United States Patent Office 2,740,115

Eaterated War. 27, 1956

2,748,115 2
Baumé since if a more ccacentrated acid is employed
METHODS OF PRODUCING TRPLE the mass sets so quickly that it cannot be handled. As
SUPERSPEBSPEACE the result of the conventional operation an extremely
Leroy Henry Facer, Phelps, N. Y., assigno, by mesne moist product results which is not self-drying. After a
5 cure of several days in a large pile this mass is still wet and
assignments, to Glen E. Cooley, Schenectady, N. Y.,
Warren Dungara Foster, Ridgewood, N.J., Halfdan must be kiln dried preferably under continuous agita
Gregersen, New York, N. Y., Magazis . Gregersen, tion. This period of cure is necessary because of the slow
Englewood, N.J., and Dasia S. Lara, New York, N.Y.,
trustees action of a weak acid, its moisture is reduced to 2%
or less and the dry mass which results is composed of
No Drawing. Original application July 9, 1942, Serial O hard lumps of various sizes which thereupon must be
No. 456,324. Divided agad his application April 19, crushed and ground. This dry product creates a large
1951, Serial No. 22,931 amount of irritating dust which is so harmful to all who
7 (Clairs. (C. 7-4) have to handle it in mass that respirators or gas masks
must be continuously used and even so unless precau
As is well known to the practitioners of the fertilizer tions are continuously observed much damage to health
art, the three major products of importance in any com results.
plete or mixed fertilizer are nitrogen (N), phosphorus According to the principles set out in my parent ap
(P205), and potash (K2O). The material most widely plication by the use of phosphoric acid more concentrated
used as a source of phosphates, either in a mixed fer than that used in the prior art I am able to make a triple
tilizer or alone, is superphosphate. Superphosphate gen 20 superphosphate of an unusually high degree of avail
erally is made by treating ground phosphate rock with ability and water-extractability without kiln or other
sulphuric or other strong mineral acid in order to con artificial drying. I completely dispense with all of the
vert the phosphate in the rock, which is in a form in expensive specialized apparatus and processes which oth
which it cannot
it can be so used.
be used by the piant, to a form in which ers use in this connection and my product at no point
25 in its development is dusty or harmful to workers. While
In my co-pending parent application, Serial Number other practitioners use excess water to keep their mate
450,324, filed July 9, 1942, of which this application is rial from hardening to a point which prevents it from
a division, I describe and claim other processes all de being readily disintegrated and later dry out this ex
pending upon processing a phosphatic or related com cess water, use an excess of concentrated acid in a first
ponent or crae containing a metailic (minor) element 30 stage thereby securing an intermediate product which can
either by a direct use of materials which conventionally be handled and treated mechanically and then add addi
are either wasted or mist be expensively reprocessed for tional phosphate rock to utilize the excess acid. Since
effective use, or by the use of such materials in a man use concentrated acid it operates quickly without neces
ner to produce at one operation both a major product sity for storage for curing purposes. My end product,
and a minor bit important by-product. As in my par 35 without heating or grinding, is in the form of dry pellets
ent application this invention is particularly concerned from which no dust evolves.
with the maximum utilization of a strong mineral acid Another basis of economy in my process is my use of
or acids in a manner which saves time, cost and mate rock ground no finer than that generally employed for
rials. By the use of the principles of this invention, I ordinary superphosphate. For example, I find that in
avoid processes which are expensive in capital, materials, 40 making these concentrated phosphatic products I can
labor and other operating costs and secure a better prod use phosphate rock ground so that 60% passes through
uct, physically and chemicaliy. a screen with one hundred meshes to the inch. I use all
As is well known in the fertilizer industry, so-called of such rock as it comes from the grinding mechanism,
triple superphosphate, which is a much concentrated not separating the fine from the coarse. Rock for use
product containing from 45% to 48% "available phos 45 in making triple superphosphate is now ordinarily ground
phoric acid' considered as P2O5 of which approximately so that from 80% to 90% passes through a hundred
90% is water-extractable and in the form of mono mesh screen. This fine grinding is an expensive opera
calcium phosphate, is made by acidulating phosphate tion. By this coarse grinding, not only save expense, but
rock with phosphoric acid (HaipO4). in the fertilizer also I slow down the reaction (during this mixing opera
industry, the phosphatic content of a fertilizer has long 50 tion) so that the resulting acidulated mass can be han
been called "phosphoric acid” but in fact it is a phos dled much more readily.
