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Roy Amitava 197605 PHD 261183
Roy Amitava 197605 PHD 261183
A THESIS
Presented to
by
Amitava Roy
In Partial Fulfillment
March 1976
PURIFIED PHOSPHORIC ACID PROCESSES \
Approved:
D. Muzzf^(/
H.C. Ward
3
Date approved by
.
Chairman:
A<//7 4
11
ACKNOWLEDGMENTS
Dr. G.L. Bridger. I wish to thank him for making possible the financial
Allied Chemicals, DuPont Co. and Kaiser Chemical Company for providing
Dr. H.C. Ward for serving in the reading committee and for the assistance
love, and understanding, sufficient thanks for what they have done for me
ACKNOWLEDMENTS . . ..
LIST OF TABLES . ..
LIST OF FIGURES . . .
SUMMARY
Chapter
I. INTRODUCTION
Chapter page
Conclusions
Recommendat ions
APPENDICES
BIBLIOGRAPHY 136
V
LIST OF TABLES
Table Page
Table Page
Table Page
LIST OF FIGURES
Figure Page
SUMMARY
has been the area of liquid mixed fertilizers. Coupled with this growth
has been increased emphasis on the quality of the phosphoric acid used
processes which are presently used for the manufacture of phosphoric acid
Wet process phosphoric acid, on the other hand, is less expensive but
process acid but less expensive than commercial electric furnace acid.
was about 90% of theoretical. Higher total yields were obtained with
process to produce high purity phosphoric acid from low grade phosphate
grades of Florida and North Carolina phosphate rocks, from Florida phosphate
slimes, and from Florida phosphate matrix. The compositions and yields
of the acids produced were found to be almost identical for all grades
of phosphate rock used, and even when phosphate slimes were used the acid
produced was of about the same composition except that the Al 0 content
producing high purity phosphoric acid from waste materials and matrix
concentrate with sulfuric acid. The acidulated mass was then dried or
filterable mass was obtained when the acidulate was dried for 20-60
Three extraction stages with 9 minutes of contact per stage were found
The recovery of ^^0 from the rock was above 90%, except when the rock
was digested with sulfuric acid containing 937o H SO, the yield in that
wastes.
1
CHAPTER I
INTRODUCTION
ore and major end products such as ammonium phosphate, triple super-
There are two basic methods in commerical use for the production
of phosphoric acid - the wet process and the furnace process. In the
P + 5 (1-2)
4 °2 " V l O
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impurities and the major industrial markets for this acid are in the
The overall reaction with sulfuric acid may be subdivided into three
simplified steps.
is as follows:
ation.
4
made from different types of phosphate rock by means of the wet process
the wet process merchant acid are calcium, iron, aluminum, magnesium,
and fluorine. Exclusive usage for wet process phosphoric acid is found
has opened a new field of use for wet process phosphoric acid (1). All
thus supplying two of the three major plant nutrients, viz., nitrogen
and phosphorus.
sludge when the acid is ammoniated. Several methods have been used to
overcome the sludge formation problem of the clear liquid mixed fertilizer.
One method which has been successfully used to impede the degradation
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conventional wet process phosphoric acid which has been further processed
of low impurity wet process phosphoric acid using other methods (13,27,
34,35). Slack (38) and Noyes (31) both have good reviews of methods
method has gained widespread commercial acceptance. All the wet acid
produced in the United States and most of that produced in the world is
by many investigators, beginning about 1872 (38). One of the most active,
(16,18,23,24).
acid by using two chemical routes. The first process is essentially the
one developed by Drees (11) and is used for producing low impurity
phosphoric acid by using a certain chemical route which uses the con-
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9
reaction:
but not the dicalcium phosphate which forms, or the impurities present.
to step E.
recycle to Step E.
a low impurity phosphoric acid which will be suitable for clear mixed
only one product if desired, namely, either low impurity phosphoric acid
back to step A for attack with sulfuric acid as indicated by dotted line
back to crude phosphoric acid and gypsum and the impurities would be
removed from the system in step B along with the gypsum. If only
recycle streams the product from the process could consist of only
over other processes for producing a purified wet process acid: pro-
follows.
reactant in the conventional wet process chemistry and the P^O,- recovery
impurities in the crude acid filtrate due to the greater impurity load
follows:
stage for dissociating monocalcium. The filter cake from one dissociation
phosphate process in which only high purity phosphoric acid of any desired
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14
denning the digested mass. Most of the free water will probably, but
not necessarily, be expelled from the digested mass during this step.
acid but not the calcium sulfate which forms, or the impurities present.
phosphoric acid in the organic solvent from the solid calcium sulfate
step C.
recycle to Step C.
