Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
A THESIS
Presented to
The Faculty of the Graduate Division
by
Amitava Roy
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy in the School of Chemical Engineering
Approved:
D. Muzzf^(/
H.C. Ward
Date approved by
3
.
A<//7 4
Chairman:
11
ACKNOWLEDGMENTS
The
TABLE OF CONTENTS
ACKNOWLEDMENTS
. . ..
LIST OF TABLES
. ..
LIST OF FIGURES . . .
SUMMARY
Chapter
I.
INTRODUCTION
General Information and Statement of Problem
Objectives
Literature Survey
II.
III.
Chapter
IV.
page
CHEMICAL PROCESS FLOW DIAGRAMS
81
89
Conclusions
Recommendat ions
APPENDICES
A.
B.
C.
D.
E.
94
100
121
129
Sample Calculation
133
BIBLIOGRAPHY
,.
136
LIST OF TABLES
Table
1.
Page
5
2.
3.
4.
34
5.
6.
7.
8.
9.
55
57
63
54
66
71
10.
11.
12.
13.
14.
vi
Table
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
Page
77
78
84
86
95
98
101
102
104
. . . 106
108
vii
Table
26.
27.
28.
29.
30.
31.
32.
33.
34.
Page
109
Variation of P0r Yield, Impurity Concentration and Filtration Rate for Phosphoric Acid from First Stage in
Stagewise Dissociation of Crude Monocalcium Phosphate with
Methanol at Different Solvent Ratios
Ill
Variation of P2O5 Yield, Impurity Concentration and Filtration Rate for Phosphoric Acid from First Stage in
Stagewise Dissociation of Crude Monocalcium Phosphate
with Acetone at Different Solvent Ratios
112
113
115
118
119
122
viii
LIST OF FIGURES
Figure
Page
1.
2.
13
3.
68
70
82
4.
5.
6.
IX
SUMMARY
One of the fastest growing segments of the fertilizer industry
has been the area of liquid mixed fertilizers.
has been increased emphasis on the quality of the phosphoric acid used
for production of liquid mixed fertilizers. Of the two major commerical
processes which are presently used for the manufacture of phosphoric acid
both have certain disadvantages.
Therefore, a
solvent.
process to produce high purity phosphoric acid from low grade phosphate
materials was demonstrated by preparation of phosphoric acid from several
grades of Florida and North Carolina phosphate rocks, from Florida phosphate
slimes, and from Florida phosphate matrix.
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
was slightly higher.
content
producing high purity phosphoric acid from waste materials and matrix
which were previously found to be uneconomical.
The second process is a modification and simplification of the
above phosphoric acid-dicalcium phosphate process in which only phosphoric
acid of high concentration can be made directly by a chemical route
involving direct digestion of phosphatic materials with sulfuric acid and
subsequent extraction of dried acidulate with methanol or acetone.
The approach taken to the experimental phase of the problem for
the second process basically involved direct digestion of the phosphate
concentrate with sulfuric acid.
XI
from the rock was above 90%, except when the rock
was digested with sulfuric acid containing 937o H SO, the yield in that
case was much lower.
The process was also shown to be capable of producing phosphoric acid
of concentration up to 70%, P^O- from low grade phosphatic materials and
wastes.
CHAPTER I
INTRODUCTION
General Information and Statement of Problem
Phosphoric acid is an important chemical intermediate, used mainly
in the fertilizer field but also in other areas of chemical technology.
In fertilizer production it serves as an intermediate between phosphate
ore and major end products such as ammonium phosphate, triple superphosphate, liquid mixed fertilizer, high analysis solid mixed fertilizer
and some types of nitric phosphate.
There are two basic methods in commerical use for the production
of phosphoric acid - the wet process and the furnace process.
In the
The
+ 6CaSiO
+ 10C0
(1-1)
VlO
+ 5
(1-2)
2 " V l O
+ 6H
2 "
(1-3)
4H P
3 4
(1-4)
CaF
(1-5)
(1-6)
3SiF. + 2Ho0
4
2
(1-8)
2H0SiF,. + Si0o
2
6
2
(1-9)
the wet process merchant acid are calcium, iron, aluminum, magnesium,
and fluorine.
chemicals.
as an objectionable voluminuous
overcome the sludge formation problem of the clear liquid mixed fertilizer.
One method which has been successfully used to impede the degradation
of the clear liquid mixed fertilizer is the use of superphosphoric acid.
Superphosphoric acid is a commercial product which contains condensed
phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid
and is helpful in avoiding the sludge formation as the polyphosphates in
the acid sequesters impurities, holding them in solution.
Electric furnace grade orthophosphoric acid is sometimes used
to supply phosphorus to clear liquid mixed fertilizers.
However, use
CN
VO ON 0 0
o
H
o o
CO
CN
d
S3
o
CN
4J
O co CN C N CN
CO O O I - I O
i-l CO
CN O
o o o o
o co r^ o r^
iI O
CO
O
i-l
o o o o
o o o o
o
o
<t-
^l
CD o
P-i CO
00 N
H
00 ^> CO
O st- M
CD
O
p-l
CN CN
O O
CTi CM N
iI iI VD CO
4J
Jd
W
H P4
0)
&
m co ii oo VD
o o o o o
r^ ii
VO O 0 0
VD m
00
co vo
r^ o co o
r^ in <f- co
4J
o o o o
o o o
H
CO
ft
CO
6 o
o 0)CN
o P4
oooovo
CN O O CO O
r^ H H M oo
o o o
T3
H
O
<J
co
H CO
ft."-'
t^
H co
CN O O O O
co ON Ii r^ m
o o CT. r^
oo in oo m
<
iI C3 iI iI iI
CN
o in o
o CN
I1
CO
ctf
VD
CO O O
i-l CO O
<t-
CN O iI O
o o o o
.-I O
CO
O
O
O
U0
o o
o CN
H TH
U U
H O
W Jd
O ft,
ft. W
6 o
o x
O
ON
o o60
H
CN
i-l O
ft.
p-l
00 H
r^ CN o vo
H CM
co <t CN co m
m in m m m
CN < f < f CM
0)
0) M
W 2
U$ O
Jd CO
ft.
CO
o o
o
tf
jd
p-l
m in m m
CN
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
produced in the United States and most of that produced in the world is
manufactured by a relatively weak phosphoric acid process (38); strong
acid is obtained by concentration.
The manufacture of phosphoric acid by wet methods has been studied
by many investigators, beginning about 1872 (38). One of the most active,
the Dorr Co. in the United States, with Krustdunger-Patent Verwertungs
A.G., Switzerland, has developed a so-called strong acid process which
directly gives a product of about 33% phosphorus pentoxide content.
This process has enjoyed commercial acceptance.
one developed by Drees (11) and is used for producing low impurity
phosphoric acid by using a certain chemical route which uses the conventional wet process method as a starting point.
(I-10)
(I-ll)
CO
CO
CD
o
o
5-1
PH
o
0)
Pi
PH
PH
U Is!
bO
H
o n
a
3
4J
C
a)
<D
>
^
<-i
oj O
S co
1i
4J
Oj
PH
a
c
<u
4J
03
o
^
x: o
a o
w P4
o
x:
4J
PH
PH
5-1
fi
5-1
bO
oj
H
Q
5-1
<U
PH
PH
ffl
4J
Si
a;
4J
cd cu
J3 4J
a oj
w x:
o a
3 PH
' to 5J
a M
o<^
<tf
O
H
U
ii
CO
PM
JU
a;
PM
4-1
O M
CO
x:
PH
i-l -H
oj O
O .-I
O oj
B
3
cu
x:
o
CO
PH
O
o 3
<f
O
H
4J
Oj
jC
3
S
T3
H
O
CO
CO
H
<u
x:
3=
Keactio
a
o
H
4J
oj
H
O
O
o
a;
PH
PH
pi
C o a
o -H g
g P M
a;
bO
H
PH
(1-12)
(1-13)
(I-10)
10
ation or extraction.
to step E.
H. Stripping of the occluded organic solvent from the dicalcium
phosphate residue and subsequent recovery of the stripped solvent for
recycle to Step E.
