at the same time reduced to sulphur dioxide
(SO2), or to hydrogen sulphide ( 4,5) if the reduction has proceeded
further. The production of these gases not only entails aa loss of sul
phuric acid , but they are both disagrecable and deleterious to health .
In making acid phosphate the organic matter found in the rock is
not considered, since the amount present is usually small. Owing
to the various forms in which organic matter may occur, it is almost
impossible to judge except by actual experiment how much sulphuric
acid is required for its decomposition.
SILICA AND SILICATES,

Sulphuric acid has no direct action upon silica (SiO2) , but when
fluorides are present an indirect action occurs, which is described
below. Silicates are directly acted upon by sulphuric acid, but so
slowly that they need hardly be taken into account. The presence of
silica or silicate minerals in phosphate rock is not considered objec
tionable except in so far as they act as diluents. Phosphates con
taining high percentages of silica necessarily have aa lower percentage
of phosphoric acid than the less siliceous or purer phosphates.
8 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE ,
CALCIUM FLUORIDE .

Fluorides are present in almost all phosphate rock . Some samples

contain as high as 8 per cent of calcium fluoride (CaF2). The amor
phous phosphates as a rule contain smaller quantities of this com
pound than apatite.
Calcium fluoride reacts with sulphuric acid, giving gaseous hydro
fluoric acid (HF ) and calcium sulphate, thus:
Calcium fluoride. Sulphuric acid . Hydrofluoric acid . Calcium sulphate.
CaF , + H2SO4 = 2HF + Caso

But hydrofluoric acid (HF) acts upon the silica or silicates present
in the mass , producing gaseous silicon, tetrafluoride (SiFa), and water
or steam , thus :
Hydrofluoric acid. Silica . Silicon tetrafluoride. Water.
4HF + Sio SiF4 + 2H2O
Silicon tetrafluoride in turn is decomposed by water with the
formation of hydrofluosilicic acid (H,SiFc) and precipitation of pure
silica (SiO2) , thus :
Silicon tetrafluoride . Water or steam . Hydrofluosilicic acid . Silica .
3SiF + 2,0 =
24 SiF . + SiO
Before this last reaction takes place, however, much of the silicon
tetrafluoride escapes from the mass and can be detected by its pene
trating odor and smarting effect on the eyes and nose..
Very high grade acid phosphate can be made from rock containing
large amounts of fluorine, because, as pointed out above, many of the
products formed during the process escape as gases or vapors, leaving
the mass correspondingly richer in phosphoric acid. These gases
also, in forcing their way out of the acid phosphate, tend to render it
porous and more readily dried.. The product, therefore, can be easily
broken up and mixed with other ingredients to make a complete
fertilizer.
The main objections to using phosphates high in fluorides are, first,
the increased quantity of sulphuric acid necessary to decompose these
compounds, and, second , the noxious and even poisonous nature of
the gases evolved during their decomposition.
COMPOUNDS OF IRON AND ALUMINUM .

Iron and aluminum oxides, either in the free state or combined as

phosphates,, are the most objectionable of the impurities found in
phosphate rock. These substances even when present in very small
quantities cause a certain amount of " reversion ” in the superphos
phate, and when present in large quantities are likely to produce a
sticky acid phosphate unfit for commercial purposes .
The phosphate of iron in natural occurrences may conveniently be
represented by the formula FePO4 , although actually it is probably
 THE MANUFACTURE OF ACID PHOSPHATE . 9

of an indefinite composition. The exact reactions that take place

when this substance is treated with sulphuric acid are not known.
Unquestionably, however, the iron is distributed between the two
acids. A mixture of 66" sticky,” disagreeable physical properties
results, the composition of the solid part of the mixture changing
with the composition of the liquid part which is formed at the same
time. Both the solid and the liquid contain all three constituents
iron, sulphuric acid, and phosphoric acid. Dilution of this liquid
mass by the addition of water causes a precipitation of more jellylike
material containing relatively more iron and phosphoric acid than
sulphuric acid. The general course of the reactions are sufficiently
well known to justify the assumption that they go mainly according
to the following equations :
2FePO4 + 3H ,SO , Fe2 (SO2)3 + 2H2PO ,
But a part of the iron sulphate produced reacts with the phosphoric
acid or monocalcium phosphate in the mass forming hydrated phos
phate of iron, the gelatinous precipitate almost insoluble in water,
and when present in any quantity causing the acid phosphate to be
sticky and difficult to handle. The reactions may be represented
thus :

Iron sulphate. Phosphoric acid . Water or steam. Hydrated iron Sulphuric acid .
phosphate
Fe2( SO4 )3 + 2H,PO4 + 48,0 # 2FePO4.2H2O + 3H2SO4
According to Fritsch , however, two per cent of iron oxide in the
raw material is not objectionable, because the quantity of iron
sulphate produced therefrom remains unaltered in the superphos
phate. It is true that in properly made acid phosphate nearly all of
the phosphoric acid is soluble in water even though there is suſficient
iron present to cause part of it to revert, but Fritsch is probably in
error in attributing this to the fact that the iron is all in the form of
sulphate . Schneider 2 has shown experimentally that solutions of
sulphate of iron increase the solubility of iron phosphate and Cameron
and Bells have demonstrated that gypsum , lime, and phosphoric
acid also increase the solubility of this substance .
Hydrated iron phosphate may be converted into the anhydrous
and less soluble condition by reacting with anhydrous calcium sul
phate; the last -named compound being converted into gypsum, thus :
Hydrated Anhydrous Anhydrous iron
iron phosphate. calcium sulphate . Gypsum . phosphate.
FePO4 21,0 + CaSO4 = = CaSO4.26,0 + =
FePO4
1 Manufacture of Chemical Manures, pp . 78–79 ( 1911 ) .
2 Zeit. anorg. Chem. , 5, 84 ; 7, 386 ( 1894) .
3 Bul . 41, Bureau of Soils, U. S. Dept. Agr. ( 1907) .
58869 °—11–
10 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .

This last reaction partly explains why acid phosphate in excellent

mechanical condition, but with a relatively high percentage of phos
phoric acid insoluble in water is often made from rock containing
large quantities of iron and aluminum .
Compounds of aluminum react in a manner similar to those of iron,
but to a less marked degree.
Fertilizer manufacturers and authorities differ widely on the
question of what constitutes the maximum quantity of iron and
alumina that a phosphate rock can contain and still be useful in the
manufacture of acid phosphate. Wyatt 1 says that phosphates
containing from 6 to 8 per cent of iron and alumina may be used,
provided there is sufficient carbonate of lime present to produce a
dry, pulverulent mass. Schucht ?2 and Fritsch 3 are inclined to con 3

sider any quantity of iron and alumina in excess of 3 per cent as

undesirable. Stillwell 4 states that phosphates containing from 4
to 6 per cent of these oxides can be handled, but that the presence of
more than 2 per cent is objectionable.
Thousands of tons of high - grade acid phosphate, however, are now
annually made from Tennessee brown rock phosphate containing as
high as 5 per cent of the combined oxides of iron and aluminum , and
though the handling of such phosphates necessitates an increased
consumption of sulphuric acid, there seems little reason why they
should not be used in making acid phosphate, provided they are so
manipulated that a dry, readily workable product is obtained.
CARBONATES OF LIME AND MAGNESIA .

Carbonates are frequently very desirable impurities in phosphate

rock, provided they do not occur in quantities so great that the per
centage of phosphoric acid present is materially reduced. The
carbonic acid is usually combined with lime, and it is in this form
that it is considered here. Sulphuric acid acts upon calcium carbon
ate to form calcium sulphate, water or steam, and carbon dioxide,
which escapes as a gas. The reaction may be represented thus.
Sulphuric Calcium Calcium Water or Carbon
acid . carbonate . sulphate. steam . dioxide .
H.SO ,4 + CaCO , CaSO4 + 1,0 + CO2
=

If suſficiently diluted sulphuric acid is used the excess of water

combines with the calcium sulphate to form gypsum . Modifying
the above equation therefore, we obtain :
Sulphuric Calcium Carbon
Acid . Water . carbonate Gypsum . dioxide.
H.SO , + 1,0 + CaCO3 = CaSO, 27,0+ CO,
1 Phosphates of America, pp . 111-116 ( 1891 ) .
2 Die Fabrikation des Superphosphates, pp. 79-83 ( 1909).
3 Manufacture of Chemical Manuros, pp . 78–80 ( 1911 ) .
4 Industrial Chemistry , Rogers & Aubert, p . 403 ( 1912).
 THE MANUFACTURE OF ACID PHOSPHATE , 11

The advantages of having small quantities and in some cases

large quantities) of carbonate of lime present in phosphate rock are
threefold : First, the heat evolved in the reaction between carbonates
and sulphuric acid is sufficient to warm the pasty mass of acid and
phosphate rock and thus promote chemical action between these
more slowing reacting substances ; second, the escape of carbon
dioxide from the mass renders the acid phosphate porous and more
readily dried; and third, the gypsum formed prevents the formation
of the gelatinous iron and aluminum compounds and thus helps
render the product dry and in good condition for distributing or
mixing with other fertilizing ingredients.
REVERSION OF SUPERPHOSPHATE .

The reversion of superphosphate, as the term implies, originally

meant the return of the phosphoric acid to a condition insoluble (or
nearly so) in water. In reality the expression " reverted ” phosphoric
acid is now wrongly used in a much broader sense and includes all of
the phosphoric acid of superphosphate which is soluble in certain
citrate solutions . In this paper, however, reverted phosphoric acid
>

is used in the strict sense of the word.

When a superphosphate is allowed to stand and take up water
from moist air, as it sometimes does while in storage; or is diluted by
9

the soil water when it is applied to the soil ; or is added to an excess

of water, as is done in the laboratory before commencing analytical
operations, then , in any one and in all of these cases , less soluble
compounds of phosphoric acid are formed. If compounds of iron
and aluminum are present the formation of phosphates insoluble in
water is much more marked . This general process is known as
reversion, and the superphosphate is said to have reverted, and the
product is called reverted phosphate. The theory of this reversion is
now clearly understood, owing to the investigations in this country
1
of Cameron and Bell ? and Seidell, and of Bassett 3 in England, who
have shown that certain concentrations of phosphoric acid or of other
acids.must exist in the water in contact with a calcium or iron phos
phate for the solid definite “ acid ” compounds to be stable. Dilution
of the acid liquor causes the solids to decompose into more basic and
less soluble compounds. While the theory of these phenomena has
been made clear only recently, the main facts have long been known,
>

and as is so commonly the case, certain popular misconceptions have

held sway long enough to become regarded as facts even by many well
trained chemists. Thus, it is popularly held that monocalcium phos
phate is soluble in water, but dicalcium phosphate is not ; dicalcium
1 Bul. 41 , Bureau of Soils, U. S. Dept. Agr. ( 1907 ).
2 Jour. Am . Chem . Soc . , 27 , 1503 ( 1905 ) .
3 Chem . News , 95 , 21 ( 1907 ) ; Zeit. anorg. Chem ., 53, 34 ( 1907 ).
12 BULLETIN 144 , U. S. DEPARTMENT OF AGRICULTURE .

phosphate is in turn soluble in certain citrate solutions, while trical

cium phosphate is not ; and on these supposed facts methods for
separating the three compounds have been suggested. Moreover, it
is held that while the water-soluble monocalcium phosphate and citrate
soluble dicalcium phosphate are " available ” to plants, more basic
phosphates are not.
The facts are that the presence of citric acid or ammonium citrate
in the water does increase the solubility of the phosphates of lime, >

iron , and alumina, and it has been shown by field tests that phos
phates soluble in such solutions are more quickly active under soil
conditions than those which do not dissolve in the same mediums.
(
Hence a convenient control or police” method of analyzing com
mercial fertilizer containing phosphates has been developed. But
the " citrate solubility ” gives no definite information about the
constitution of the phosphate. The actual phenomena involved in
reversion can be best followed by the microscope.
Reversion is, however, a reality, and one to be carefully avoided.
The reverted phosphate is frequently difficult to handle, and even if
its mechanical condition is good and the phosphoric acid present is
classed as available according to the official method of analysis, many
consumers seriously object to its use because the percentage of water
soluble phosphoric acid present is relatively low . Moreover, reverted
phosphate is not easily susceptible to retreatment in the factory, and
usually the manufacturer can better afford to throw it away than
attempt to work it over in competition with untreated raw rock.
METHOD OF MANUFACTURE.
GRINDING THE ROCK.