acid of any desired concentration which will be suitable for clear mixed
phosphorus pentoxide when treated with phosphate rock. Due to the low
fluorine content, this acid can be used for the manufacture of calcium
phosphate for animal food. It is believed that this process will offer
can also be produced. Total process time using the acidulate filtration
processes. Fluorine evolution from the rock is almost 90% complete; this
rock, (b) reaction time and temperature and (c) drying or denning time
and temperature.
and solvent in each stage, and (c) proportion of organic solvents and
phosphate rock P-,0,.. The effect of two organic solvents on the purity
16
from the organic solvent. The product acid needed to be recovered from
Literature Survey
aqueous system were investigated by Elmore and Farr (12), who found that
tigated by Boulle and de Sallier (7), who found that addition of the
phosphate rock is treated with strong sulfuric acid or oleum for obtaining
phosphoric acid by wet methods, the most active among them being Dorr
with sulfuric acid and then leaching out the resultant phosphoric acid.
In another experiment Litvinenko ejt aJ. (26) treated phosphate rock with
75 to 100% sulfuric acid at 140 to 260°C for 20 to 120 min and obtained
18
product was in the anhydrite form. Litvinenko and Isabekora (25) then
23-24% P„0(.. Rohac e_t al. (33) found that when granules of solidified
mixture of apatite and 98% H~S0, was coated with a sulfite liquor extract,
The two processes of this type which have received the most
developed by the Davison Chemical Division of W.R. Grace and Company, and
and ground to minus 80 mesh was treated for about 2 min with 98%, technical
mainly of stiff particles of about 1/4 to 3/4 in. was then heated for
47% P.0r. In both cases about 95%> of the P„0- in the rock was recovered
2D 2D
and strong (987o) sulfuric acid could be obtained only by heating the
work was started at TVA (16,18) in which fuming sulfuric acid (oleum)
was used. In the laboratory work, the phosphate rock was mixed with
fuming sulfuric acid for about 1/2 min, into a semigranular solid, which
was then denned for 20 min in a dewar flask. The denned acidulate was
CHAPTER II
of Monocalcium Phosphate
acid was also prepared by chemical digestion with sulfuric acid of ground
were employed such that gypsum or the dihydrate form of calcium sulfate
wet process phosphoric acid reaction were weighed to the nearest ounce.
21
grade sulfuric acid used was based on the amount of H SO, required to
P„0,- which had been prepared previously using the same reactants and
This wet process phosphoric acid was used to dilute the reaction slurry
acid from the filter cake wash section of the filters along with some
the technical grade sulfuric acid was added slowly over a period of one
of the reaction slurry was never allowed to rise above 80°C during
slurry was maintained between 75°C and 80°C by heating with a large hot
22
digestion period of six hours was allowed from the initial mixing of the
phosphatic raw material, water and recycled acid until filtration was
started.
such that a gypsum cake thickness of between two and three inches resulted.
After filtration of the reaction slurry, the filter funnel and cake were
transferred to another four liter pyrex filter flask and the filter cake
was washed by adding enough wash water to cover the cake to a depth of
about two inches. The resulting filtrate was retained for use as a
preparations.
two liters of wet process acid were placed in a three-necked, four liter
pyrex boiling flask which was heated with an electrical mantle and which
heated to the boiling point after drawing a vacuum on the system. Water
of the reaction were weighed to the nearest gram. Assuming P-O,. losses
technical grade sulfuric acid used was based on the weight of H SO,
P.O, which had been prepared previously using the same reactants and
reaction conditions was also weighed to the nearest gram using an amount
wet process phosphoric acid was used to dilute the reaction slurry so that
its solids content was about that of the reaction slurry encountered in
75°C and 80°C using a hot plate. In order to insure a high P90,- digestion
digestion period of six hours was allowed from the initial mixing of the
dicalcium phosphate, water, and recycled acid until slurry filtration was
initiated.
Buchner filter funnel through Whatman Number 1 filter paper into a 500
was between one and two inches. After filtration of the reaction slurry,
the filter funnel containing the cake was then transferred to another
filter flask and the filer cake was washed with enough distilled water
p
to leach the remaining water soluble 90,-- The washed gypsum filter
cake was oven dried, weighed, and chemically analyzed for P90r in order
filtrate was also weighed and chemically analyzed for various chemical
species.
or North Carolina with wet process acid containing about 30 percent P2^5
acid was weighed to the nearest one-tenth gram, in a tared 316 stainless
slurry product. The phosphoric acid was heated with a hot plate to 80°C
was then added slowly to the hot agitated acid over a period of 15
The resultant slurry was agitated for two hours total time while
from 500 to 5000 milliliters were used for the dissociation studies.