The process up to this point will produce two products, namely,
a low impurity phosphoric acid which will be suitable for clear mixed
liquid fertilizer production and perhaps many other industrial applications,
and impure dicalcium phosphate which can be used as a fertilizer.
In addition, however, the proposed process could be used to produce
only one product if desired, namely, either low impurity phosphoric acid
or impure dicalcium phosphate.
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
phosphoric acid, only dicalcium phosphate or any proportion of the two.
It is believed that this process will offer the following advantages
over other processes for producing a purified wet process acid:
pro-
11
reactant in the conventional wet process chemistry and the P^O,- recovery
from the digestion magma.
impurities in the crude acid filtrate due to the greater impurity load
introduced by recycled dicalcium phosphate.
Steps C, D, E, and F. Production of monocalcium phosphate.
Drying
The
12
The
13
len PH
cd a
bO
4J
C
cu
fn >
.-1
O
en
H
CX
ex
TH
U
+J
en
PM
11
4J
4J
<t
CU
en
>
i1
cd
o
CO
co cd
d
o
PM
H
4J
O
cd
w o
Q
s-i
+J
I-l
+J
s
cu
T3
CX 4J
H
4J
cd
5-1
4J
D d
I
cu
M
CU
>
i-i
cd o
S en
Pn
Solv
IMP
J> S
i-l R
en
.If
s
O
CU PM
WD
Q
<t-
<t-
P-I
PM
<i-
co cd s
>
i-i
CO
+J
d
cu
o
en
S3
o
d H
cu +J
> cd
+J
i-i
WD
5-1
o cd
en a
cu
en
rH
Pn
k
O
.d
+J
O
O
O
. d 5-i
PM PM
14
(1-14)
(1-15)
not necessarily, be expelled from the digested mass during this step.
C. Extraction of the dried product with an organic solvent such
as methanol or acetone which preferentially dissolves the phosphoric
acid but not the calcium sulfate which forms, or the impurities present.
D. Filtration of the mixture to separate a solution or purified
phosphoric acid in the organic solvent from the solid calcium sulfate
residue containing the impurities. Make-up organic solvent required to
off-set losses will probably be best added here as a cake wash.
E. Separation and recovery of the low impurity phosphoric acid
product from the solution of acid in organic solvent by fractional
distillation.
step C.
F. Stripping of the occluded organic solvent from the calcium
sulfate residue and subsequent recovery of the stripped solvent for
recycle to Step C.
The process up to this point will produce high purity phosphoric
acid of any desired concentration which will be suitable for clear mixed
liquid fertilizer
15
fluorine content, this acid can be used for the manufacture of calcium
phosphate for animal food.
Process
rock, (b) reaction time and temperature and (c) drying or denning time
and temperature.
Step C. The effect of the following variables on the recovery of
phosphoric acid from the dried acidulate by solvent extraction:
(a)
16
Literature Survey
It is known that the dissociation of monocalcium phosphate to
phosphoric acid and dicalcium phosphate occurs to a limited degree in
water.
The
17
Shoeld
18
mixture of apatite and 98% H~S0, was coated with a sulfite liquor extract,
calcined at 220-300C and then countercurrently leached with water, a
phosphoric acid containing 50%, P?0
The two processes of this type which have received the most
attention in the United States are the so-called clinker process
developed by the Davison Chemical Division of W.R. Grace and Company, and
the fuming sulfuric acid process developed by the Tennessee Valley
Authority.
In the
mainly of stiff particles of about 1/4 to 3/4 in. was then heated for
20-70 min at 200-240C and was immediately extracted in a countercurrent
system consisting of either fixed bed leach columns or filters. Five
stages of extraction were needed in the leach column system to obtain
a product acid containing 50% P^O^
In both cases about 95%> of the P0- in the rock was recovered
2D
19
and strong (987o) sulfuric acid could be obtained only by heating the
acidulate to 200-240C.
fuming sulfuric acid for about 1/2 min, into a semigranular solid, which
was then denned for 20 min in a dewar flask.
20
CHAPTER II
EXPERIMENTAL PROCEDURES AND MATERIALS
acid was also prepared by chemical digestion with sulfuric acid of ground
phosphate rock of any grade or phosphatic by-products or phosphate matrix
or dried dicalcium phosphate residues resulting from the previous
dissociations of monocalcium phosphate in the presence of an organic
solvent.
were employed such that gypsum or the dihydrate form of calcium sulfate
resulted in the reaction slurry.
One to two-gallon batches of wet process phosphoric acid containing
around 25 to 30 percent P90_ were made in a 316 stainless steel reaction
vessel with a volumetric capacity of around seven gallons.
Predetermined
21
In order
22
plate.
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.
Approximately
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
was agitated by a two-bladed propeller driven by an electric motor.
A water-cooled glass condenser was connected to the water vapor outlet
which eventually discharged the water condensate into a two-necked flask.
A vacuum was drawn on the condensate receiver by attaching a connection
to a water aspirator.
23
Water
P.O, which had been prepared previously using the same reactants and
reaction conditions was also weighed to the nearest gram using an amount
corresponding to 25 weight percent of the total reactor charge.
This
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
commerical wet process acid manufacture.
The reaction procedure was initiated by adding water, ground
dicalcium phosphate, and recycled phosphoric acid reactants in a tared
316 stainless steel reaction beaker, while vigorously agitating its
content with a propeller type mixer.
24
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
to leach the remaining water soluble
p
90,--
cake was oven dried, weighed, and chemically analyzed for P90r in order
to determine the amount of undigested phosphate.
filtrate was also weighed and chemically analyzed for various chemical
species.
Preparation of Monocalcium Phosphate
Batches of monocalcium phosphate were prepared by reacting
acidulation grade ground phosphatic raw material from either Florida
25
or North Carolina with wet process acid containing about 30 percent P2^5
which had been previously prepared from ground phosphatic materials
from either Florida or North Carolina, respectively.
acid was weighed to the nearest one-tenth gram, in a tared 316 stainless
steel reaction beaker large enough to contain the monocalcium phosphate
slurry product.
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 offcenter necks were used for a reflux condenser and sample port.
Approximately 100 grams of the monocalcium phosphate reactant were
weighed into the flask and the flask was then placed in a water bath
which had been pre-set at the desired reaction temperature. A Blue M
26
Electric Company Model MR-3262A water bath was used with capability
of maintaining the bath temperature within +0.1C of a temperature between
0C and 90C. A quantity of organic solvent corresponding to the desired
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 agitation was started immediately.
and the filtrate was quantitatively transferred to a beaker from which the
solvent was evaporated by the use of an infra-red lamp.
At this
time, the reaction flask was quickly removed from the water bath and the
slurry was filtered in a nine centimeter diameter Buchner funnel through
27
to the desired solvent/m.c.p. P90,- ratio was weighed into a flask and
then heated on a steam bath to the desired reaction temperature. The
heated solvent was transferred to the reaction flask and vigorous agitation
was started immediately.
28
The mixture
required to produce
29
Fluorine compounds
Substances
30
passed repeatedly through the mill until 70 weight percent of the grounded
material passed through a 200 mesh U.S. standard screen.
Extraction of Dried Acidulate
The extraction of dried acidulate in the presence of acetone or
methanol was studied using various extraction stages, various extraction
time periods and different degrees of dryness of the acidulate. A Buchner
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
could be held in contact with the acidulate for a period of time.
A known amount of dried acidulate was evenly spread out in the
Buchner funnel fitted with Whatman Number 42 filter paper. A quantity
of organic solvent corresponding to the desired solvent/rock P90,_ ratio
was weighed to the nearest ounce and poured in the Buchner funnel.
Corresponding to the desired contact period of the solvent with the
acidulate the polyethylene tube was pinched.
after the desired time period and the filtrate collected in the filtration
flask.
The above procedure was repeated for several stages and the
Materials
The different materials used in this study are listed below.
Organic Solvents Used for Monocalcium Phosphate Dissociation and
Extraction of Dried Acidulate
Methano1.