phate sait or salts including more or less free acid and In one illustration of my method of producing my
is stated in terms of P2O5. Except as specifically indi triple superphosphate, divide 813 pounds of ground
cated, however, I herein use the term "phosphoric acid' phosphate rock which I am to use into two parts, for
to mean H3PO4. 55 example one of 713 pounds and the other of 100 pounds.
To secure phosphoric acid, phosphate rock is pre I place the larger quantity of rock in an ordinary super
viously acidulated with sulphuric acid to produce phos phosphate mixing pan or like mixer and add to it 1227
phoric acid and gypsum. The phosphoric acid is washed pounds of phosphoric acid of 87% (or correspondingly
from the gypsum and results in a dilute H3PO4 of ap more if an acid of the concentration of 70% or 75%
proximately 41% or 30 Baumé. An amount of phos 60 is to be substituted) and mix in the ordinary way with
phoric acid up to approximately 2% of the weight of the the application of no extra power. Ordinary (conven
gypsum is left therein after the washing process has been tional) phosphoric acid may be employed or that pro
completed. At least 5% of the phosphoric acid is lost. duced in accordance with the novel method which I have
This dilute acid which results from this process before described in my said parent application and described and
it can be used for making triple superphosphate must be 65 claimed in my copending application Serial Number
concentrated to 60% or 70%-that is, approximately 221,932, filed April 19, 1951, likewise a division thereof.
43 to 50 Baumé. Phosphoric acid is also made by This is purely a mixing operation.
volatization by heat, but this invention is only indirect From the time of completing this first mixing opera
ly concerned with that process.
The conventional method of producing triple super one offorwardly
tion
several
may handle the mass so produced in any
different ways:
phosphate includes the acidulation of phosphate rock with 1. After the mixing operation has been concluded, in
phosphoric acid of no greater concentration than 50 from a minute to two minutes, for example, I may place
 2,740,15
s
e.
4.
the mixture in a den where ieave it for a few minutes found that it is often advantageous to make the above
tintil it hardens. This hardening places the mass in a separation of the phosphate rock on the basis of the
Sifiriently plastic condition to be handled as easily as or side of the particles. As before stated, the rock is ground
dinary superphosphate in the den. Then I disintegrate relatively coarsely. It need not be ground finer than
it and pass it while still hot and steaming, although not for 60% to pass through a hundred mesh screen. Such
as hot as ordinary superphosphate, into a pelleting drum separation on the basis of particle size is particularly use
such as that described in my said co-pending parent ap ful when one uses rocks which present particularly diffi
cult problems of digestion. In such cases I apply the
plication. Thereupon as the drum is revolved I add the entire quantity of the acid to the coarse particles and use
additional hundred potands of phosphate rock. At this 0. finer material for the later step. If the characteristics of
time excess acid which I have used in the mixing pan has the rock and degree of grinding used are such as to pro
come to the surface of the particles and immediately
unites with the ground rock which is added. This rock duce noted
materially more than the 14% of fine material above
I add all but this fraction of the fines to the coarse
adheres to the surface and physically absorbs the acid
which thereupon proceeds to react with the tri-calcium 5 rock and apply to it all of the acid. -
It will be understood that in the above operation no
phosphate to form available P2C5, this crystallization
"drying' the pellet throughout, the coating having estab matter how carried out I over-acidulate the phosphate
rock in the first stage. By adding the second quantity
lished the identity of each pellet. The resulting pellet of ground rock, as described and claimed in other em
is of the type described and claimed per se in my co
pending application Serial Number 432,350 filed February 20 bodimentsthis excess
in my said co-pending applications, I absorb
acid and put it to effective use in converting
24, 1942. unavailable P2O5 to an available form, this chemical action
2. Alternatively I may use a screw conveyor to move in itself drying my pellets. By the over-acidulation of
this acidulated mixture directly from the mixing pan to a relatively coarse rock in the first stage, I am able to main
pelleting drum omitting the intermediate step of permitting tain the entire mass in a sufficiently plastic form to be
it to harden to a plastic state in a den. This conveying handled as easily as ordinary superphosphate.