A two-bladed propeller and shaft made of 316 stainless steel and driven
by an electric motor was inserted in the center neck while the two off-
center necks were used for a reflux condenser and sample port.
weighed into the flask and the flask was then placed in a water bath
Electric Company Model MR-3262A water bath was used with capability
solvent/monocalcium phosphate P^O,- ratio was weighed into a flask and the
solvent was then heated on a steam bath to the desired reaction temperature.
The heated solvent was transferred to the reaction flask and vigorous agit-
ation was started immediately. The agitator was rotated at 425 revolutions
milliliter pipette whose tip had been removed so that any large solid
particles in the slurry would not be prevented from being sampled. The
which retained particles larger than nine microns using a water aspirator
approximately one inch resulted. After recording the time required for
the resulting filter cake was washed with a very small amount of ambient
temperature solvent used in the reaction. The filter cake was dried at 105°C
and the filtrate was quantitatively transferred to a beaker from which the
solvent was evaporated by the use of an infra-red lamp. Both filter cake
content of the flask after the desired reaction time period. At this
time, the reaction flask was quickly removed from the water bath and the
The filter cake from the first and second stages of the stagewise
to the desired solvent/m.c.p. P90,- ratio was weighed into a flask and
heated solvent was transferred to the reaction flask and vigorous agitation
all the calcium oxide in the rock to calcium sulfate anhydrite, were
weighed to the nearest ounce. Assuming P?0_ losses of 3.5 percent due
acid used was based on the amount of H SO. required to produce a phosphoric
stage, the mixture formed stiff puttylike particles, about 1/8 to 3/4
mixture became hard and porous. The dry product or acidulate was then
converting all the calcium oxide in the rock to calcium sulfate anhydrite,
were weighed to the nearest ounce. Assuming P-0,. losses of 3.5 percent
material.
29
were 240° to 270°C. The resultant acidulate was then held in an insulated
this denning period ranged from 320° to 350°C. The dry product was then
and pestle until the largest particle passed through a U.S. standard
18 mesh screen. The dried acidulate from the direct acidulation process
were pulverized by hand with a mortar and pestle until most of the
Company was used to grind the Florida flotation concentrate and phosphatic
passed repeatedly through the mill until 70 weight percent of the grounded
funnel fitted with Whatman Number 42 filter paper was used to carry out
the extraction steps. A Hoffman clamp was used to pinch the polyethylene
tube, attached to the stem of the funnel, so that the organic solvent
was weighed to the nearest ounce and poured in the Buchner funnel.
acidulate the polyethylene tube was pinched. The pinch clip was released
after the desired time period and the filtrate collected in the filtration
flask. The above procedure was repeated for several stages and the
Materials
Price,
Chemicals Dollars per Pound Pricing Basis
Scientific Company.
Two types of phosphate rock were used in this work. The phosphate
The North Carolina phosphate rock obtained from the Texas Gulf Sulfur
pebble used in this work were obtained from Occidental Chemical Company.
The phosphate slime was obtained from the Mobil Chemical Company's slime
recovery and bene fieiation pilot plant in Clear Springs, Florida. The
soft phosphate with colloidal clay (Calphos) was obtained from Thompson
Sales Co., Inc. All of the above raw materials were subjected to
work. All the materials were also dried at 105°C before using. Chemical
acid.
water were used during the course of this study. All monocalcium phos-
33
Ground Florida
34.28 49.50 1.28 1.33 0.25 3.84 0.00
Concentrate (I)
Ground Florida
Concentrate (II) 34.02 49.71 1.31 1.43 0.24 0.00
Ground Florida
33.48 48.17 1.62 1.69 0.26 0.00
Concentrate (III)
Ground Florida
33.04 47.88 1.70 1.79 0.32 0.00
Concentrate (IV)
Ground Florida
32.31 45.96 1.82 1.96 0.31 0.00
Concentrate (V)
Ground Florida
28..88 41.16 3.26 3.16 0.37 0.00
pebble
Ground Florida
14,.30 18.23 14.78 4.76 0.00
slimes
Ground Florida
Phosphate Matrix (I)
20..20 28.89 2.02 0.56 0.17 1.81 0.00
Ground Florida
Phosphate Matrix (II) 15.,84 21.71 2.51 0.62 0.26 1.90 0.00
Ground Florida
11. 57 14.56 8.93 0.96 0.22 0.98 0.00
Phosphate Matrix (III)
Ground N. Carolina
Concentrate (I) 32.93 54.01 0.80 0.87 0.27 3.99 0.00
Ground N. Carolina
30.60 49.10 0.72 0.52 0.22 0.00
Concentrate (II)
Ground Florida
Concentrate (I) 0.07 0.09 0.36 0.49 2.94 27.13
Ground Florida
0.03 0.07 0.17 0.43 0.59 3.73 28.58