The phosphate rock is first put through a crusher and broken in

a
pieces not larger than a walnut. This crushing is hardly necessary in
the case of Florida pebble phosphate or the screenings from the hard
rock phosphate, since the pebbles and fragments are usually small
enough to be fed directly to the mill.
The pulverizers for phosphate rock that are probably most widely
used in this country are thoso of the roller type, in which the material
is crushed by steel rollers revolving within a steel ring. Sometimes
the ring within which these rollers revolve is rigid and the power is
transmitted through the rollers . In another form of mill, the ring is
revolved by a shaft, and the rollers are revolved in turn by the ring.
There are a number of different makes of these pulverizers, but
space does not permit a detailed explanation of their construction.
For convenience they all may be placed in one of two broad classes,
namely, the type which combines both grinding machinery and
screens in one, and the type which discharges the partly ground
material into elevators to be subsequently screened or separated, the
coarser material being returned to the mill for further grinding.
 THE MANUFACTURE OF ACID PHOSPHATE , 13

Mills of the first type occupy but little space, do not require auxil
iary screens and conveyors , and the grinding is all finished in one
operation. The fact, however, that the pulverized phosphate is not
separated from the coarser rock until forced through the screens
within the mill cuts down somewhat the efficiency of this type of
machine, since considerable space and power is always taken up by
material already ground. Another disadvantage of this type of mill
is that any clogging of the screens or break in the same necessitates
the shutting down of the entire mill while the damage is repaired.
The manufacturers of the o her type of mill claim to have overcome
these disadvantages in their machines; the ground material is con
tinually discharged from the mill and separated from the coarser
rock by passing through revolving, or over vibrating screens. Any
trouble with a screen can be corrected without stopping the mill by
simply cutting off the supply of rock to that screen . Since the mate
rial flows over the screens instead of being forced against them as in
the case of the other type of mill, the repairs necessary on the screens
are reduced to a minimum . This type of mill, however, with its
auxiliary screens and conveyors, takes up considerable space , costs
more to install, and requires a greater amount of supervision. In
Plates I and II these two types of roller mills are shown .
The amount of material which can be pulverized per hour depends
on the size of the mill, the character of the phosphate rock used, and
the degree of fineness to which it is ground. A mill of the size usually
employed in fertilizer factories may grind from 10 to 12 tons per hour
of Tennessee brown rock phosphate to pass a 60-mesh sieve, but this
mill will probably not grind more than seven or eight tons of pebble
phosphate to the same degree of fineness in that period of time.
1
A very ingenious ball mill is that of Pfeiffer. The grinding is done
by means of steel balls or flint pebbles and the separation of the fine
material from the coarse is effected by means of a current of air.
All loss of time due to the clogging and repairing of screens is thus
avoided and a product of any degree of fineness can be obtained by
simply regulating the strength of the air current.
The degree of fineness to which phosphate rock is ground often
has a very important effect on the acid phosphate produced there
from . Phosphate rocks low in carbonates and high in iron and
aluminum are but slowly acted upon by sulphuric acid , and should
therefore be gound very fine. Phosphates containing large quan
tities of carbonate of lime are acted upon quite rapidly, and conse
quently do not require extremely fine grinding. In ordinary practice
the rock is usually ground so that 80 to 90 per cent will pass a 60
mesh sieve, but in working with less soluble phosphates it is fre
quently desirable to grind them so that 80 to 85 per cent will pass an
80-mesh sieve .
1 German patent No. 116,195 .
14 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .

QUANTITY, STRENGTH , AND TEMPERATURE OF SULPHURIC ACID .

The quantity and strength of sulphuric acid which should be used
in treating phosphate rock is a perplexing problem , yet many manu
facturers give it little consideration , proceeding in a " rule of thumb "
manner without regard to the composition of the rock. The reason
why many of these latter obtain such good results may be explained
by the fact that they have been using one grade of rock for years
and have thus learned by actual experience the proper proportions
of acid and rock to use . A sudden change in the composition and
grade of the phosphates often results in a loss of both acid and rock
in attempts to find the quantity of acid required for this new mate
rial. While actual trial mixings should be made when testing out a
new grade of phosphate , these tests should be intelligently con
ducted with due regard to the composition of this rock. Take, for
example, a sample of high - grade Florida hard rock phosphate having
the following composition :
Per cent.
Moisture . 0.5
Calcium fluoride (CaF2). 4.5
Tricalcium phosphate (Caz(PO4 )2) . 80.0
Calcium carbonate ( CaCO3) . 3.5
Aluminum phosphate (AlPO4 ) .. 6.0
Silica (SiO2) . . 5.5

Total ... 100.0

The problem is to convert the phosphoric acid of this rock into a

soluble form and yet obtain a dry product which can be uniformly
spread on the soil or readily mixed with other ingredients to make
up a complete fertilizer . The reactions which are desired may be
represented in their simplest form, thus:
( 1 ) Conversion of tricalcium phosphate to monocalcium phos
phate and calcium sulphate :
1 molecule 2 molecules 1 molecule 2 molecules
Caz( PO4)2 + 2H2SO4 = CaH ( PO4)2+ 2CaSO ,
Wt . 310 Wt. 196 Wt. 234 Wt. 272

( 2) Conversion of calcium fluoride to hydrofluoric acid and calcium

sulphate :
1 molecule 1 molecule 2 molecules i molecule
CaF2 + H2SO4 2HF + Caso
Wt. 78 Wt. 98 Wt. 40 Wt. 136

( 3) Conversion of iron phosphate to iron sulphate and phosphoric

acid :
2 molecules 3 molecules 1 molecule 2 molecules
2FePO , + 3H ,SO., == Fe2(SO )3 + 2H3( PO. )
=

Wt . 302 Wt. 294 Wt. 400 Wt . 196

 THE MANUFACTURE OF ACID PHOSPHATE , 15

( 4) Conversion of aluminum phosphate to aluminum sulphate and

phosphoric acid :
2 molecules 3 molecules 1 molecule 2 molecules
2A1PO4 + 3H2SO4 = Al (SO4)3 + 2H,PO,
Wt . 245 Wt . 294 Wt . 343 Wt. 196

( 5) Conversion of calcium carbonate to calcium sulphate, carbon

dioxide, and water :
1 molecule 1 molecule 1 molecule 1 molecule 1 molecule
CaCO3 + H2SO4 CaSO4 + CO2 + H2O
Wt. 100 Wt . 98 Wt . 136 Wt . 44 Wt. 18

If 196 parts by weight of sulphuric acid are required to convert

310 parts of tricalcium phosphate into monocalcium or soluble phos
phate , then 0.632 part of acid will be required for every 1 part of tri
calcium phosphate. If we use ordinary “chamber acid ” of 50 ° B.
strength which contains, according to the table on page 5, 62.18
per cent of sulphuric acid , 1.016 parts will be necessary for every 1
part of tricalcium phosphate. 1
In Table III, modified from one prepared by Wyatt,” is given the
quantity of sulphuric acid of various strengths necessary to bring
about the reactions outlined above.
66
Table III. – Weight of chamber acid ”. of various strengths required to convert one
pound of each of the ingredients of phosphate rock into soluble compounds.