operation need not take over five minutes because by that Particular note should be made of the fact that at no
time the mixture will have set sufficiently so that it can point do I apply external heat. There is no kiln drying
be handled as above; that is, I add the additional one
hundred pounds of phosphate rock late in the pelleting or other form of dehydration. By use of excess acid until
the final stage of the operation, keep the mass suffi
operation and during the revolution of the drum.
3. I may empty a mixing pan into a form such as de 30 ciently add more
plastic so that it can be readily handled. Then I
phosphate rock so that the excess acid is utilized
scribed and claimed in my Patent Number 2,061,567,
dated November 24, 1936. After the mass so emptied pellets are therebyof“dried'
in the production additional phosphatic salts and the
and hardened. At no time is
has hardened in the block which is so formed, I may any appreciable amount of moisture driven off. These
scrape the material from the top of the block in the man 35 pellets when fully cured and ready for use, however, have
ner described and claimed in my Patent Number a moisture content of about five percent, in contrast to
2,213,243, dated September 3, 1940, and place it in the the usual two percent. My process avoids the dustiness
pelleting drum as before. It will be understood that this which has caused so much difficulty in the making and
action is a conveying and disintegrating one. handling of triple superphosphate.
4. Again alternatively inay nix the phosphate rock As is known to those skilled in this art triple super
and phosphoric acid as above in a special movable multi 40
purposed den such as shown in Figure 16 of my said phosphate as conventionally produced is high in free acid,
application, Serial Number 432,350, filed February 25, to such an extent that it is difficult to store in bags for
1942, parent to the parent hereof, and after the mixing more than a few weeks. My triple superphosphate, how
operation has been completed remove the paddles there ever, is both low in free acid and that which does persist
from. After a few minutes of hardening to a plastic state is encased within a pellet the exterior of which is without
the paddles may be again introduced and revolved. They free acid. It will be noted that the freedom from dust
both in my manufacturing operation and in the resulting
will gradually dig their way into the mass and disintegrate product arises from the retention as water of crystalliza
it and pellet it at the same time. After the desired degree tion of the moisture which others drive off by heat, there
of pelleting has been secured I add the additional one by breaking down these crystals by dehydration into an
hundred pounds of ground phosphate rock. 50 noying and harmful dust. The curing period in a large
In all of the four methods described above for handing pile necessary in the conventional operation because of
this material, I may add other fertilizing material either the time taken for the weak acid to become effective
to the pelleting druin in forms 1 to 3 inclusive or to the starts this dehydration of the crystals and the later kiln
special movable den of form 4. in connection with form
4 it will be understood that I prefer to use a plurality of 55 drying The
completes it.