Concentrate (II)
Ground Florida
0.04 0.09 0.24 0.44 0.73 3.24 28.47
Concentrate (III)
Ground Florida
Concentrate (IV) 0.01 0.17 0.32 0.49 0.94 4.87 29.43
Ground Florida
Concentrate (V) 0.04 0.21 0.41 0.53 0.84 4.11 30.42
Ground Florida
Pebble 0.02 0.19 0.34 0.47 0.91 4.07 29.83
Ground Florida
Slimes 0.01 0.11 0.34 0.51 2.93 27.10
Ground Florida
0.02 0.13 0.31 0.48 3.03 27.73
Phosphate Matrix (I)
Ground Florida
0.05 0.13 0.49 0.73 3.95 30.41
Phosphate Matrix (II)
Ground Florida
0.13 0.24 0.58 0.93 3.87 29.42
Phosphate Matrix (III)
Ground Florida
0.07 0.12 0.38 0.81 3.63 28.73
Phosphate Matrix (IV)
Ground N. Carolina
0.01 0.07 0.19 0.23 0.38 29.57
Concentrate (I)
Ground N. Carolina
Concentrate (II) 0.00 0.03 0.10 0.13 0.31 30.13
erials from either Florida or North Carolina with wet process phosphoric
acid which had been produced using ground phosphatic material from the same
were ground so that the largest particle passed through a U.S. standard
were used during the course of this study. All the acidulates were
The sulfuric acid used for digesting ground phosphate rock during
for chemical analysis and the numerous chemicals used in analyzing these
samples for the various chemical species were all reagent grade chemicals
for the purpose of analyzing for various chemical species is given here.
In almost all cases, analytical methods were used which have been approved
Analysis of Phosphorus
There were three types of analysis which were used in this work to
Chemists (AOAC) official methods 9 was employed for this analysis (20).
for this analysis (20). The method basically involves leaching the
with distilled water. The water leach is analyzed for phosphorus using
phosphorus.
employed for this analysis (20). The method basically involves dissolving
aqua regia and analyzed for phosphorus using the volumetric ammonium
The AOAC official method 33 was employed for this analysis (20).
The calcium oxalate precipitate is then washed and titrated with standard
was employed for these analyses (20). This method of analysis for
curves.
Analysis of Fluorine
flask while stripping the evolved hydrogen fluoride with steam. The
The AOAC official method 5 was used for this analysis (20). This
A method developed by Hill and Jacob (19) was used for this analysis.
105°C.
CHAPTER III
low impurity phosphoric acid from various grades of phosphate rock and
phoric acid - dicalcium phosphate process was carried out in which only
directly from various grades of phosphate rock and low grade phosphatic
Dissociation Solvents
rejection from the purified acid product while using the most promising
water present in the crude monocalcium phosphate react ant and 3) proportion
40
product acid P90t- yield at the level investigated for methanol and
four hours of reaction time as was obtained after one hour, and any
acid P.-^,- yield, product acid impurity concentration and filtration rate
Tables 5 and 6. The product acid P 9 0 q yields, the product acid impurity
Tables 5 and 6 are the values obtained after one hour of dissociation
It has been shown (11) that the product acid P Oq yield increased,
41
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the total major cation impurity content of the product acid decreased
from the overhead stream of the fractionation stage. It has also been
shown (11) that the best dissociation temperatures for methanol and
percent P90_ yield in the product phosphoric acid increases with each
in the third stage is quite small compared to the first two stages.
The P90 yield in product acid resulting from the dissociation of crude
methanol per pound of monocalcium phosphate ?90 in the first stage. This
reverse reaction. As the ratio was increased above six pounds of methanol
p
per pound of monocalcium phosphate 90,-5 the product phosphoric acid P^r
to product acid ?90[- in the first stage, while the cumulative P^s y^ e ^
46
in the second stage after treating crude monocalcium phosphate with six
stages. The maximum conversion was about 87% of the theoretical after
treating crude monocalcium phosphate with six, seven and five pounds
successive stages.
ratios in each stage. The product phosphoric acid yield resulting from
percent P90(- increased as the solvent/P 0,. ratio increased, and became
PA. Although the product phosphoric acid yield resulting from the
phosphate P90,- was used. Higher total yields were obtained with solid
Tables 5 and 6 also show the total major cation impurity (CaO,
per pound of monocalcium phosphate P?0t. after which the decrease was not
as pronounced. As can be seen from Tables 5 and 6, the total major cation
lower than the total major cation impurity concentration in the product
filtrate P90_ that resulted per hour per square foot of filtration area.