31
Chemicals
Price,
Dollars per Pound
Pricing Basis
Methanol
0.051
Freight on Board
Gulf Coast Producer
Acetone
0.140
Delivered,
Eastern U.S.A
Sulfuric Acid
(93.1% HoS0,)
2 4
0.022
Delivered,
Eastern U.S.A.
Sulfuric Acid
(98% HoS0.)
2 4
0.023
Delivered,
Eastern U.S.A.
Oleum
(15% free S03>
0.025
Delivered,
Eastern U.S.A.
Oleum
(20% free S03)
0.025
Delivered,
Eastern U.S.A.
Oleum
(30% free SO )
0.026
Delivered,
Eastern U.S.A.
32
Acetone.
Scientific Company.
Phosphatic Raw Materials
Two types of phosphate rock were used in this work.
The phosphate
The
Sales Co., Inc. All of the above raw materials were subjected to
pulverization to reduce them to acidulation grade before usage in this
work.
Chemical
33
Table 3.
Material
Description
1.33
0.25
3.84
1.31
1.43
0.24
0.00
48.17
1.62
1.69
0.26
0.00
33.04
47.88
1.70
1.79
0.32
0.00
Ground Florida
Concentrate (V)
32.31
45.96
1.82
1.96
0.31
0.00
Ground Florida
pebble
28..88
41.16
3.26
3.16
0.37
0.00
Ground Florida
slimes
14,.30
18.23
14.78
4.76
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
Phosphate Matrix (III)
11. 57
14.56
8.93
0.96
0.22
0.98
0.00
Ground Florida
Phosphate Matrix (IV)
7.53
11.30
3.51
2.27
4.78
1.11
0.00
Ground N. Carolina
Concentrate (I)
32.93
54.01
0.80
0.87
0.27
3.99
0.00
Ground N. Carolina
Concentrate (II)
30.60
49.10
0.72
0.52
0.22
0.00
20.43
27.53
10.46
3.71
0.74
0.00
25
AL 2 0 3
Ground Florida
Concentrate (I)
34.28
49.50
1.28
Ground Florida
Concentrate (II)
34.02
49.71
Ground Florida
Concentrate (III)
33.48
Ground Florida
Concentrate (IV)
Fe
2 3
Free
Water
CaO
0.00
0.00
34
Table 4.
Material
Description
Ground Florida
Concentrate (I)
0.07
0.09
0.36
0.49
2.94
27.13
Ground Florida
Concentrate (II)
0.03
0.07
0.17
0.43
0.59
3.73
28.58
Ground Florida
Concentrate (III)
0.04
0.09
0.24
0.44
0.73
3.24
28.47
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
Phosphate Matrix (I)
0.02
0.13
0.31
0.48
3.03
27.73
Ground Florida
Phosphate Matrix (II)
0.05
0.13
0.49
0.73
3.95
30.41
Ground Florida
Phosphate Matrix (III)
0.13
0.24
0.58
0.93
3.87
29.42
Ground Florida
Phosphate Matrix (IV)
0.07
0.12
0.38
0.81
3.63
28.73
Ground N. Carolina
Concentrate (I)
0.01
0.07
0.19
0.23
0.38
29.57
Ground N. Carolina
Concentrate (II)
0.00
0.03
0.10
0.13
0.31
30.13
0.00
0.00
0.05
0.10
0.17
30.33
35
phatic materials were initially prepared by reacting ground phosphatic materials from either Florida or North Carolina with wet process phosphoric
acid which had been produced using ground phosphatic material from the same
region.
were ground so that the largest particle passed through a U.S. standard
18 mesh screen.
size distribution
36
for chemical analysis and the numerous chemicals used in analyzing these
samples for the various chemical species were all reagent grade chemicals
obtained from the Fisher Scientific Company, Will Scientific, Inc., or
J.T. Baker Chemical Company.
Chemists (AOAC) official methods 9 was employed for this analysis (20).
This volumetric ammonium molybdate method basically involves digesting
the sample in aqua regia followed by the precipitation of the phosphorus
in a suitable aliquot using ammonium molybdate as the precipitation
reagent.
for this analysis (20). The method basically involves leaching the
water soluble phosphous from a weighed sample of the solid material
with distilled water.
37
phosphorus.
Citrate Insoluble Phosphorus.
employed for this analysis (20). The method basically involves dissolving
phosphorus from a weighed sample of the solid in hot neutral ammonium
citrate solution after removing the water soluble phosphorus. The
remaining citrate insoluble phosphorus in the sample is then digested in
aqua regia and analyzed for phosphorus using the volumetric ammonium
molybdate method described above for total phosphorus.
Analysis for Calcium
The AOAC official method 33 was employed for this analysis (20).
This analysis for water soluble calcium basically involves digesting
the sample in aqua regia followed by the precipitation of the calcium
in a suitable aliquot using ammonium oxalate as the precipitating reagent.
The calcium oxalate precipitate is then washed and titrated with standard
potassium permanganate solution.
Analysis for Iron, Aluminum, and Magnesium
The AOAC official Atomic absorption spectrophotometry method 29
was employed for these analyses (20). This method of analysis for
iron, aluminum, and magnesium basically involves digesting one gram of
the sample in hydrochloric acid followed by evaporating the sample to
dryness, then subsequently diluting it to appropriate volume with water.
Light absorption at appropriate wave lengths was measured with a Beckman
440A atomic absorption spectrophotometer and compared with standard
curves.
Analysis of Fluorine
The AOAC official method 9 for fluorine in pesticides was employed
38
The
Size Distribution
39
CHAPTER III
phoric acid - dicalcium phosphate process was carried out in which only
high purity phosphoric acid of any desired concentration can be made
directly from various grades of phosphate rock and low grade phosphatic
by-products and wastes.
water present in the crude monocalcium phosphate react ant and 3) proportion
40
four hours of reaction time as was obtained after one hour, and any
differences in the data are apparently due to experimental errors alone.
Methanol solvent.
acid P.-^,- yield, product acid impurity concentration and filtration rate
when methanol was used as dissociation solvent for dissociating monocalcium phosphate containing 32 and 47 percent P 9 0 q are shown in
Tables 5 and 6.
It has been shown (11) that the product acid P Oq yield increased,
41
0)
PH
QJ
cu
ai m
4-1
4-1
pc;
s-i 4-i
4-1 P H
r-H
-H
O1
P H CO
^
<4-| S-i
O Pd
^ .
en
rQ
(-J
H
4-1
CtJ
J-l
4-1
.-H
-H
4-1
> C
t-H
CU
C
O
H
4-1
Ctf
S-l
4-1
CO
5-1
0)
4-1 P-i
OJ C M
S-l C O
I-H
cu
4-1
4-1
T3
CU
H
Q
C
-H
rt
H
pH
LO
LO
vO
LO
vD
CO
ro
CO
LO
PH
vD
H
t-H 4-1
Ct5 CtJ
4-1
O
VD
vD
CO
<U W
4-1
(T5
.
ti
4-1 .
H ft
^
w
O
CU .