following analysis (Wiley No. 156,397-146) may
movable multi-purposed dens so that the entire operation be taken as typical of my triple superphosphate manu
while on a batch basis may be continuously carried factured in the above manner:
forward. Per cent
The above ratio of about seven parts of rock to be first Moisture at 100 C-------------------------- 5,35
mixed with all of the acid to one part cf rock to be added 60 Total phosphoric acid------------------------ 50.20
later is illustrative and not definitive. As is well known
to those skilled in this art, details of treatinent of each Insoluble phosphoric acid--------------------- .04
shipment and each source of phosphate rock vary in ac Available phosphoric acid.-------------------- 50.16
cordance with particle size and chemical analysis, includ Water soluble phosphoric acid----------------- 49.25
ing factors other than B. P. L. As is made clear through 65 . It will be noted that I secure without the application
out this specification I produce Rn intermediate product of external heat a triple superphosphate which is pal
(after the first mixing and before pelleting), which is
sufficiently plastic to be readily handled. Consequently pably dry. For simplicity in the sub-joined claims I state
that the concentration of the acid is such that no more
this ratio of the one portion of rock to the other portion
will be changed in order always to achieve my charac 70 water in the
is present in the finished product than that required
acidulation reacticn with all of the phosphate
teristic physical consistency. Thus the choice of this exact rock employed to produce superphosphate and to furnish
ratio is a matter more of physical than chemical con substantially all of the water evaporated by the natural
sideration. -
As stated at greater iength in my said co-pending ap heat of reaction and all of the water of crystallization re
plication Serial Number 450,324 parent hereto also have quired by the complete hydration of the end product. It
 5 2,740,115
is to be understood, however, that I also seal within 6
each pellet, the exterior surface being dry to the touch, mined quantity of concentrated phosphoric acid with said
an additional amount of moisture, the presence of which Selected major portion of said ground phosphate rock,
is disregarded in the claims. the predetermined amount of concentrated phosphoric
It will be readily understood by those skilled in this acid being the amount sufficient to react with all of the
art that my process as described and claimed herein said predetermined quantity of ground phosphate rock
may be advantageously applied to the manufacture of and in excess of the amount sufficient to react with said
Superphosphate of any desired quantity of P2O5 greater Selected major portion of said phosphate rock, and the
than twenty percent (within the chemical upper limits), concentration of the said phosphoric acid being above
twenty percent being the figure which can readily be 10 about 50 Baumé and sufficiently high to limit and con
reached by the acidulation of phosphate rock by sulphuric trol the amount of water present to that required by com
acid. For simplicity in the sub-joined claims I am using plete reaction of the entire predetermined quantity of
the term "triple superphosphate' to include any super ground phosphate rock and the entire predetermined
phosphate containing a percentage of P2O5 greater than quantity of phosphoric acid, and to furnish water of
that which can be obtained by the directed use of sul 5 crystallization of the triple superphosphate produced
phuric acid. after loss of water evaporated by the natural heat of re
It will be understood that by the above process I se action; disintegrating the mass formed by said mixing
cure a triple superphosphate both of a higher degree of and reaction of said phosphoric acid and said selected
availability than that common at present and also one major portion of said rock to form disintegrated small
particles which are chemically active and over-acidulated;
which has a higher ratio in percent of its available P205 20 Subjecting
in water-extractable form and in addition has the pe to form coalesced said disintegrated small particles to movement
culiar crop-producing capacity which is explained at larger particles of desired size; and
length in my said parent applications. I completely avoid thereafter adding the said minor portion of said prede
the expensive process of kiln drying and the product is termined quantity of ground phosphate rock to coat the
not dusty and harmful to health, 25 said coalesced larger particles, thereby reacting said minor
Although I am presenting for purposes of illustration portion of said ground rock with the said excess quantity
only certain preferred embodiments of my invention it particulateof phosphorictripleacid to form substantially dry, coalesced
superphosphate.