The filtration rates of the slurries resulting from the stagewise dissociation
phosphate were somewhat lower than the filtration rates of the 32 percent
48
acid P90_ yield, product acid impurity concentration and filtration rate
P^O yields, the product acid impurity concentrations and the dissociation
slurry filtration rates are the values obtained after one hour of
The P^Oc yield in the product phosphoric acid resulting from the
ratio from 6.4 to 8.2, while similar results obtained from the dissociation
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total yields were obtained with solid than with slurry monocalcium
phosphate.
Tables 7 and 8 also show the total major cation impurity (CaO,
with 1.6 to 3.1 pounds of acetone per pound of monocalcium phosphate P90,-
acetone per pound of monocalcium phosphate P.O., the total major cation
When the data concerned with the product acid impurity concentrations
when using methanol solvent (see Tables 5 and 6) are compared with those
when using acetone solvent (see Tables 7 and 8), it can be seen that
Al 0 in the product phosphoric acid were generally much lower than when
acetone was the dissociation solvent. However, when acetone was used as
54
the dissociation solvent, the concentrations of CaO and MgO were generally
much lower than when methanol was the dissociation solvent. This pre-
methanol rejects iron and aluminum impurities better than acetone and
of pounds of filtrate P?0 that resulted per hour per square foot of
filtration area. It can be seen from the above two tables that the
methanol solvent (see Table 9) are compared with those with acetone
higher dissociation slurry filtration rates than when methanol was used
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runs are presented in Table 10. The detailed results are given in
54 percent P90_ along with the filtration rate of the dissociation slurry
which resulted from the dissociation with methanol and acetone of crude
table also shows the types of phosphatic materials, the type of dissociation
Reaction and filtration temperatures for acetone and methanol were 50°C
phosphate was used for these experiments. The crude monocalcium phosphates
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major cation impurities (CaO, Fe?0 , A1?0 , MgO and total major cations)
period.
From the results given in Table 10 it may be seen that the P90,-
yields of the acids produced varied from 32.93 percent to 28.17 percent
in MCP. The P90,- yield, when similar amount of methanol was used as
However, P90,- yield in the product acid was slightly higher, when mono-
concentrations in the product acid were more or less identical for all
60
where the Al 0 content was slightly higher. It can be seen that the
rejected from the product phosphoric acid. When methanol was used as
product phosphoric acid were generally much lower than when acetone
was the dissociation solvent. However, when acetone was used as the
much lower than when methanol was the dissociation solvent. However,
even though methanol rejects iron and aluminum impurities better than
acetone and acetone rejects calcium and magnesium impurities better than
while using acetone as the dissociation solvent was much higher than
when using methanol. For example, the filtration rate of the slurry
per square foot for acetone compared with 19 pounds of filtrate P^O,- per
producing phosphoric acid of much greater purity than that from current
materials.
The data resulting from these experiments were used to evaluate the
acid.
P 0 and ground to 70 percent through 200 mesh was used. The sulfuric
to about 100°C and intimately mixing it with the phosphate rock for
about 2 min. The product from this mixing consisted of stiff particles
of about 1/8 to 3/4 in. The mixture was then heated for about 30 min
62
at 250°C, after which it became hard and porous. The dried acidulate
contact time in each of the three extraction stages. After each extraction
tions of sulfuric acid, the P?0 yield, the P?0,- concentration and percent
impurity in the product acid along with the filtration rate of the extracted
acid which resulted from the stagewise extraction of dried acidulate, which
of dried acidulate with acetone. These tables also show the percent total
acid that appear in Tables 11 and 12 are shown in Tables 13 and 14 along
acid on the basis of 54% P90,-' Tables 13 and 14 also show percent H SO.
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that percent i>90t. recovery from the rock remained somewhat constant
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in the product acid was rather sharp. The total major cation impurity
When the data concerned with the product acid impurity concentrations
when using methanol solvent (see Table 13) are compared with those using
acetone solvent (see Table 14), it can be seen that the choice of solvent
the product acid. When methanol was used as the extraction solvent, the
generally lower than when acetone was the extraction solvent. However,
when acetone was used as the extraction solvent, the concentration of CaO
and MgO were generally much lower than when methanol was the extraction
phosphoric acid was slightly higher when methanol was used as the
extraction solvent.