Quantity and strength of acid required .

Material acidulated - Ingredient.
48 ° B. 49 ° B 50 ° B. 51 ° B. 52º B. 53 ° B. 54 ° B. 55 ° B.

Lbs . Lbs. Lbs. Lbs. Lbs , Lbs . Lbs . Lbs .

Tricalcium phosphate ( Ca3 (PO4)2 ). 1.060 1.040 1.016 0.992 0.970 0.948 0.927 0.907
Calcium fluoride (CaF2) . 2 , 117 2.067 2. 019 1. 972 1.928 1.885 1. 843 1. 803
Iron phosphate ( FePO4 ) . 1.640 1.601 1.564 1.528 1.494 1.460 1.428 1.397
Aluminum phosphate (AlPO4).. 2.023 1. 975 1 , 929 1.885 1.842 1.801 1. 761 1.723
Calcium carbonate ( (CaCO3 ) . 1. 652 1. 613 1.576 1.539 1.504 1.471 1. 438 1.407

Table IV gives the quantities of sulphuric acid of various strengths

required for every 100 pounds of the phosphate rock.
TABLE IV. — Quantities of “chamber acid ” required ( theoretically) to convert 100 pounds
of Florida hard rock phosphate into acid phosphate .
Strength and quantities of acid required
for 100 pounds of rock.
Components of rock. Per cent.
48 ° B. 50 ° B. 52 ° B. 54 ° B.

Pounds. Pounds. Pounds . Pounds.

Tricalcium phosphate (Ca3( PO4)2) 80.0 84.8 81.3 77.6 74.1
Calcium fluoride, (ÇaF2) . 4.5 9.5 9.1 8.7 8.3
Iron phosphate, ( FcP04).
Aluminum phosphate, ( AlPO4). 6.0 12.1 11.6 11.1 10.6
Calcium carbonate, (CaCO3). 3.5 5.8 5.5 5.3 5.0
Silica , ( SiO2) . 5.5
Moisture, ( 8,0 ) . .5

Total .. 112.2 107.5 102.7 98.0

1 Phosphates of America .
16 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE ,

It has been found, however, that the quantity of sulphuric acid

theoretically required to convert phosphate rock into acid phosphate
does not always produce the best results. The physical condition of
the acid phosphate is just as important as its chemical composition ,
and sometimes the proper mechanical condition can not be obtained
except by sacrificing some of the water- soluble phosphate. In factory
practice it is often well, therefore, to add a little less sulphuric acid
than is necessary to satisfy the equations outlined above.
The strength of sulphuric acid used is another detail of great impor
tance in the production of acid phosphate. The quantity of strong
acid sufficient to bring about the desired chemical reactions is of such
small bulk and has such a viscosity that it is difficult to obtain an
intimate mixture with the ground phosphate; moreover, the calcium
sulphate produced, being much less soluble in strong than in weak
sulphuric acid , forms a relatively insoluble coating over the phos
phate, preventing further action by the acid .
On the other hand , if very dilute acid is employed, the amount
required to bring about the necessary chemical reactions is so great
and so much water is contained therein that it is almost impossible to
obtain a product in good mechanical condition. The strength of acid
with which the best results are ordinarily obtained ranges from 50 °
to 55 ° B. , though phosphates very high in iron and aluminum com
pounds sometimes yield better to slightly stronger acid .
There is considerable difference of opinion concerning the tempera
ture at which sulphuric acid should be added to phosphate rock .
Some manufacturers, however, give little heed to this important
point, mixing their acid and rock in the same proportions winter and
summer at whatever temperature the air happens to be. Others
believe in heating the acid to 50 ° to 55 ° C. before using, while many
others claim it is bad practice to use acid at a temperature below 25 °
or above 30 ° C.
It is obvious that this matter should not be disregarded entirely ,
for in mixing acid and rock either very low or excessively high tem
perature may seriously affect the product. No definite rule, however,
can be prescribed, for here again the composition of the phosphate
-

used is the controlling factor.

Phosphates containing large quantities of carbonates heat up
rapidly when mixed with sulphuric acid . If the mixture becomes
very hot violent frothing occurs and the mass is apt to overflow from
the pan. Rocks of this type should not be treated with hot acid .
When dealing with phosphates high in compounds of iron and alumi
num, however , it often saves time to use acid heated to a temperature
of 50 ° to 55 ° C. The reactions then begin promptly in the pan and
1 Bul. 33, Bureau of Soils, U. S. Dept. of Agr., pp . 41-42 (1906 ).
 CONSTRUCTION
Bul . 144 , U. S. Dept. of Agriculture . PLATE I.

2.NTERIOR
ROLL
MILL
RING
IFig
OF
.-
le amin
S so gre
possiblet
gth of sci
from 3

temper
nate rod OPERATION
CLOSED
EADY
importar
ROLL
MILL
1.ING
FOR
Fig
R.-

inter 20
Other
nile mant
below 3

entire!
nigh ten
howerer,
hosphate
VIR

heat up
becomes
ow from
ot acid.
 Bul . 144 , U. S. Dept. of Agriculture .
PLATE II .

FIG. 1. - CONSTRUCTION OF ANOTHER TYPE

OF RING ROLL MILL.

FIG. 2. - RING ROLL MILL IN OPERATION.

H

HEAD
RING
7100

S
ROL

RO
 THE MANUFACTURE OF ACID PHOSPHATE . 17

the mixture can be dumped without fear of its cooling before the final
chemical changes take place.
MIXING THE ACID AND ROCK.