4-1 P H
*d
J-l
d)
M
d
PH
="1
O
CM
cu cu
H
ft
rt
g
ft
n)
0) H
CU S-l
>ti ( ^
S
3
O
S-l >^ -H
O
S-l -U
S-i <T5
m
3
S-I
O PH
H O
PH
tf
C
o
TI
4-1
CU O
H
CU
^ - / pc;
en
o
-H
LO
-u
o
d
CM
Ptf P H
LO
LO
LO
vD
CO
VD
CM
H en
J-l - H
3
en
ft cti
VD
CO
CM
PH
LO
00
C
CM-H
PH
T3
i-H t-H
td
LO
vD
-H
O
4J
C
<
(1)
O
4-1
S-l
a)
4-1 - H
PH
-d
CM
LO
PH
CO
CO
VD
CO
CM
LO
PH
^ ^ -s
CU
3
s-i
U
LO
LO
CM
>-> LO
4-1
S-i
ctf
3
SH
4-1
C
O
S
LO
PH
e
2 e <u
H
O
d
O
S-l
CJ T3
r - l M-l
CM
toO
4-
CO
. ctf .
ft-d
o
en - H <rS
o
S-I
w
si
o
PM H
u
pH tf
H
O
en
in
H
Q
CU
en
H
is
cu
bO
cd
u
CO
vO
LO
a o
*d
CO
vO
LO
r-i en
C ^
U
(T5 O o
o
m
4-1 pd LO
0)
<3
rf
-d
4-1
CU
VD
rt O 4-i
. H
O
4-i
ctf
CD <4-l CD
S
O
S-l P H
<4-l tf 3 g
o a
*a
*a
M
tf
*a
X)
CO
CO
vD
JQ
CO
CM
CO
vD
vD
CO O H
T3 PH
a
LO
3
5-IO
O CU CM
PH
ft PH
0)
JDIH
g O
*a
VD
CM
vD
vD
CM
CM
CO
CM
VD
42
60
GO
PH
>,
>,
m
GO
CM
PH
13
PH
Cti
CD
aj e
H
u -u
o
M-l
fi
CD H
cd o
U ctf
a)
M-l
>->
o
H
C
U
O
Ctf H
SH 4J
PH
4J Cd
i-H H
H O
M-l O
CO
CD en
JC H
4J T3
4J M-l
C O
CO
co 5-i
CO 3
U
O
ax:
CD
SH
CD
C
W
5-i
o
CN
PH
a) C
CO
rQ cd
CD S-i
ft
43
m
o
CM
03
cu
CM
4J
cu
c c
4J
0J
PS
4J
0)
CU
>
, - 1 5-1
O
0)
c/> P-i
4J
5-1
cu
<
4J
0J 4J
5-. P M
4J
CJ
o
H
CJ - t r 4J
O
- H CO 03
5M
i-l PH
5M
4J
4J
i1
0}
^ pd
H
5M
O
4J
PM
i-l
W
H X3
pM 1-3
c <t
CU
*d
CU CU
5M
UM - H
ii
^^.
r^
M-<
UM
<t
o
<t
CM
CM
r^
ii
CM
I1
CM
i1
CM
O
i1
CM
O
CM
CM
O
vT)
CM
O
CM
O
CM
O
CM
O
CM
o
r^
ii
CM
a\
O
CM
i1
CM
CM
H CTJ
Q
4J
5M
U
O
CTJ O
^
o o s
C O u
o3 p i o
X
m
4 J CU m
CU 4J
x:
4J
H
03 CO
x : oJ
cu
CO
O
X
CM
CU
4J CTJ
03 T 3
cu
toO
oJ
4J
co
x : -H x :
CU U
o
to o 03
O i-l W
X PM
4J
CM
e
e
o
3 H
o3
*d
4J
0}
5-1
CU
H
O
i-i
}
a
O
4M
cu
J-I
CTJ
oJ *d
H
a
5M
CI
CO
CO
cu
CO
I-l
Jg
CU
XJ
--'
.
co pti
CO
00
r^
en
r^
r^
m
r^
m
r^
00
CTi
00
r^
r^
oJ o3
4J o
ii
o
en
<}
00
i1
CO
i1
VD
VO
C^i
CO
i-l
i-i
l-l
ii
CO
iI
CO
ii
o
o
i-l
O
CM
CM
ii
00
CM
I-l
r^
o
l-l
i-l
I1
m
o
00
i-l
l-l
l-l
vo
l-l
\D
O
>X>
O
m
o
\D
O
o
o
m
o
00
en
v>
O
00
l-l
cr>
VO
CM
r^
o
r^
o
<t
o
o
o
r^
o
PM
o
o
r^
m
r^
m
I1
v>
00
CO
O
>>
<J-
<
m
CM
en
o
m
< !
<!-
v>
CO
r^
<t
m
r^
v>
CTi
<f
o
m
CM
CTi
<t
m
m
CO
00
O
O
<J-
<f
CO
\D
CO
cr.
CO
CO
<}
r^
VD
XI
CM
ii
<}
O
00
<f
!>,m
CO
CNJ
CU 0J
& pq
H
^
iJ
<
4J T 3
CJ - H
CO
CM
CU
CM
rt
in
T3
O
C H
CNJ-H o
4J
CM
CU
i-l
4J
O
'H 3
>M T 3
i-l
i-i
a
u
ii
CTi
r^
CM
CU
vD
CM
o
en
o
en
<ico
CM
CM
CO
CO
<t
<}
<}
<J<t
CO
x>v D
x>< }
XI
CM
i1
i-l
l-l
i-l
I1
vr>
r^
00
CTi
O
iI
c
01
c
o
H
4J
O
03
CU
PS
CM
CM
i-l
i-l
oJ
C
OJ
4J
O
XI
4J
CU
TJ
CU
4J
H o
oJ
M-t
UM
T3
ci
3
CO O
T ) CM
Xi
CU
5-1 C M
O
PO g
c
c
T3
Xi
Xi
>
>
Xi
ii
ii
i1
i-i
en
vT)
\D
CTi
en
Xi
I1
CM
r^
X5
r^
Xi
X>
XI
ii
i-i
oo
CTi
CJ
in
3 n o
O cu CM
r^
r^
r^
r^
r^
r^
i-i
i-i
i-i
i-i
ii
r^
i-i
00
CC)
00
00
00
00
00
CM
CM
CM
CM
CM
CM
CM
ii
C U CM
5M
XI
03
H
CJ
<C
T)
i-l
oJ cu
4J
O
CM
CU
00
03
T3
CO
4J
aJ
O
CT
4J
H CO
JM -i-l
cu
cu o
toO >H
aJ
4J
vT)
CT
r^
00
B-2
5M
g Pn
CU
r^
CJ
H
I-l
4J
m
en
5-1
>, C
O
H
4J
I1 03
4M CO 5M
4J
o
CM I1
C o H
g O
H
i1 4 J
C*J
CM
u
u
ci
5M
CM
cu o
a <c
T3
3
d /~< O
o u-1 H
cu
C cu Cu
o cu R
g
n cu
CM H
cu
3
u
o
4J
O
CO
oJ
Pro
-I
->
CU
X I UM
O
&
3
S3
CO
CU
00
03
4J
CO
ii
i1
ii
ii
i-i
ii
44
CT3
CD
m u
OJ
4-1
Cd
P^
OJ
4-1
Cd
J-l
4-J
H
-H
[i4
<
4-)
PH
C
O
-H
1
fi
O
4J
O
CO cd
rl
\
J-l
4-J
J-l 4-J
Ct) M-l K
i-l
S-J O -r-l
U
pn
i1 co
o
o
CNJ
ON
I-l
o
CNJ
CNJ
o
m
I-I
ON
I1
I-I
o
CNJ
13
rl
cd
CD
rl
J-l
o
si
,n
Pn 3
O
r - j CO
Ctf
i1
Cd
4-1
3
13
O
5-1
P-l
rl
13
CD
4-1
CJ
O
V w '
4-1
H
S-l
3
X-N
l O H
O l
OJ
P-I
CO
H
X!