rates when using methanol solvent (see Table 11) are compared with those
using acetone solvent (see Table 12), it can be seen that the choice of
73
solvent dictated the filtration rate of the extract. When methanol was
used as the extraction solvent, the filtration rate was lower than
cost per unit of product is determined. The low impurity phosphoric acid
acids since its impurity content is lower than that of wet process acid,
but higher than that of furnace acid. The present marketing prices (8)
for tank car quantities of wet process phosphoric and furnace grade
ton and $152 per ton respectively. It may be seen that there exists a
phosphoric acid so that the low impurity acid could probably be successfully
H.SO. are somewhat similar, the choice of sulfuric acid for digesting
2 4
phosphate concentrate was made on the basis of total P90r yield in the
product acid and also the total major cation impurity content of the
11 and 12 the sulfuric acid containing 98, 103.30, and 104.50 percent
extracted with either acetone or methanol gave the best P?0 yield
in the product acid. Tables 13 and 14 show that the total major cation
with the increasing sulfuric acid concentration. The lowest value of the
was obtained when sulfuric acid containing 104.50 percent H SO, was used
for digesting the Florida phosphate concentrate and the acidulate thus
ever, at this point, it should be mentioned that the choice of the type
product acid desired. The use of sulfuric acid, containing either 103.30
required between the acidulation and extraction stage when the sulfuric
acid from the acidulate was made on the following basis. Methanol and
acetone are the cheapest of all the solvents considered with methanol
being cheaper than acetone (Table 2). Both methanol and acetone are
from the extracted filtrate with the use of low quality heat.
temperature of slightly less than the normal boiling point of the solvent
to be used for the subsequent extraction step. The cooled acidulated mass
slurry which filters much more rapidly than that corresponding to the
pressure steam for fractionation and filter cake drying should result
acetone would require much less energy for solvent fractionation and
per stage, methanol and acetone produce approximately the same filtrate
P?0 yield and the same P?0 concentration in the product acid. The total
slightly higher when the dried acidulate is extracted with methanol than
with Sulfuric Acid and Subsequent Extraction of the Acid with Methanol and
Acetone Solvents
are presented in Tables 15 and 16. Tables 15 and 16 show the Po0 yield,
77
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acid along with the filtration rate of the extracted phosphoric acid
which resulted from the stagewise extraction of the acidulated mass, pre-
pared from various phosphatic material, with methanol and acetone respec-
tively. Tables 15 and 16 also show the type of phosphatic materials and
the total percent P90c. in the acidulated mass. Sulfuric acid used for
15 and 16 are for each stage of those experimental runs made using not
the P90c. yields of the acids produced varied from 95.04 percent to
materials, was extracted with methanol. The P9°r yield, when similar
that the choice of solvent dictated which major impurities were pre-
acetone was the extraction solvent. However, when acetone was used
as the extraction solvent, the concentrations of CaO and MgO were generally
or waste materials.
81
CHAPTER IV
Figure 5 shows the flow diagram for the production of low impurity-
diagram is presented along with the total mass flow rates and the
compositions of the main flow streams for each process variation based
used in the material balance for the flow sheet presented below are
are given here. The process produces 1000 tons per day of product P90_
percent CaO, 1.3 percent Fe20„, 1.3 percent A l ^ , 0.3 percent MgO and
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P 0 ratio of 6.0 tons of methanol per ton of P90[-> being equally divided
pounds of filtrate P90,- per hour per square foot. Chemical analysis of
as follows: 67.0 percent P90t-» 1.38 percent CaO, 0.92 percent Fe_0 ,
1.12 percent A1_0 , 0.35 percent MgO, 0.58 percent F and negligible
percent sulfate. The solvent content of the wet extracted filter cake
is 0.4 tons of methanol per ton of wet filter cake. When using acetone,
filtrate P„0._ yield during extraction. The filtration rate of the extracted
J
2 5 °
phosphoric acid is 150 pounds of filtrate P90,. per hour per square foot.
acetone is as follows: 67.0 percent P90,-, 0.82 percent CaO, 1.19 percent
Fe90 , 1.33 percent Al90 , 0.14 percent MgO, 0.98 percent F and negligible
percent sulfate. The solvent content of the wet extracted filter cake
A flow diagram showing the major processing steps and the major
flow streams in the process when producing low impurity phosphoric acid
the streams entering and leaving each of the major processing steps.
with Tables 17 and 18. Total mass flow rates and compositions of the
main process flow streams when producing low impurity phosphoric acid
(1000 tons per day of product P90 output) by extraction with 6.0 tons of
84
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methanol per ton of P~0 in dried acidulate, being equally divided among
three stages, are shown in Table 17 while the total mass flow rates and
compositions of the main process flow streams when producing low impurity
phosphoric acid (1000 tons per day of product P^O^. output) by extraction
with 6.0 tons of acetone per ton of P^O- in dried acidulate are shown in
Table 18.