When the manufacture of acid phosphate was first suggested by

Liebig, and for many years afterwards, the mixing process was all
done by hand. Certain proportions of acid and rock were dumped
into shallow , open pits or troughs and worked with hoes in a manner
similar to that in which mortar is mixed. The material was then
allowed to stand in the pit until the chemical reactions were complete
and the superphosphate dry enough to be dug out. The modern
factory process has almost entirely displaced this pioneer method of
making acid phosphate. Machines are now employed which are
capable of mixing efficiently, in two to five minutes, quantities of
rock and acid weighing from 1 to 2 tons .
There are several types of mixers or acidulators used in this country ,
and the following general description applies to almost all of those
ordinarily employed : A cast-iron revolving pan from 4 to 8 feet in
diameter and from 1 to 2 feet deep is driven by pinions. The pan is
equipped with either one or two agitators or stirring devices which
consist of heavy iron spiders having four arms fitted with steel plows.
These stirrers are driven by bevel gears. In the center of the pan is
the discharge hole , which is closed by a valve operated by a lever.
This same lever also controls a scraper which is lowered into the pan
as the plug is raised. Figures 1 and 2 , Plate IV, show the construc
tion of an efficient acidulator .
The weighed charges of acid and rock are run into the revolving
acidulator at the same time and stirred for at least two minutes or
until an intimate mixture is obtained . The lever which controls the
scraper and discharge valve is then lowered and the material ejected
into the “ den ” directly below or into a car which hauls it to the
storage shed and dumps it on a pile.
Both the “ den " and " open dump " systems of making acid phos
phate are employed in this country. Each has points to recommend
it and each has certain objectionable features.
THE DEN SYSTEM .

This system was devised in order that the reactions between the
phosphate rock and sulphuric acid might take place rapidly and
yield a dry, pulverulent product of high availability (so called ) in the
least possible time.
As fast as the charges of acid and rock are mixed they are dropped
into a closed , brick -lined chamber (den) , which is filled to within a
short distance of its top . Here the chemical reactions taking place
18 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE ,
raise the temperature to 120 ° to 250 ° C. Carbon dioxide, steam , and
gaseous compounds of fluorine work their way out of the mass and
escape through the flue at the top of the chamber, leaving the acid
phosphate in a dry, porous condition .
After standing in the den for about 24 hours the reactions are
practically complete and the material is ready to be removed. The
heavy wooden doors at opposite sides of the den are then opened and
the acid phosphate is removed. Frequently the floors of the den
are so constructed that they can be opened and the acid phos
phate discharged into a hopper or upon an acid-proof belt beneath,
whence it is taken up by elevators and dumped on the storage pile.
The emptying of the den is not only a disagreeable operation , but is
attended with considerable danger. The temperature of the acid
phosphate contained therein , even after standing from 24 to 36
hours, is still very high (from 130° to 150° C.) , and the fumes given
off by this hot material are quite poisonous. Great care must be
exercised in digging out the phosphate to prevent large masses of the
loose material from falling upon the laborers .
In order to do away with these dangers efforts have been made to
empty the dens mechanically. A number of processes have been
devised 1 in most of which the excavator or cutter is introduced into
the chamber after the acid phosphate is cured. Special forms of
chambers are required in some of the processes , while in others the
excavating device is adaptable to almost any form of den after the
latter has undergone some slight alterations. The more general
scheme of emptying the dens mechanically is as follows:
A device consisting of an endless chain, which either rotates on a
shaft or can be moved laterally in the den, is fitted with knives or
teeth which cut or break up the acid phosphate and at the same time
convey it to a chute. This device is either introduced horizontally
at the top of the den or vertically at the side. In the former case
the cutter is so arranged that it is mechanically lowered or sinks
automatically after completing the circuit of the chamber. If the
cutter is introduced vertically at one end of the chamber it cuts
away the pile of acid phosphate from the side . It is claimed that the
latter method is less likely to cause the material to pack. The
removal of acid phosphate mechanically seems to be ordinarily a
rather slow process, since the cutters or scrapers, if run at any
great speed , cause the material to become heated and gummy.
One process of emptying the dens more rapidly consists of a combined
cutter and fan. The latter helps keep the material cool while exca
vation is going on . Another method of emptying the den consists
of having the floors mounted on rollers so that one side of the chamber
may be swung open and the whole mass of acid phosphate wheeled
U.S. Patents 892,593 , 899,042, 940,583, 949,055, 956,792, 1,013,334, 1,037,464, 1,033,854, 1,070,296.
 THE MANUFACTURE OF ACID PHOSPHATE . 19

out and broken up where there is a good circulation of air. Me

chanical excavators have not been successfully worked in the factories
of this country, however, and the old -style chamber or den is employed
almost entirely.
The den system is the only one which can be successfully employed
where it is necessary to absorb the fumes given off in the manufacture
of acid phosphate . Each den is equipped with a flue near the top,
which allows the gases and vapors from the freshly made acid phos
phate to escape or be drawn off by means of a fan. The flue leads
into a washer or scrubber, which consists either of aa wooden tower in
which jets of water are constantly spraying or of a number of com
partments through which the gases are made to circulate while they
are continually sprayed with water. Under such conditions the
gaseous compound silicon tetrafluoride is decomposed with precipita
tion of silica and formation of hydrofluosilicic acid, as shown in the
equation on page 8. The hydrofluosilicic acid, together with any
hydrofluoric acid which may have escaped from the mass of acid
phosphate, is absorbed by the water. The acid solution thus pro
duced is used to some extent in the manufacture of fluosilicates of
the alkalies which are used in the production of enamel.
Both the initial cost and running expenses of the “ den ” system are
greater than those of the “ open -dump" method, but a high-grade
product in excellent mechanical condition can be obtained in a
short time by the former method without allowing the objectionable
fumes to escape into the atmosphere . Most factories are equipped
with at least two dens (sometimes four) built close together, with
the acidulator or mixer placed on the dividing wall above them . In
this way work can be carried on with little interruption, for while
one den is being emptied the other may be filled. The capacity of
the dens varies from 50 to 300 tons, depending on the size of the
mixing plant. THE OPEN - DUMP SYSTEM .

The “ open-dump" method is largely used in the South Atlantic

States . The mixture of acid and rock is discharged into an auto
matic dump car and carried to the storage shed , where it is dumped
on an open pile. In order that the chemical reactions may get a fair
start before the mixture spreads out in thin layers, it is allowed to
heat up and thicken somewhat in the mixing pan ; frequently it is
permitted to remain in the dump car until it has nearly set. Many
operators, however, claim to obtain good results by dumping the
material almost immediately. Sometimes, in order to prevent the
acid phosphate from spreading, a partly open bin is employed. The
material after standing in this bin for 8 or 10 days is taken up by
elevators and dumped on a storage pile.
The acid phosphate made by the “ open -dump" method naturally
takes much longer to arrive at its maximum availability and optimum
20 BULLETIN 144 , U. S. DEPARTMENT OF AGRICULTURE .

mechanical condition. It is usually kept for at least one month be

fore shipping, but adverse weather conditions may delay shipment
considerably longer and even seriously affect the quality of the final )
product. The production of acid phosphate by the " open-dump"
method is impracticable in the vicinity of towns or in a rich farming
country unless phosphate rock very low in fluorine compounds is used,
for the fumes given off during the process are not only so obnoxious
as to constitute a nuisance, but are quite injurious to both animal
and vegetable life. At points where these fumes do no harm , how
ever, and where the climate is not too cold , an excellent product is
obtained by this method at less cost and with less danger than by
the “ den ” system .
THE DRYING OF ACID PHOSPHATE .