will be readily understood that changes may be made 3. A process of manufacturing particulate triple super
therein within the spirit of my invention and the scope phosphate which comprises: dividing a predetermined
of my broader claims. The advantages of this inven 30 quantity of ground phosphate rock into a selected major
tion will be clear from the above discussion and the ap and a minor portion; mixing and reacting a predeter
pended claims. These advantages include the production
of triple superphosphate of unusually high availability mined quantity of concentrated phosphoric acid with
and water-extractability after a short curing period and said selected major portion of the said ground phosphate
with low free acid, cheaply, simply, without kiln or other phoricrock, the predetermined amount of concentrated phos
artificial drying and without the development of dust. acid being the amount sufficient to react with all
Practice of my invention results in an end product which of the said predetermined quantity of ground phosphate
is pelleted and has the high crop-producing capacity of said rock and in excess of the amount sufficient to react with
the parent of my said parent application. selected major portion of said phosphate rock, and
I claim: 40 the concentration of the said phosphoric acid being be
1. A process of manufacturing triple superphosphate tween about 70% and about 87% acid and sufficiently
in particulate form which comprises: dividing a prede high to limit and control the amount of water present
termined quantity of ground phosphate rock into a se to that required by complete reaction of the entire pre
lected major and a minor portion; mixing and reacting a determined quantity of ground phosphate rock and the
predetermined quantity of concentrated phosphoric acid entire to
predetermined quantity of phosphoric acid, and
furnish water of crystallization of the triple super
with said selected major portion of the said ground phos phosphate produced after loss of water evaporated by
phate rock, the predetermined amount of concentrated
phosphoric acid being the amount sufficient to react with the natural heat of reaction; disintegrating the mass.
all of the said predetermined quantity of ground phos formed by said mixing and reaction of said phosphoric
acid and said selected major portion of said rock to form.
phate rock and in excess of the amount sufficient to react 50 disintegrated
with said selected major portion of said ground phosphate and over-acidulated; small particles which are chemically active
rock, and the concentration of the said phosphoric acid particles to movementsubjecting said disintegrated small
to form coalesced larger particles
being sufficiently high to limit and control the amount
of water present to that required by complete reaction of tion of desired size; and thereafter adding the said minor por
the entire predetermined quantity of ground phosphate 55 rock of said predetermined quantity of ground phosphate
rock and the entire predetermined quantity of phosphoric reacting to coat the said coalesced larger particles, thereby
acid, and to furnish water of crystallization of the triple said excess said minor portion of said ground rock with the
superphosphate produced after loss of water evaporated tially dry, coalesced quantity of phosphoric acid to form substan
by the natural heat of reaction; disintegrating the mass particulate triple superphosphate.
formed by said mixing and reaction of said phosphoric 60 phosphate 4. A process of manufacturing particulate triple super
acid and said selected major portion of said rock to form which comprises: dividing a predetermined
disintegrated Small particles which are chemically active minor quantity of ground phosphate rock into a major and a
and over-acidulated; subjecting said disintegrated small amountportion; mixing said major portion and the entire
particles to movement to form coalesced larger particles 50 Baumé necessary toacid
of phosphoric
form
of the order of more than
triple superphosphate from
of desired size; and thereafter adding the said minor 65 said predetermined quantity of ground phosphate rock
portion of said predetermined quantity of ground phos thereby producing an over-acidulated moist essentially
phate rock to coat the said coalesced larger particles, solid mass which can be readily handled and is disin
thereby reacting said minor portion of said ground rock tegrable in the manner of ordinary superphosphate; dis
with the said excess quantity of phosphoric acid to form integrating said mass into particles; and further process
coalesced particulate triple superphosphate. ing the resulting particles without the addition of external
2. A process of manufacturing particulate triple super heat under conditions avoiding any substantial evapora
phosphate which comprises: dividing a predetermined tion of moisture, and so as to obtain a dry final product,
quantity of ground phosphate rock into a selected major said further processing including adding to the outside
and a minor portion; mixing and reacting a predeter 75 surfaces of the disintegrated particles while still moist
and over-acidulated the said minor portion of said pre
 2,740,115 -w 8
7
determined quantity of the phosphate rock thereby caus which comprises dividing groundpelleted
8. A process of manufacturing superphosphate
phosphate rock into a
ing adherence of said added rock to said moist outside major and a minor fraction, mixing said major fraction
surfaces and its chemical bond thereto, the concentration and the entire amount of phosphoric acid necessary to
of the acid being such as to supply not more than the 5 form triple superphosphate from all of said phosphate
amount of water required in the entire acidulation re rock, placing said over-acidulated mixture in a den and
action while furnishing the water evaporated by the natu leaving it there until it hardens into a plastic mass, dis
ral heat of reaction and the amount required to furnish integrating said mass, and while it is still hot and steam
substantially the full aimount of water of crystallization ing passing it to a pelleting drum and pelleting it with
for the completely hydrated yet dry final product. O the addition of said minor fraction of said rock thereby
5. A process of manufacturing superphosphate which utilizing all of the acidic component of said mass and
comprises grinding phosphate rock into relatively coarse causing the
and fine particles, mixing the coarse particles and the en palpably drypellets to pass from a palpably moist to a
tire amount of phosphoric acid necessary to form triple then unused acid and the
state by
the
chemical reaction between the
freshly added rock by which
superphosphate from all of said phosphate rock thereby almost all of the free moisture present at the beginning
producing an over-acidulated liquid-containing plastic of the pelleting operation becomes water of crystalliza
mass winich can be readily handled, the concentration of tion thereby assuring the integrity of the pellets thereafter.