CO
eel
4-1
4-1
o
si
ex
CO
J-l
M-l
CNl
T-l
60
^S
en
o CNl
&
rt
6 PQ
en
ii
m
o
HJ
v^
4-J
13
<:
O
CD
CN
CD
P4
5-1
CD
ON
CtJ
H
Cd
ON
<i-
en
J-l
ex
t3
M3
tH
CD
<u
O
-(->
J-l
CD
<t-
J-> - r l 3 Pn
O > H T3
H
O
<r
Ct)
CD
i-l
r-^
<r
ON
en
m
<r
cd x)
4.) cu
Si H
4-)
O
cd
M-l
M-i - d
O C
3
O
T3 P-i
jH
3
J-i
rQ
^
O
<J-
CD
j-i p.,
C
O
t>
g
o CNJ
rl
P-.
m
o CNl
c
CD
4-1
ex
SI
cd
H
J-l
CD
CD
4-1
CD
>^
>
CNl
T-l
r-i
<i-
m
<r
s*\D
ON
ON
i-l
t--
r-^
t--
I-l
t - <
t-1
00
g o d
-W
CO
CD
CO
3
J-l
o
M-l
CO
CD
H
4-1
H
C
O
60
cd
4-1
CO
13
ex
S-l 4-1
O
M-l
fj
en
H
CO
^-1
na
CD
J^
C
3
M-4
C
O
rl
CJ
~ \
4-1
CD
cd H
O
H
4-1
cd
J-i
CD
Si
4J
t - <
r-(
J-l
4->
4-1
Cd
^^
rl
CO
CD
4-1 1 3
>.
rQ
4-1 M-l
CJ
13)
CD
CO
CD
5-1
CD
ex
ex j n
P-I
cd
s-i cd
4-1
o
J-l
S-l
t - <
CD
J-I
T3
CO
J-l
CD
Si
CO
O
S-l
CD 3
J-l O
CD
J-l
13
CD
rl
cd
4J
rQ
CD
C
t - <
CD
rl
CNl
en
cd CD
CD g
H
u
CD
CD
J-l
CD
J-l
fi
O
o
CD i-l
4J 4J
Cd O
m
o
en
T3
o
si
4-J
cd
-C
CD
CO
fH
CO
CD
60
rQ
4J
t - <
ON
cd
4-1
cd
t - <
00
t - <
H
4-1
i-i
CD
CO
si
--^
i1
CD
CNJ
X P-I
3
!3
.
^
<!"
00
CD
J-i
CJ
m
4-1
O
Ct)
<t
m
<r
<J-
(D
4-1
'rl
CD
, D M-l
rl
J-l
e_>
>>
~
r d
4-1
P-i
t H
5-1
P-i
rl
C
3
<:
,1
<r
T3
11
O
P-I
CO
4J
4-1
C
CO
13)
CD
CNl
-rl
O
O
SI
Acid
C
CNl-H
P-I
CD
4-1
P-I
cd
O
r d
Cti
cd
<D
6-S
CD
t-1
o
e
S-l
CD
P-.
i-l
cd
si
4-1
CO
CJ - H
rl
CO
H
CO
ll
4-1
13)
o <c
^
o
4-J
Cd
O
>>in
\
m
o
A
en
m
4-1
CO
P-.
~
oa
num
4-1
O
CNJ
S o
H
CD
Xi
cd
CD
SI
J-i
CO
SI
60
ex
CO
H
CO
ON
CNJ
Dre
P-I
CO
J-l
CD JH
42 ed
rl
^
3 4J
C
CO
4J
i1
res
CNJ
g not
he f
isso
CD
CD
si
H
rQ
CD
S-l
SI
o
CD
jd
H
13
45
the total major cation impurity content of the product acid decreased
and the filtration rate of the dissociation slurry increased with
increasing dissociation temperature.
shown (11) that the best dissociation temperatures for methanol and
acetone were 55 and 50C respectively.
The data in Table 5 resulted from experimental runs involving the
stagewise dissociation with methanol and crude Florida monocalcium
phosphate containing 32 percent ^^0
ratios in each stage.
percent P90_ yield in the product phosphoric acid increases with each
subsequent treatment through a total of three stages, although the yield
in the third stage is quite small compared to the first two stages.
The P90
increased rapidly
p
90,-5
P^r
y^ e ^
46
became relatively constant at 43 percent conversion to product acid P90,in the second stage after treating crude monocalcium phosphate with six
and seven pounds of methanol per pound of P90,- in MCP in successive
stages.
treating crude monocalcium phosphate with six, seven and five pounds
of methanol per pound of unreacted monocalcium phosphate P90,- in three
successive stages.
The data in Table 6 resulted from experimental runs involving the
stagewise dissociation with methanol and crude Florida monocalcium
phosphate containing 47 percent ^?0
ratios in each stage.
47
filtrate P90_ that resulted per hour per square foot of filtration area.
The filtration rates of the slurries resulting from the stagewise dissociation
of 32 percent P90t_ monocalcium phosphate decreased as the methanol solvent/
P C^ ratio increased.
48
ratio on product
acid P90_ yield, product acid impurity concentration and filtration rate
when acetone was used as the dissociation solvent in the stagewise
dissociation of monocalcium phosphate containing 32 and 47 percent P90[are shown in Tables 7 and 8 respectively.
P^O
slurry filtration rates are the values obtained after one hour of
dissociation reaction periods in each stage.
The P^Oc yield in the product phosphoric acid resulting from the
first stage of the stagewise dissociation of crude Florida monocalcium
phosphate containing 32 percent P90C.J increased with increasing solvent/
P 0[_ ratios up to 6 and then, remained somewhat constant at approximately
30 percent conversion to product acid P90c. with increasing solvent/P90
ratio from 6.4 to 8.2, while similar results obtained from the dissociation
of crude monocalcium phosphate containing 47 percent P90j- show that
percent P90
It is seen from
49
co
O
H
-M
-H
-M
O
m
oCNI
aj
aj
PL,
pen
QJ
4->
&
a
a;
>
-!
O
CO
O
CM
P-i
4->
oj
cj 4-1
cr 4-1
I-I
-H
CO
J-l
M-l f C
O \
cj
qj
4-1
o oo
4J
oM
S
B^
4-1
H
CO
cj
cj
3 *a
H -H
O S - J O )
i-l
O
M
CTJ Ii
ccj
O f^
4-1
O
CO
M-l
0)
Td
nd
3
U
CJ
M-i
4-i
QJ
s-i
cd
J*, J-i
J-l
J-I
CNl
CO
CO
CO
CO
CO
CO
CNl
o
co
o
co
o
co
o
co
CO
CO
CO
. N
vD
O
CNl
. r>
co
.^
o
co
vD
CNl
vD
vD
m
o
m
o
o
co
CO
O
co
a>
00
vD
a>
r^
CO
r^
r^
vD
vD
o
r^
m
o
a>
< !
vO
0)
ii
CNl
I1
CNl
I-I
CO
I1
CO
ii
ii
vD
ii
i-H
i-H
i-H
i-H
CNJ
CNl
ON
CNl
00
CNl
I1
< !
< !
CNJ
co
CNl
CNl
a>
CNl
r^
I-I
CNJ
CNJ
vD
co
CNl
CNl
I1
CNl
i1
CNl
I1
CNJ
I1
i-H
i-H
i-H
i-H
i-H
a>
o
o
r^
I-l
< !
< !
iI
I1
CO
I1
ii
ii
CNl
i1
iI
r^
<
co
o CNJ
o <d
QJ
PM
SM
0)
PM
o
a>
a>
m
vD
r^
co
o>
r^
o
CNJ
I1
co
a>
a>
a>
ii
CO
co
co
co
co
a>
o
O
cj
CJ
V
Cj
in
T1 Tt
r^
co
r^
CNJ
< !
ii
ii
i-l
i-l
I-I
i-H
o
o
CNl
CNJ
CO
i-H
i-l
i-H
i-H
o
o
co
o
o
'O
-H 4-i
CNJ-H o
a
PM
<d 0)
T3
O
r^
I-H"
CJ "H
4-J
J-l
Cj 0) O QJ
4J -H 3 PM
O >-< T3l
H
O
CNJ
00
CNJ
CNl
ro
< !
r^
CNJ
co
a>
vO
CO
co
CO
CO
co
< !
< !