89
CHAPTER V
Conclusion
Dissociation Process
study of the process for the production of low impurity phosphoric acid
methanol and acetone was studied by subjecting the insoluble residue from
acid increases with each subsequent treatment through three stages. The
commercial grade phosphoric acid, and that this concentration was achieved
directly from the dissociation step after removal of the solvent and with-
Florida phosphate rock and North Carolina phosphate rock are significantly
process to produce high purity phosphoric acid from low grade phosphatic
grades of Florida and North Carolina phosphate rocks, from Florida phos-
phate slimes, and from Florida phosphate matrix. The compositions and
yields of the acids produced were found to be almost idential for all
grades of phosphate rock used, and even when phosphate slimes were used
the acid produced was of about the same composition except that the Al 0„
high purity phosphoric acid from any grade of phosphatic raw material,
follows:
mass is obtained when the acidulate is dried for 20-60 minutes at 250°C
number of extraction stages and optimum contact time per stage. Seven
stages were used. Total contact time was plotted against the total yield
for the extraction of phosphoric acid from the dried acidulate with either
were achieved directly from the extraction step after removal of the
the rock was above 907o except when the rock was digested with sulfuric
acid containing 93% H_S0, the yield in that case was much lower.
Recommendations
with good filtrate ?90 yield in the product acid still occuring.
phosphoric acid with methanol and acetone from dried acidulate, obtained
in lesser time.
used to determine which of the sulfuric acids should be used for digesting
APPENDIX A
and acidulate were then dried or denned so that the resultant monocalcium
phosphate and acidulate material contained from 41.6 to 47.0 and 11.7
that the largest particles passed through U.S. standard 18 mesh and 2
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APPENDIX B
acetone and methanol after different reaction time periods using different
Tables 21 and 22 shows the P90,_ yields, the major cation impurity
containing 54 percent total P^O resulting from the first stage of the
slurry sample until the top portion of the cake appeared dry and after
pounds of filtrate P90,- per hour per square foot of filtration area was
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103
first stage using methanol and acetone respectively. The filtration rates
along with the dissociation reaction time for each experiment. The
pound of total P90t- in unreacted MCP and 8.16 pounds of acetone per pound
Tables 25 and 26 show the P90 yields, the major cation impurity
containing 54 percent total P^r resulting from the third stage of the
listed. The unreacted monocalcium phosphate P90,_ ratio are shown along
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with 8.16 and 8.12 pounds of acetone per pound of total P^^. in unreacted
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containing 54 percent total P90c. resulting from the first stage of the
Tables 29 and 30 show the ?90j- yields, the major cation impurity
containing 54 percent total P^^ resulting from the second stage of the
shown along with the dissociation reaction time for each experiment.
29 and 30 were obtained from dissociation for one hour of crude monocalcium
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to filter the slurry sample until the top portion of the cake appeared
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Pounds of
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Methanol
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4-1 J-i •H O
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H
Pounds of
.-H <
Percent Solvent
CO d 4
•U » H C
6.23
6.28
6.26
6.20
MCP
O c
H mc
O J
MH CNf
O PM £
Per Pound
d ^
•H C
45.67
45.67
46.20
46.20
MCP
1 +
md c
o -p c
CM C
PM J
Methanol
Methanol
4-1
Total
Acetone
Acetone
d
CU
>
i-H
O
CO
CO
trate II
Carolina
Carolina
i-H ^s
trate I
Raw
cu m
Concen-
Concen-
(32.9)
(30.6)
•H O
North
North
JH CN
CU P M
4-) B-S
128
ratios are shown along with the dissociation reaction time for each
experiment.
Table 10.
129
APPENDIX D
different overall contact time divided equally in each stage and using
The dried acidulate was prepared from ground Florida phosphate concentrate.
total overall contact time and also contact time for each stage and overall
and 2 in. deep Buchner funnel. A Hoffman clamp was used to pinch the
desired period of time. The filtrate collected, after the solvent has
been in contact with the acidulate, was analyzed and percent P~0 recovery
total P90q; yield in the product acid resulting from the stagewise
40 80
Total Contact Time (Minutes)
contact time was increased above 36 minutes the product phosphoric acid
contact time was increased above 25 minutes, the product phosphoric acid
yield was slightly higher when extracted with methanol than with acetone.
It can be seen from Fig. 6 that when extracting the dried acidulate
percent P^O^ in product phosphoric acid resulted when the overall contact
per stage were carried out with both acetone and methanol. The dried
Methanol 3 9 27 96.21
Acetone 4 9 36 97.01
Methanol 4 9 36 97.57
APPENDIX E
SAMPLE CALCULATION
The sample calculations listed below are the same as those given
by Drees (11):
phosphoric acid,
rock containing 34.28 percent P?0_ and 49.50 percent CaO, technical grade
it was assumed that a wet process acid would be produced that contained
67.0 percent P~0 and 2.0 percent free sulfuric acid. It was also
rock would be digested by the sulfuric acid leaving the remaining 3.5
gm P 0, gm • P?0 digested
fL2 D
(100.00 gm • rock) (0.3428 -T") (0.965 p n . r-)
& x
gm • rock gm • Po0r in rock
= 33.08 gm • P 0 digested.