Acid phosphate which is carefully made, especially that produced

by the " den " system , seldom requires any subsequent drying. It is
customary abroad, however, to dry superphosphates artificially, par
ticularly when they contain an excess of phosphoric acid or are in a
poor mechanical condition due to improper mixing. There are two
general methods employed in drying acid phosphate. The first con
sists of the application of artificial heat and the second of adding
some material to take up or combine with the water or free phos
phoric acid present.
In Europe a number of machines for artificially drying acid phos
phate have been patented . Among the most efficient of these are
the dryers of Lutjens and of Moller and Pfeiffer.1 In both of these
machines the disintegrated acid phosphate is submitted to the action
of a current of hot air under pressure. No direct heat can be used
in drying acid phosphate because of the tendency of the material to
revert at high temperatures .
The second method of drying acid phosphate is often practiced in
this country when the material is too sticky or wet (due to faulty
manipulation ) to be uniformly spread on the field or mixed with
other fertilizer ingredients. Such a condition when due to an excess
of phosphoric acid can be frequently remedied by mixing the sticky
mass with small percentages of phosphate rock or limestone. If the
condition is due to the presence of a large proportion of iron and
aluminum , the addition of finely ground peat or calcined gypsum
will dry the material. In expelling the water from acid phosphate
by artificial heating the value of the fuel consumed must be added
to the cost of production, but no matter how the drying is done it
entails additional handling, which is always expensive and should be
avoided .
1 Fritsch , Manufacture of Chemical Manures, pp. 123-129 (1911 ).
 THE MANUFACTURE OF ACID PHOSPHATE . 21

STORING THE ACID PHOSPHATE.

In order that the acid phosphate produced may contain a maximum

quantity of soluble phosphoric acid when ready for shipment, it is
usually stored in well- ventilated buildings for at least two weeks.
During this time the quantity of the so -called available phos
phoric acid should steadily increase. This is especially true of prop
erly mixed acid phosphate made by the “ open dump" method where
the heat is not sufficiently great to bring about rapid chemical
reactions .
On the other hand, the storing of acid phosphate for protracted
periods in large piles often seriously impairs its mechanical condition
and sometimes its chemical composition. The pressure exerted on
the material in the lower part of the heap, coupled with its con
traction as the mass cools, tends to pack it. When the formation of
gypsum is still in progress the superphosphate often becomes so
closely cemented that it is difficult to break up. Again, improperly
mixed acid phosphate or that high in compounds of iron and alumi
num when closely packed is very apt to become gummy or to revert.
Porter 1 states that in making acid phosphate by the “ open dump”
method the material should not be discharged on the pile until it is
stiff enough to " set up."
The storing of acid phosphate in medium -sized piles, however,
should cause no trouble , provided it is not allowed to stand too long
and the climatic conditions are not unfavorable. Even when the
material improves by storing it is hardly economical to keep it over
a few months, as the interest on the money invested more than
counterbalances the added value of the product due to the increase
in available phosphoric acid .
In Table V, the figures of which are taken from Fritsch, the
changes taking place in stored acid phosphate made from three
different samples of Tennessee phosphate (A, B, and C) are shown.
TABLE V. - Changes taking placein acid phosphate madefrom Tennessee rock on storing
from 2 to 41 months.

Composition .

Directly aſter mixing. After storing for 2 } months. After storing for 4 } months.
Sample.
P205. Fe2O3 + Al2O3. P205 . Al2O3 + Fe2O3. P205 . Al2O3 + Fe2O3.

Insol . Insol . Sol . Insol . Insol . Sol . Insol. Insol . Sol .

Per cent. Per cent. Per cent. Per cent. Per cent. Per cent. Per cent. Per cent. Per cent.
A. 2. 27 1.16 2.35 1. 21 0.82 2.30 1.00 1.31
B. 2. 20 1.05 1.34 2.33 1. 20 1.05 2. 23 1.12 1.30
C. 1.98 1.01 1.57 2.32 1.17 1.31 2.48 1. 12 1.38

?
1 Jour. Ind. Eng. Chem. , 3, 108 ( 1911 ). 2 Manufacture of Chemical Manures, p . 137 ( 1911 ) .
22 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .
It is not stated whether the acid phosphate was made by the " open
dump” or “ den ” method, but an inspection of the table will show
that little change has taken place in the material after keeping several
months. In Table VI are given the analyses of two piles of acid
phosphate sampled after standing certain definite periods of time.
The acid phosphate in both cases was made by the " open -dump"
system .
TABLE VI. - Analyses of acid phosphate from two piles after standing for certain periods.
Available Insoluble
Time of storage. phos- phos Moisture .
phoric phoric
acid . acid,

No. 1 : Per cent. Per cent. Per cent .

3 days . 15.70 2.05 12. 80
10 days . 16.63 1.02 12. 70
6 months . 16.93 .47 13. SO
No. 2 :
13 hours . 15. 55 1.50
3 days . 15.70 1. 80 12.60
6 months . 17.19 .18 13. 94

Although the percentage of available phosphoric acid continued to

increase after storing the material for several months , this increased
availability was largely offset by a corresponding rise in the moisture
content of the product.
DISINTEGRATING THE ACID PHOSPHATE.

Before acid phosphate can be bagged and shipped it must be broken

up and put through coarse sieves . In the case of superphosphate
which has been carefully made it often suffices to throw the material
by means of shovels upon inclined screens , the force of the impact
being great enough to disintegrate the lumps. When dealing with
acid phosphate, however, which has been improperly made or stored
for a long time, it is often necessary to use a machine for breaking up
the material. The ordinary crushing devices do not answer for this
purpose, owing to the tendency of the acid phosphate to pack or be
come sticky when pressure is applied , so disintegrators of a special
type must be employed .
In aa machine like that shown in Plate V, figures 1 and 2, complete
pulverization is brought about by submitting the material to innu
merable shocks , but in such manner that no opportunity is given the
acid phosphate to pack or gum together.
The disintegrator consists of a number of concentric cages made up
a

of steel bars, all of which are inclosed in a casing. The cages are
usually four in number, the first and third attached to a shaft which
revolves in one direction and the second and fourth attached to
 THE MANUFACTURE OF ACID PHOSPHATE. 23

another shaft having the same axis but revolving in the opposite
direction . The casing can be readily opened and the cages slid apart
and cleaned , as shown in Plate V, figure 2 .
The acid phosphate is fed through a hopper into the inner or smallest
2 revolving cage and is thrown by centrifugal force against the bars and
into the second cage, which is revolving in the opposite direction,
From the second it is thrown into the third and then into the fourth,
finally being discharged from the machine thoroughly disintegrated
by the numerous impacts it has received. Two scrapers fitted to the
outside cage prevent the material from adhering to the casing and
clogging the machine.
After disintegration the acid phosphate is ready to be bagged or
mixed with other ingredients to make a complete fertilizer.
COST OF PRODUCTION.