< !
co
m
co
vD
co
VD
CO
CO
CO
SM
0)
a,
PM
i-l
CO
0)
H
O
w P-,
qj
QJ
w o o
H S
Q
-H
-M
QJ
0) M3)
CO d
H
J-l
Cj
J-l
4-1
i-l
CJ -H
0)
PM
txO
Cj
4-i
CO
o CNJ
4-1 T 3
4-1
Cj
cj d
H
O
vD
ii
J2
o PL,
u 4-1
o
a
O
co
CO
J-l -H
2 CO
PH cd
g PQ
H v~/
n o
cj
0)
U
Cj
Cu
a>
vD
CNJ
ii
r^
PM
CO o
c
e
O
O
<N
CNJ
iOH
a
H
o o o
x:
x: m
PM PM
g
vD
i-H
. N
i-H
u o
f
CN
cj cd
X! X! "-N
pu & CJ
CO
oCO
CO
i-H
PM
P*
4-1
m
o
V
<d
a;
a>
-H
i-l
4-1
4-1
Cj
Cj
O
4-1
O
*tJ /"-N O
a; C
a;
o
co
CNJ
<t
CNl
o< N
J-l
O
r - ) CO
O
O
r^
CNl
co
i-H
ovD
o
CNl
T-\
QJ
r^
a>
ro
ro
oCO
o
co
i1
CNl
CNl
>H
cd T3l
X!
vD
om
PM
ro
4-1
H
CO
rCt
KJ
<N
a; C
C -H
o cd
4-J
oI1
Cj
S-J
4-1
PM
o
m
JD
a
o
S-J PM
4-1
H
S-J
O
0) J-J
M-l Q)
M-l PL,
H
4->
4-1
O
H
4-1
Cj
U
4J
i1
H
PM
4-J
o
co
a) o <J
QJ
4-1
P4
e
a
0) QJ
0j
QJ
J-l
M-l
QJ
J 2 T3l
H
qj
^
Cj
i1
Cj
qi 4J
O
O
4-1 H
0)
O M-l
<
O
*d
QJ
4-1
O
Cj
QJ
U PM
s H
a
CO O
T3l PM
qi
rO
vD
i-H
rO
CNJ
CNJ
T3l
rQ
rQ
rO
CNJ
CNl
< !
< !
vO
vD
a>
rQ
rQ
vD
< !
i1
ii
rO
CO
I1
rO
CNl
I1
rO
i-H
CNJ
rO
vD
ii
i-l
r^
00
v>
r^
CO
a>
JD
i1
vD
vD
vD
vD
i-l
i1
vo
i-l
i-H
CO
CO
co
CO
CO
CO
< !
ql s-j o
O QJ CNJ
PM pi. PM
rO
i-H
rO
CO
CNl
i-H
vD
CNl
CNl
CNl
i-H
i-H
.
.
vD^
.
.
vD^
VD
i-H
i-H
i-H
CO
CO
CO
CO
co
CO
< !
. r>
CO
#N
co
. #N
i-H
CO
.
#N
r^
QJ
I-l.
rQ
Cj
S-J
QJ
, D IW
co
QJ
60
O cd
4J
CO
53
iI
i1
ii
i1
CNJ
CNl
CNI
CNl
CNl
<N
50
P-i
CJ 0)
4-J 4-J
M-l
O
CU
U
<
bO
ni n u C
Pi
U Pn O
4J
-H
C r-4 CT 4J
O -H W
d
H
h J-l 4J
Ctf M-l X -<
J-l O
Pn
X)
bO
M-l
hJ
PM
cu
03
d CJ
S O
H
t - I 4-J
03 cd
4-1 O
inH
Ol
CN
P-i
Xt
O
JM
P-l
cu
CM
CJ
X)
X)
bO
Xt
>iin
4-1
H 03
J-l -H
MM
3 en
Pu flj
bO
e
CJ
CM
M
CM
4-1 X >
-H
CTJ CU
PM
CD 6
CU O
CM
O <
H
J-l 4->
O
MM CJ
O
CD - H
4 J 4-1
Ctf O
J-l 03
CJ
xl
H 4-1
O CJ
<C CU
O
4-1 }-l
aj cu o <D
4-J H 3 C M
LO
CJ
<H
P-i
Xt
t - I ,-1
MM
Cu
o^-d
X)
CJ 5-1
O
H CJ
4J
O
Ctf H
J-l 4->
4 J 03
r-4 H
r-4
O
MM
CM
<C
CO ctf x t
CJ 4-J (U
O O 4J
W H O
a>
aj
O M-l cu
<
O U CM
Cl CJ
MM X ) D
S
o c;
xl
cu d
oo
J-l
JM
CU
CJ
J-l
oo
CU CJ
3 u o
rd
m
CM
CD
60
6 o aj
0
53
cu
w o
O O
N
CM P U CM
M-l
O
W
W
-H
XI
M-l
O
a ^
cu
XI
,JO
CU
-CJ
4J
4J
CJ
03 J-l
3 CJ
03 O H
X t CM
CJ
4J
CO
X)
cu
0j
cu
cu J-i
X)
51
cd
cu
PM
5-1
u
u
d
CD
>
l-J
o
CO
u
d
cu
o
PM
d
o
r-<
u
cu
PM
r^
<t
<:
x:
u
cd M-i
5-i
O
o
o
i-J
.
^ " N
cu
u
cd CO
Xi cd
a.
CO
I1
PM
w
u
cd
d
o
u
3
r-<
co
5-1
u
cd
u
PM I1
C J r-<
cu
XJ
CJ
co
PM
LQ
Ol
CN
PM
CTi
CO
r-t CO
5M -r-t
3
CO
&
pq
co
CN
(N
O
vO
C^
vO
CO
vO
CO
00
vO
o
V
m
o
m
o
m
o
m
o
O
V
o
V
o
V
5M
cu
cd
u
PM
m
o
CO
m
o
co
o
m
o
CO
CO
CO
co
m
vO
O
o
V
O
co
(N
CO
CTi
O
m
co
CO
vO
(N
CO
(N
CO
CO
CO
CO
(N
(N
CO
CO
CO
CO
(N
CTi
(N
m
o
CO
m
o
m
o
vO
O
m
o
o
CN
CO
CTi
(N
CTi
(N
CO
CO
O
CTi
CTi
O
vO
O
o
V
o
V
PM
d
cu
o
o
V
O
V
cd
d x)
CM-H - H
PM
O
XJ <
4J
d
CU
cd cu
CTi
(N
4-1 -r-t
O > H ^ PM
H
XJ
O
CTi
CO
CO
CO
CO
CO
CO
co
(N
CTi
LO
vO
CO
vO
CO
O
co
co
CO
m
o
CN
CO
5M
PM
cd
cd XJ
xi
LO
PM
XJ
x)
XI
xt
rO
LO
M-l no
O
d
5M
CM
<u
CU
i
S3
(N
(N
CN
CN
X)
CO
XI
CTi
iI
CO
XI
CO
CN
<t
CM
PM
CO
CU
50
cd
4J
CO
XI
(N
.1
CN
vO
r-~.
- rs
rs
- rv
r*
CTi
.1
C^
.1
CTi
.1
CTi
i1
CO
d
3
CTi
vO
XI-
co
.1
Xi
<t
co O
X J PM
5M
cd
H
CTi
VO
vO
CO
cu
4J
CO
rO
CO
<
cu
P4
m
o
H3
a cd
d
o
P4
r-<
(N
CTi
<t
>> m
u
PM
CU
vO
vO
CO
cd u o
u
cd ( N
CO
vO
CO
r-~.
B-S
XJ
co
a; o
toJU
vO
CO
r-~.