33.08 gm • P 0 digested
n r-, 7T7;—7 r r : rr = 49.37 gm • phosphoric acid.
r r
0.67 gm • P„0,-/gm • phosphoric acid ^
//n oi u u • . U M no gm • sulfuric acid
(49.37 gm • phosphoric acid) (0.02 **• : : : —)
gm • phosphoric acid
= 0.99 gm • free sulfuric acid in
phosphoric acid.
Since each mole of CaO requires one mole of HoS0. for calcium
2 4
sulfate anhydrite precipitation:
gm • H SO
(0.8518 gm • mole H_S0 ) (98.082 •— \ ) - 83.55 gm • H_S0
2 4 gm • moie H0bU, z 4
required for calcium
sulfate anhydrite
precipitation.
83.55 gm . H SO, for calcium sulfate anhydrite +0.99 gm I^SO^ for
84.54 gm • H 2 S0 4
86.27 gm * sulfuric acid required.
0.98 gm • H7S0^
gm • sulfuric acid
135
are as follows:
BIBLIOGRAPHY
3. Baniel, A.M. and Blumberg, R., British Patent 1,142,719 February 12,
(1969).
4. Baniel, A.M., Blumberg, R., and Alon, A., French Patent 1,396,077,
April 16, (1965).
5. Baniel, A.M., Blumberg, R., and Lavie, S., German Patent 1,801,856,
August 7, (1969).
11. Drees, C.B., "A New Process for the Production of Low Impurity
Phosphoric Acid," Ph.D. Thesis, Georgia Institute of Technology,
Atlanta, Georgia, November, (1972).
12. Elmore, K.L. and Farr, T.D., "Equilibrium in the System CaO-P 0 -H ? 0,"
Industrial and Engineering Chemistry 32, 580-586 (1940).
15. Goret, J. and Winand, L., French Patent 1,531,487, July 5, (1968).
137
16. Hand, Jr., L.D., Potts, J.M. and Slack, A.V., "Use of Concentrated
Sulfuric Acid and Production of Granular Normal Superphosphate,"
Journal of Agricultural and Food Chemistry, 11, 44 (1963).
18. Hignett, T.P., Slack, A.V., Potts, J.M. and Hand, Jr., L.D. U.S.
Patent 3,161,467, December 15, (1964).
19. Hill, W.L. and Jacob, K.D., "The Composition and Properties of
Superphosphate," Journal of the Association of Official Agricultural
Chemists 17, 487-505 (1934).
22. Kimura, T., Tago, A., Minagawa, Y. and Kaneko, Y., Japanese Patent
7,445,895, September 8, (1972).
23. Legal, Jr., C.C., Pryor, J.N. , Tongue, T.O. and Veltman, P.L.,
"Phosphoric Acid by the Clinker Process," Industrial and Engineering
Chemistry, 49,334 (1957).
24. Legal, Jr., C.C., Tongue, T.O. and Wight, E.H., U.S. Patent
2,504,544, April 18, (1950).
27. Melamid, M. and Grotzinger, L., German Patent 280,969, April 17,
(1914).
29. Murakami, K., Okabe, T. and Tanaka, H., Japanese Patent 6,828,005
December 3, (1968).
31. Noyes, R., Phosphoric Acid by the Wet Process, Noyes Development
Corporation, Park Ridge, New Jersey (1967).
33. Rohac, J., Nodvornik, R., and Hrusovsky, J., Czech Patent 103,132,
March 15, 1962.
34. Ross, W.H., Durgin, C.B. and Jones, R.M., U.S. Patent 1,451,786,
April 17, (1923).
35. Ross, W.H., Jones, R.M. and Durgin, C.B., "Purification of Phosphoric
Acid by Crystallization," Industrial and Engineering Chemistry 17,
1081-1083 (1925).
36. Rubin, A.G., "A New Route to High Quality Phosphate Fertilizers,"
Presented in 1971 as a process developed by Bohna Engineering and
Research, Inc. of San Francisco, California.
38. Slack, A.V. (Editor), Phosphoric Acid, Parts I and II, Marcel
Dekker, Inc., New York, New York (1968).
42. Winand, L. and Martin, M., French Patent 1,435,877, April 22, (1966).
139
VITA.
attended public schools in Calcutta and Bombay, and graduated from Bharda
New High School in Bombay in June 1964. He attended the Loyola College