the acid being such that no more water is present than 9. A process of manufacturing a pelleted superphos
that required in the acidulation reaction with all of the phate which comprises dividing ground phosphate rock
phosphate rock employed to produce superphosphate and 20 into a majorand a minor fraction, mixing said major
to furnish substantially all of the water evaporated by fraction and the entire amount of phosphoric acid neces
the natural heat of reaction and all of the water of crystal sary to form-triple superphosphate from all of said phos
Iization required by complete hydration of the end prod phate rock, disintegrating said mixture after it has hard
uct, and thereafter mixing with said mass said fine par ened into a plastic mass, and pelleting it while it is still
ticles of the phosphate rock thereby utilizing all of the hot and steaming with the addition of said minor frac
acidic component of said mass, thereby combining the tion of said rock thereby utilizing all of the acidic com
remaining free acid and the last added phosphate rock ponent of said mass and causing the pellets to pass from
as superphosphate and converting the entire mass to a a palpably moist to a palpably dry state by the chemical
dry6.and non-coalescent
A process condition. superphosphate which reaction between the then unused acid and the freshly
of manufacturing added rock by which almost all of the free moisture
comprises grinding phosphate rock so that substantially 30 present
sixty percent thereof is relatively fine and the remainder comes water at the beginning of the pelleting operation be
of crystallization thereby. assuring the in
relatively coarse, mixing the coarse particles and the en tegrity of the pellets
tire amount of phosphoric acid necessary to form triple thereafter.
superphosphate from all of said phosphate rock thereby 10. A process of manufacturing pelleted triple super
producing an over-acidulated liquid-containing plastic phosphate which comprises dividing ground phosphate
mass which can be readily handled, the concentration of rock into a major portion and a minor portion, said major
the acid being such that no more water is present than portion being sufficient in amount so that when it has
that required in the acidulation reaction with all of the been mixed with the entire amount of phosphoric acid
phosphate rock employed to produce Superphosphate and necessary to form triple superphosphate from all of said
to furnish substantially all of the water evaporated by phosphate rock it will produce an over-acidulated liquid
the natural heat of reaction and all of the water of crystal
containing plastic mass which can be readily handled,
lization required by complete hydration of the end prod the concentration of the acid being such that no more
uct, and thereafter mixing with said mass said fine par
water is present than that required in the acidulation
ticles of the phosphate rock thereby utilizing all of the reaction with all of the phosphate rock employed to
acidic component of said mass, thereby combining the produce Superphosphate and to furnish substantially all
of the water evaporated by the natural heat of reaction
remaining free acid and the last added phosphate rock as and all of the water of crystallization required by com
superphosphate and converting the entire mass to a dry plete hydration of the end product, mixing said major
and non-coalescent condition.