50
cd
a)
co
XJ
cu r-<
x: u
Q H o
tz>
r-<
vO
CO
I1
vO
vO
LO
>>
5-1
(N
00
cd cu
a. a.
cu id
5-1 cu
PM H
ii
cd
I1
vO
CN
I-3
<
oO
cd
5-1 cu
r-< M-l 5-1
O
3
I1 Ti
u
CtJ CU cd
o 5-1 5-1
4-)
vO
r^
ffi
5M
PM
cd co
x)
H x:
5-1 o
o cd
<t
vO
vO
5M
X)
r-<
CU
6
3
MM
O
LO
CO
PM
o
IT)
CM
CU
X>
3
5M
CJ
co
CTi
CO
O
vO
r-t X)
CJ
P^ o
PM
o
d
o
S
m
m
r^
CO
o
o
CT.
o
Xi
cd
x:
a.
co
o
x:
o
o
o
d
o
r-<
CU
u
5M 4-1 O
4J PM T - (
il
4J
r-t t r cd
PM CO 5M
4-)
S-i
u o
cd
cu
d
o
u
cu
o
<
cd cd
CD xJ
5-1 cu
CU d
M-l r-<
M-l cd
r-< u
CU MM
4-1 o
4-1
i1
CO
CTi
.1
52
m
CU
CM
OJ CD M-l
<
4-1 4J O
05 OS
0
&> U 4J O
4J P M " H
C t-l
4-1
00
M3
CM
cr oJ
-H
4-1
H pL,
Otf -M J-l iI
S-l O W -H
4-1
rH
oo
ft
PM
00
CO
H
X
pM 1-3
<4-l
Cu
05
M3
nd
.S
i-H
4-1
cu
05 05
u o
ft
CM
y
M3
M3
o in
s-i o l
CM
M3
4-1
S-I
C/)
M3
nd
50
CM
CM
M3
>>m
4-1
H CO
U -H
oo
PM
co
CU 05
& PQ
M3
O
CM
oJ cu
cu S
OO
S-I
o
m
CM
CM-H
CJ
T-l
4J
05
S-I
O
Ctf
M3
i-H 4-1 U
05 CU O CU
4-1 M-l p CM
O > H M3
cu
T-<
4->
M3
CM
CU
05 M3
d -u cu
O
O
4-1 H
CU
O M-i
<
O
&2
3
O
CM
M3
ft
ON
>1
M3
S-l
3
O
M3
CO
S-l
CU
00
m
SM
O
CU
CM
SM CM CO
ft
CU
CU
X
M-l 00
E O 05
3
4-1
CU
CO
CU
J-i
ft X
cu
CO
-H
H
C
4-1 O
05 - H
SM 4J
4-1 ctf
i-H - H
H
O
M-l O
CO
CU CO
X
-H
4-1 M3
4-1 <4-l
CM
3 C
c!
4-1
O
05
CU
S-i C M
<W -O 5
O Ci
CO O
M3 C M
<:
CO
M3
^ <u
d u
o
M-I
<d cu
c
o
CU
4-1
m
MJ
=> c -H -u
CM
4J
O
0
os
cu
CM
CU
S-l
X O
EH 6
M3
53
tent.
total yields were obtained with solid than with slurry monocalcium
phosphate.
Tables 7 and 8 also
with 1.6 to 3.1 pounds of acetone per pound of monocalcium phosphate P90,in the first stage of the stagewise dissociation of monocalcium phosphate
containing 47 percent P90,-. However, above a ratio of 3.1 pounds of
acetone per pound of monocalcium phosphate P.O., the total major cation
impurity concentration in the product phosphoric acid was relatively constant at approximately one percent.
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
the choice of solvent dictated which major cation impurities were
preferentially rejected from the product phosphoric acid.
When methanol
and
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
acetone rejects calcium and magnesium impurities better than methanol,
the total major cation impurity concentration in the product phosphoric
acid is approximately the same when dissociating with methanol or acetone
using similar reaction conditions the only exception is when monocalcium
phosphate containing 32 percent P0 was dissociated with methanol. This
irregularity can be attributed to the lower ratio of solvent/P 0
in
respectively.
55
ared
5-1
4-1
S-i
tt)
S-i
4-1
il
H
pt4
o cu
S-i
o> P-i
c
o
OJ
>-.
5-1
S-l
o i1
3
<
S-i
OJ
si
4-J
H
W
tt)
J3
a
CO
o
XJ
P-I
e
3
H
o
I1
tt)
o
o
cu
T3
3
S-l
o
M-l
c
o
CN
P-i
4-1
QJ
O
S-i
QJ
P-i
o
o
CO
CO
H
Q
xi
w
a
H
w
13)
QJ
IT)
5-2
r^ O
a o o
a
o
o
4-1
d ^o
a; o
>
ii
CO
Pi
0)
4-1
tt)
xs
3 a
B-2
<f
H
4-1
a.
o
4J
il
a
rt
S-i
LOP-I
*>
tt)
4-1
xi
tt)
o
xi
P-I
CtJ
13)
i-l
S-I
o
11
e
o
CN
P-i
C
i-i
P-i
B-2
LOO
CN O
g
CO
CN
P-i
C
H
C
O
- H QJ
H
60
4-1 \
P-, tt)
Ct) 4-J O
4-1
Pi
CJ g
CO
QJ
S >
3 i-l
g o
co mw
O
CN c
P-i
-H
P-i
LOO
r-- O g
<t- CN
P-i
C
i-i
P-i
e-2
L O O
CN O
g
CO
CN
P-i
C
O
tt)
4-J
a . M-i
fli
H
O
P-i
LOO
t^ sn
P-iCNJ3I
- H H"
O
O
Q)
<
s-i
QJ
. - I T3)
tt) i - l 4-1 P-i
4-1 Q) O
O -H
H
>H t J
O
r^
r^
vo
vo o
co
0>
<t-
co
CTi
CTi
CTi
CN
CTi LO
CTi CO
CN CT>
CTi LO
CT> 0 0
CN 0 >
<t"
CN
LO
il
o o
<t- o
LO
cn A
c^
il
r-CN
Il
i-l
O
r-LO
CN CN
i - l v>
i-l O
O
r-- L O L O
CN CN V40
iI VO "S>
CN
LO
CN
LO
O
H
S-i
o
si
a
CO
o
J3
a.
4J
o
CN
co
LO
O
CN
LO
CN
vO
CO
VO
00
LO
CN 0 0
-CN
MD
A
CO
r-0>
co
VO CN
CO
vO
00
VO
O
CN
00
co
co
LO
VO
o-
co
00
r^
co
CO
co
o-
r--
<t
i-i
11
o
co
VO
oo
O
co
CO
o
CN
CO
CO
i-l
~ vo
O
CO
VO
VO
11
LO
oo
VO
co
co
S-i
QJ
X l U-l
vO
co
CN
il
CN
VO
CN
i-l
00
11
CO
vO
O tt)
-U
JZ!
CO
4-1
cu
fX
to
H
M-l
O
a
>
Q)
il
o
CO
CO
4-1
QJ
CO
QJ
S-i
a.
QJ
S-i
T3)
i-l
<H
LO
LO
LO
LO
LO
LO
LO
LO
4-1
LO
H3)
O
5-1
P-I
CO
QJ
60
CN
P-i
00
00
3
rt
4->
o
tt)
aj
Pi
.s
*d
ii
QJ
i-i
LO
CU
S-i
tt)
S-l O
QJo
a
e
cu
h H
QJ
j ^
4-1
CN
<)
co
S-i
a.
co
CO
00
ovO
.~ r^.
VO
CO
I-I
CN
i-l
4-1
-d
tt)
S-l
ctj 4-i
,-1
T-I
a>
ii
CJs
CN < )
.~CO
O
00
P-i
l O O
r^ o g
CO
Fn
QJ
toO XJ
tt) 4-1
U
QJ 5-1
en
U-l
QJ
<t"
0>
CN
co
CO H
O
tt)
i-l 4-1
4-1
tt)
Pi
tt)
QJ
CO
H
CN O
g
CO
CN
P-i
C
i-l
<t"
CN
CNM-l
O
P-i
C
C
i-l
CO P-i
O O
i-l
4-1 X I
H
tt)
QJ Pn 4-1
M
S-l
tt)
tt)
P-i
4-1
'
a 4 s-i 5-2
lOU
H J D
CO 4-1 CN O
g
H
QJ
CN
pH 4-1 lI \
1I CO
P-i
C
tt) - H S-l ' i - l
H
P i P>4 JX! Pn
S-i
O
QJ
60 CN
tt) c o
4-1
U
CO
QJ
Xl
O 4-1
tt) i-l
tt)
H
P-i
5-2 m o
<t"
> '
o
g
~
Si
4-1
QJ
Pn
4-1
4
tt) M-l a
Pi
O co
M-l
3
S-i
o
& cu
o> x: r-4-1 H < f
si
4-1
H
CN
P-i
C
i-l
IT)
O
QJ
13)
14-1
P-i
<f
~ \
CO
r> O
Pn
a.