The cost of producing acid phosphate depends on a number of

factors, which vary widely. These are the size , location, and equip
ment of the plant and the cost of the sulphuric acid employed in the
process .
The use of rock mills which grind the largest quantity of rock with
the least expenditure of time and power and the employment of
mixers having a capacity of 2 tons instead of 1 ton tend to reduce
the cost of acid phosphate per ton. Plants located at seaports,
where the cost of manufacturing sulphuric acid is less and the price
of Florida rock usually lower, can often produce acid phosphate
cheaper than those located at inland points . On the other hand,
factories located at inland points which are within easy access of
the phosphate fields can obtain their phosphate rock cheaper than
those more distant from the source of supply. Again, those plants
which have their own acid factories can manufacture sulphuric acid
cheaper than it can be bought by companies which do not make
their own acid .
The initial cost of producing acid phosphate by the den system is
greater than by the open -dump method , but since the material can
be shipped much sooner when made by the former method, the
greater cost is compensated somewhat by the more active capital.
At inland points, such as Atlanta, Augusta, and Birmingham , the
cost of producing acid phosphate (16 per cent citrate soluble) , exclu
sive of oſlice expenses, varies from $6.75 to $8 per ton . At seaports,
such as Charleston, Savannah, Baltimore, and Norfolk , the cost
ranges from $6.20 to $7.50 per ton . In Table VII is given the cost
of producing acid phosphate at a plant running under good condi
tions located at a seaport and using Florida phosphates.
24 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .

TABLE VII. — Average cost per ton ( 2,000 pounds) of acid phosphate manufactured in a
den -system plant located at sea port and running at full capacity of 500 tons per week .
Phosphate rock (1,133 pounds), at $5.09 per ton .. $ 2.576
Sulphuric acid (1,080 pounds) , at $4.75 per ton .. 2. 565
Direct labor...... . 264
Five-eighths superintendent's salary . .091
Power, oil , and waste .... .232
Insurance on $60,000 , at 1.55 per cent.. .035
Taxes on $75,000 , at 1.25 per cent.. .036
Depreciation on $60,000, at 10 per cent . .231
Interest on $75,000, at 6 per cent .... .173

Total cost per ton . 6. 203

The figures given in Table VII were compiled from data obtained
through personal inspection of the principal fertilizer factories of
the South and East . The costs do not include overhead charges,
which vary greatly according to the size and number of the plants
run by a company .
DISPOSAL OF PRODUCT.

Acid phosphate is sold on the basis of its so -called available phos

phoric -acid content, and is worth f. o . b . the factory from 40 to 56
cents per unit, depending on the location of the plant and grade of
the product.
The availability of phosphoric acid is determined by its solubility
in a solution of ammonium citrate. There seems to be no scientific
basis for the assumption that the amount of phosphoric acid thus
dissolved is equivalent to the quantity which is readily available to
crops . It is, however, a convention accepted by the fertilizer trade
as well as by many agronomists and agricultural chemists .
The phosphates of South Carolina (27 per cent P,03) and those of
northern Africa (26 to 30 per cent P,0z) yield as a rule acid phosphate
containing 14 per cent available phosphoric acid .
Florida land -pebble phosphate gives an acid phosphate containing
16 per cent of available phosphoric acid, and the highest grade rock
from Florida, Tennessee , and certain islands in the Pacific Ocean
( containing from 35 to 38 per cent P,0z) yield a product containing
from 18 to 21 per cent of available phosphoric acid.
Acid phosphate is usually put up in 200 -pound sacks and shipped
in closed box cars . The sacks are treated with a solution of silicate
of soda, paraffin , or some other substance to prevent the acid phos
phate from acting upon them .
The latest official figures on the output of acid phosphate are those
for 1909 , which show a total production of 3,062,834 tons. It is
needless to say that the production has increased enormously since
these figures were compiled.
1 The unit is 1 per cent of a ton, or 20 pounds. One ton of 16 per cent acid phosphate contains 320
pounds P206.
 MI Bul . 144 , U. S. Dept. of Agriculture . PLATE III .

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Bul . 144, U. S. Dept. of Agriculture . PLATE IV .

AKT

FIG. 1. - FAN FOR MIXING ACID PHOSPHATE .

JAN
Fig . 2. - FRONT OF PAN BROKEN AWAY TO SHOW INTERNAL CONSTRUCTION.
Bul . 144 , U. S. Dept. of Agriculture . PLATE V.

Fig. 1.-ACID PHOSPHATE DISINTEGRATOR CLOSED- READY FOR USE.

A
A

FIG. 2. -ACID PHOSPHATE DISINTEGRATOR OPEN TO SHOW CONSTRUCTION AND

ACCESSIBILITY .
 THE MANUFACTURE OF ACID PHOSPHATE . 25

DOUBLE ACID PHOSPHATE.