7. A process of manufacturing particulate triple super portion
and
and all of said acid, mixing said mass so formed
said minor portion of the phosphate rock, and re
phosphate which comprises dividing a predetermined 50 volving said mass upon itself to form pellets, said second
quantity of ground phosphate rock into a major and a portion of said rock being sufficient in amount so that
minor portion, mixing said major portion and the entire the pellets are coated and remaining free acid combined
amount of phosphoric acid of the order of more than as superphosphates and the pellets converted to a dry and
50 Baumé necessary to form triple superphosphate from non-coalescent condition.
said predetermined quantity of ground phosphate rock 53 11. A process of manufacturing a pelleted superphos
thereby producing an over-acidulated moist essentially phate which comprises dividing ground phosphate rock
solid mass which can be readily handled and is disia into a major fraction and a minor fraction, mixing said
tegrable in the manner of ordinary superphosphate, dis major fraction with the entire amount of phosphoric acid
integrating said mass into particles, and further process ile:ressary to form superphosphate from all of said rock,
ing the resulting particles without the addition of external and further processing the resulting mass without the addi
heat under conditions avoiding any substantial evapora tion of heat under conditions avoiding any substantial
tion of moisture and so as to obtain a dry final product, evaporation and so as to obtain a dry final product, the
said further processing including adding to the outside concentration of the acid being such as to supply not
surfaces of the disintegrated particles while still moist R more than the amount of water required in the acidulation
and over-acidulated the said minor portion of said pre 5 reaction of all of said phosphate rock and evaporated
determined quantity of the phosphate rock thereby calls by the natural heat of reaction and the amount required
ing adherence of said added rock to said moist outside to furnish substantially the full amount of water of
surfaces and its chemical bond thereto, the concentration crystallization for the completely hydrated final product,
of the acid being between about 70% and about 87% said further processing including conveying said mixture
acid and being such as to supply not more than the to a rotatable drum, said conveying operation being of
amount of water required in the entire acidulation re
action while furnishing the water evaporated by the natu abecomes
length sufficient so that the said over-acidulated mass
plastic during it, placing said plastic mass and
ral heat of reaction and the amount required to furnish said minor fraction of said phosphate rock in said drum
substantially the full amount of water of crystallization is and revolving said drum to form pellets thereby utilizing
for the completely hydrated yet dry final product.
 2,740,115
all of the acidic component of said mass, the pellets no more water is present thanOthat required in the acidu
being dried by the chemical reaction between the then lation reaction with all of the phosphate rock employed
unused acid and the freshly added rock. to produce superphosphate and to furnish substantially
12. A process of manufacturing superphosphate which all
comprises dividing ground phosphate rock into a major andofalltheofwater evaporated by the natural heat of reaction
the water of crystallization required by com
and a minor fraction, mixing said major fraction and the plete hydration of the end product, said first portion of
entire amount of phosphoric acid necessary to form triple said rock being sufficient in amount so that when all of
Superphosphate from ail of said phosphate rock, pouring
Successive mixtures so formed into successive layers in said acid is added thereto it reduces said rock to a mate
rial which considered in its totality has the characteristics
a form thereby creating a block of over-acidulated super 0. of
phosphate, removing the form, scraping material from ingmoist sand, adding said acid to said first portion, agitat
the top of the block and conveying it to a pelleting drum, said the mass so formed to produce pellets and adding
such scraping and conveying operation being effective masssecond during
portion of said rock to said last mentioned
a later portion of said agitation said second
to place in said drum disintegrated plastic material, and portion of said rock being sufficient in amount so that
mixing said material and said minor fraction of said 5 the pellets are coated and remaining free acid combined
phosphate rock.
13. A process of manufacturing triple superphosphate as superphosphate and the pellets converted to a dry and
non-coalescent condition.