The double acid phosphate now marketed contains from two to

three times as much soluble phosphoric acid as ordinary superphos
phate, and is therefore very valuable in the manufacture of concen
trated fertilizers. Before the discovery of extensive deposits of
high -grade phosphate rock, both in this country and abroad, the
making of double superphosphate was widely practiced, since it
afforded a ready means of utilizing low - grade phosphates . Now,
however, most of the commercial rock is so high in phosphoric acid
that it is unnecessary to resort to schemes for enriching the soluble
product obtained therefrom , but in Germany, France, and several
other foreign countries, as well as in the State of South Carolina,
where a comparatively low grade of phosphate is mined, this process
is still used with considerable success .
The two main chemical reactions involved in the manufacture of
double acid phosphate are : First, sufficient dilute sulphuric acid is
added to phosphate rock to convert the hypothetical tricalcium
phosphate into phosphoric acid and gypsum ; and second, the phos
phoric acid thus obtained is used to convert the tricalcium phosphate
of aa fresh supply of rock into monocalcium phosphate . The reactions
in their simplest form may be represented thus :
( 1 ) Caz(PO .)2 + 3H ,SO , = 2H2PO4 + 3CaSO,
(2 ) 4H2PO4+ Caz(PO4) 2 = 3CaH (PO4)2
The process, however, is by no means as simple as it at first appears,
for there are several distinct operations which not only require the
watchfulness of a competent superintendent but the control of a
skillful chemist.
The phosphate rock and dilute sulphuric acid (16 ° B.) are run into a
vat simultaneously and stirred thoroughly for 15 or 20 minutes. It
is inadvisable to use warm acid to decompose the rock or to stir for a
protracted period, since under such conditions the compounds of
iron and aluminum are dissolved only to be precipitated again later
on , causing the reversion of a part of the phosphoric acid. The
quantity of sulphuric acid required to bring about the desired reac
tions should be carefully ascertained from analyses of the raw material,
since either an excess or an insufficient quantity will cause trouble
in the subsequent operations.
The muddy solution is run into a tank from which it is pumped to a
filter press where the sediment and gypsum is separated, the clear
phosphoric-acid solution being run into evaporating pans. The
residue in the filter press is then washed with water till the washings
have a concentration of 0.25 ° B. or less. These washings are used to
dilute the sulphuric acid employed in the process.
26 BULLETIN 144, U. S. DEPARTMENT OF AGRICULTURE .

Before the phosphoric acid produced can be used for making

double acid phosphate it must be concentrated. This is usually done
by evaporating in iron pans lined with stone or some acid - resisting
material. After concentrating to about 56 ° or 58 ° B. , it is run into
lead - lined tanks from which it is drawn or pumped as required.
The mixing of this phosphoric acid with phosphate rock and all sub
sequent operations are practically the same as those employed in
making ordinary acid phosphate, but the final product often has to
be artificially dried since it contains but a small percentage ofgypsum .
Ordinary acid phosphate, as we have seen, is largely a mixture of
soluble lime phosphate and gypsum , the latter having been formed
from calcium sulphate by extracting the excess of water from the
mass . Double acid phosphate, however, consists chiefly of soluble
lime phosphate with but little calcium sulphate to act as a dehy
drating agent, and therefore requires artificial heating to drive off
the excess of water.
SUMMARY.

The general procedure followed in making acid phosphate involves

numerous details of great economic importance which are not
thoroughly understood .
The raw phosphatic materials which have been used in the acid
phosphate industry are bone, guano, apatite, and phosphate rock.
Of these substances the last named has practically displaced the
others as a source of phosphoric acid.
The process of making acid phosphate was devised in order to
produce phosphoric acid in a soluble, or so -called “ available ,” con
dition ; this done by the action of sulphuric acid on tribasic phos
phates whereby less basic and more soluble phosphates are produced.
A knowledge of the composition of the raw materials is of the
greatest importance in the manufacture of acid phosphate, since
not only the phosphate of lime but all the impurities contained in the
rock are acted upon by sulphuric acid and influence the composition
and physical condition of the finished product.
Much phosphate rock contains organic matter which consumes a
certain amount of sulphuric acid, but owing to the various forms in
which this material occurs it is almost impossible to determine
except by actual trial the quantity of acid required to decompose it.
Silica is acted upon only indirectly by sulphuric acid.
Calcium fluoride, which is present in nearly all phosphate rock,
is acted upon by sulphuric acid, resulting in the formation of gaseous
hydrofluoric acid . This gas in turn acts upon silica and silicates,
producing silicon tetrafluoride. The silicon tetrafluoride is decom
posed by water, forming hydrofluosilicic acid and silica. The
 THE MANUFACTURE OF ACID PHOSPHATE , 27

presence of fluorides is objectionable because of the obnoxious

fumes evolved in treating with acid ; otherwise this impurity is not
objectionable.
Compounds of iron and aluminum are the most dreaded of the
impurities occurring in phosphate rock. These elements when
present in small quantities are very apt to cause a certain amount of
reversion to take place, and when present in large quantities may
render the product sticky and unfit for use. By careful' handling,
however, phosphates high in iron and aluminum compounds may be
made to produce high-grade acid phosphate.
Carbonate of lime, which is present in nearly all phosphate rock, is
a rather desirable impurity when the quantity is not excessive . The
decomposition of this compound by sulphuric acid is attended with
considerable heat which promotes chemical reaction between the
more slowly acting substances in the mass ; moreover, the calcium
sulphate produced therefrom acts as a drier for the acid phosphate.
In the manufacture of acid phosphate the rock is first ground to
pass a 60 -mesh sieve, and then mixed with an equal weight (approxi
mately) of " chamber acid.” The quantity, strength, and tempera
ture of acid used have an important influence on the quality of the
product .
After thorough mixing in a cast - iron pan the material is discharged
into a “ den ” just below the mixer or into a car which takes it to a
shed and dumps it on a pile. When the “ den ” system is used the
reactions take place rapidly and the product can be dug out in 24 to
36 hours, practically ready for shipment. The method of emptying
the " dens " by hand , however, is attended with some risk owing to
the poisonous nature of the fumes evolved from the freshly made acid
phosphate and to the danger of large masses of the material falling on
the laborers .
In the “ open dump" system the acid phosphate requires a long
time to reach its maximum availability, and unless it is properly
made may never be fit for use .
The storing of acid phosphate in large piles for protracted periods
sometimes causes reversion owing to the pressure on the material in
the lower part of the pile; this pressure also tends to compact the
material. The storing of well-made acid phosphate in medium -sized
piles, however, should cause no ill effects.
Properly made acid phosphate should require no artificial drying,
since the calcium sulphate formed in the process takes up the water
to form gypsum . It is nearly always necessary , however, to disin
tegrate and screen the material before shipping. This is often done
by simply throwing the product upon inclined screens, but some
times disintegrating machines must be employed .
28 BULLETIN 144 , U. S. DEPARTMENT OF AGRICULTURE .

Acid phosphate is sold on the basis of its so -called available phos

phoric acid, and has a value of 40 to 56 cents per unit. The marketed
product contains from 14 to 21 per cent of phosphoric acid, depending
on the raw material used in its manufacture.
Double acid phosphate is made by treating phosphate rock with
sufficient diluted sulphuric acid to produce free phosphoric acid, and
then using the phosphoric acid thus obtained to decompose a fresh
batch of rock. The final product contains from two to three times
as much phosphoric acid as ordinary acid phosphate, and is very
useful in the making of concentrated fertilizers.

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WASHINGTON : GOVERNMENT PRINTING OFFICE : 1914