which comprises dividing ground phosphate rock into a 16. A process of manufacturing a pelleted mixed super
k major and a minor fraction, placing in a container said
major fraction and the entire amount of phosphoric acid
necessary to form triple superphosphate from all of said
phosphatic fertilizer which comprises dividing ground
phosphate rock into a major and minor fraction, mixing
phosphate rock, introducing paddles into said container said major fraction and the entire amount of phosphoric
thereby mixing the mass, after such mixing has been acid necessary to form triple superphosphate from all
completed removing said paddles and leaving the mix of said phosphate rock, placing said over-acidulated mix
ture untreated until it has become plastic, re-introducing 25 ture in a den and leaving it there until it hardens into
said paddles into said container and revolving them in a plastic mass, disintegrating said mass, thereupon adding
order to form pellets, introducing into said container said another fertilizer material to said mass, and while the
minor fraction of said phosphate rock and continuing mixture so formed is still hot and steaming from said
such agitation so that the pellets are coated whereby they original mixture of phosphate rock and phosphoric acid
are dried by chemical reaction between the freshly added passing the combined mixture to a pelleting drum and
rock and the then unused acid. pelleting it with the addition of said minor fraction of said
14. A process of manufacturing a pelleted superphos rock thereby utilizing all of the acidic component of said
mass and causing the pellets to pass from a palpably moist
phate of relatively high phosphatic content which com to
prises separating ground phosphate rock into a first por theathen palpably dry state by the chemical reaction between
tion and a second portion, said first portion including almost allunused acid and the freshly added rock by which
of the free moisture present at the beginning
relatively coarse rock particles and said second portion of the pelleting operation becomes water of crystalliza
consisting only of relatively fine rock particles, mixing tion thereby assuring the integrity of the pellets there
said first portion with an acid solution which contains after.
an acid of phosphorus in an amount sufficient to acidu 17. A process of manufacturing a complete pelleted
late said entire amount of said rock, the concentration 40 mixed
of the acid being such that no more water is present than groundsuperphosphatic fertilizer which comprises dividing
phosphate rock into a major and minor fraction,
that required in the acidulation reaction with all of the mixing said major fraction and the entire amount of phos
phosphate rock employed to produce superphosphate phoric acid necessary to form triple superphosphate from
and to furnish substantially all of the water evaporated
by the natural heat of reaction and all of the water of 45 itallhas
of said phosphate rock, disintegrating said mixture after
hardened into a plastic mass, and thereupon adding
crystallization required by complete hydration of the end nitrogen-bearing and potash-bearing fertilizer materials
product, said first portion of said rock being sufficient in and pelleting the resulting mixture while it is still hot and
amount so that when all of said acid is added thereto steaming from the original mixture of acid and rock with
it reduces said rock to a material which considered in its the addition of said minor fraction of said rock late in the
totality has the characteristics of moist sand, adding said 50 pelleting operation, thereby utilizing all of the acidic com
acid to said first portion, agitating the mass so formed ponent of said mass and causing the pellets to pass from a
to produce pellets and adding said second portion of said palpably moist to a palpably dry state by the chemical
rock to said last mentioned mass during a later portion
of said agitation, said second portion of said rock being reaction between the then unused acid and the freshly
added rock by which almost all of the free moisture pres
sufficient in amount so that the pellets are coated and ent
remaining free acid combined as superphosphate and waterat ofthecrystallization
beginning of the pelleting operation becomes
thereby assuring the integrity of
the pellets converted to a dry non-coalescent condition.
15. A process of manufacturing a pelleted superphos the pellets thereafter.
phate of relatively high phosphatic content which com References Cited in the file of this patent
prises separating ground phosphate rock into a first por 60
tion and a second portion, said first portion including UNITED STATES PATENTS
relatively coarse rock particles and a second portion con 389,566 Glaser ---------------- Sept. 18, 1888
sisting only of relatively fine rock particles, the ratio of 1,146,222 Wilson et al. ------------ July 13, 1915
said first portion to said second portion being of the 1916,114 Ober et al. ------------- June 27, 1933
order of seven to one, mixing said first portion with an 65 2,061,567 Facer ----------------- Nov. 24, 1936
acid solution which contains an acid of phosphorus in 2,106,223 Nordengren ------------- Jan. 25, 1938
an amount sufficient to acidulate said entire amount of 2,136,793 Gabeler et al.----------- Nov. 15, 1938
said rock, the concentration of the acid being such that