P-I
i D O
6-2
il
i-l
i-i
CN
CN
a
CtJ
o
C
o
CJ
si
tt)
J3
tt)
J3
4-J
4-i
cu
g
4-1
QJ
QJ
QJ
QJ
oa
4-1
a)
o
<
T3)
i-l
QJ
H
QJ
4-1
QJ
O
4-1
QJ
<
<
LO
TJ
CNH
P-i
O
cj
tt)
56
used for these experiments were solid materials which had to be pulverized
prior to dissociation.
The Po0
57
<1)
4J
i-t
5-1
JM
CU
|3
I-I
-rM
5M \
irM
- i trj
MM
Cd -rM \
CU pM LO O
4-J
o
Cd MM
CM -U
PM ftf
O
CM PM
cd
5M
4-J
iI
H
a cd
cd
CU
CT
cd en
X)
CU CO
U i1
u u
Cd o
g LO
m
MM
o a
X)
rM
-U
u
a
LO
O
CM
CM
O O
m
4J
CD
> MM
i-l
O
en co
>>
MM
5M
<;
nj
I-I
LOCM
CD
H
i H v - ' .
O
iM
cd
O
rM
CM
C_)
5M
(=!
cd
^ g
cd
a
^ d o
a
O
co
TM
LO
-U
O CM
.-I
i-l
oo m
O
ON
^
ON
ii
ON
rCO
ON
CM
LP) VO
CO
O
i-M
LO
ON
i-l
r^
<f
-I
CM
i-M
CM
CO
00
O
LP)
CM
ro
ON
< f ON
.-I < f
r-
ON
00
O
i-M
ON
CO
CM
VO
<f
r-
LO
r-
i-M
LP)
i-M
CO
ON
<f
ON
CM
co
iI
i-M
CO
rO
LO
CO
o
ON
<f
VO
O
o <f
LO
i-M
CO
VO
vo O
00
LO
<f
LP) r
<f
O
<f
rO
i-M
LO
ON
O
<f
<f
--I
--I
i-M
CO
ON
CM
LO
ON
00
CO
CM
CO
00
CM
ON
CM
00
CM
ON
r-
co
O O
o o
r- r< !
< !
a;
>
H
d
cu
>
ii
o
en
o CU
d d
cd o
4J
XI
4-1
cu a
g <
1
CO
CD
co
Pi
II
CU
"N
cd
LO
5 T-I
o
cd 5M
CM
ftf CU C M
^.^
d
cu co
a
d <h
o co
CJ v_x
i-M
CM
ON
CM
CO
CM
O O
co co
O
vo
00
O O
< !
< !
vo vo
ON VO
AO
VO 0 0
i-M CM
< f ON
LP) O
< !
< !
LO
CM < j CM i - l
CO i-M
CM < j -
ON
CM
00
CM
O
CO
0 0 ON
CM CM
r^
ON
CM
CM
O
vo
O O
O O
O O
< !
< !
00
i-M
< !
< !
LO
LO
LO
LP)
< !
< !
< !
< !
cu
d d
cd
x\
4-1
O
4J
CU
O
cu
d d
cd o
4-1
O
4J
cd
TJ
cu
4-1
o cd
5M
i-M
PM
4J
<U
<
cu a
g <
d o
cu
o <t
co
d ^s
o
CJ
d
cu co
co
o ^s
d
o
CJ 1-1
CU
g
1
H
>M
^1
cd
II
i-M
LO
00
i-M
CM CM
< !
< !
4J
>->
I1
4J
ON
vo
cu
a a
rM
C M <u
O
C M pcj
CO
<!
CM
4-J
-(, O
4-J CD
co o cd
ON
!=)
5M
4J
<-i
H
xi
5M
CU
CM
mctf CJ
cu g
4J O
CM 5M
d
d
cu CM
a
~N
I-I
X)
PM
LO
o d cu
CU 5M T M
X) U
4J
5M
<
Cd
4J
CU
ON
LP)
VO
CMd
CM H
o Su CeD
a
H
ON LP)
0 0 iI
iI
CM
-U
VO CM
ON O N
iI
O
cd
CJ>
O
CU 3
~ 4J
rl X l
d
>M o nd cu
5M TM
o
3
5-4 4-J
H
CD cd
O
5M
I1
CD
cd C M
d.
S-d
nd
<
CD
cu
u u
cd o
a'w
(0
CU
PM
cu !-<
5-I
-rM
CM
O CU
X
U CO
CM CM CU
CM
LP)
jj'd
cd
X
a
to
CU ^ w
^
5
o
5-1 4J
cu
LO
CO
nd
5M
d
fU
u cd
d PM
-i-t
a
g co
X
-t-J
>
O
CO
5M
CD
4J CM
rM
5M < f
vo cd cd
.d
P
W)
CD
cJ co a)
3 2 g
o o
CM
CD
5M
o jc-d
a
i
cd
co O
CO r
<1)
CD i1
MM x )
O
x)
5M
d
O O
n T-(
Cd 4J
g
Cd
cd
0 , 0
CO O
PL,
O
ON
CO
X)
d
a cd cd
3 JJ
0
P-(
<f
CM
cd
nd
H
5M
O
i-M
PM
I-M
CU
4J
cd
u
4-1
cd
nd
>M
^i
-N
LO
o cu
d d
cd
X
4-1
O
4J
CU
cu a
g <
d
cu co
o
d CM
o CO
CJ ^s
1-1
1-1
cd
d
>M
*-i
cd
nd
>
<U
4J
?M
4-1
o
i-M
PM
>
1-1
cu
CD
4-1
>M
5M
4-1
cd
O
i-M
PM
cd
*-l
4J
cu
d d
O
cd
X
4-1
cu
g
O
4J
c
u
O
<
o cu
d d
cd o
X
4J
4J
CU
cu a
g <
d o
cu
a co
co
d ^s
o
CJ
o cd
i-M
PM
o cu
d d
cd o
X 4J
4-J
cu
cu o
g <
5M
4J
CU
i-M
rM
X
X
5M
4J
cd
CU
CM
cd
cd
d
H
/-N
5M
ON
O 00
i-M CM
PM ,
-'
CM
O
5M CM
O
w
i-M
PM
M
T3
H
58
C
O
ID
pQ
+J
C
Ctf CO
I
i-l
4-i
fn
C
O
14-1 - H
u
I-H
H
Pu
cd
QJ
5H
ctf
5H
pn
mo
tti
U
4-1
iI
S-i
cti O H
U ctf
o
3 OCN
5H
ON
4-i < ;
-u
o
ctf M-l
CN4-I
(3j O P-i P H
O
5-i
P-i
cd
QJ
VD
VD
h
<-l
CN
CN
CN
CN < f
CO CO
. - i <1-
I-H
<n <f
<l- o
CN ON
i-l O
<N CO
CO ON
4-1 ! - ) 4-)
O ctf ctf
H g
O
P-i
4-1
oO
C
QJ
<-H
vD O
i^- oo
r- o
CN CN
CN
O
o
m
m
o
r-
o
i-l
o o
o o
5H
>> QJ
4-1 P H
H
U
<f
3 m
a,
& w
fl
-H
co
4-1 Ctf
C PQ
QJ
w
O
a; -i-i
P-i
TJ
i-H
QJ
m o
<l- r -
i n i^CN CN
<r <r
ON <t"
CN
o I-I
ON
CN
<N
CN
<t- m
< f en
m CN
m <t-
ON
i-l
v>
<f
o
O
I-I
r-
Cu
CN
vO
CN CO
vo <f
vo o
<t- ON
vo O
oi
3
4-1
C
5^ "d a)
m P-i - H o
o
o u
P HCMCJ
-H
4-)
<ti
o m
<l- r -
oo <tm
00
00
<r I-I
CN
VO
CN
CO
CN
r^ oo
vo oo
CO CO
<N
CN
CN
CN
0 0 ON
oo m
CN CN
CO
O
CN CO
o I-I
CO CO
Pa)
H
13
C QJ
E-f
-H
4-1
C O
(U
CN
4-1
O
H -O
~
pH O ct!
vo
CN
4->
O
nj
PH
QJ S
< N 5H
O PH
O O
<h <1-
CN CN
o o
CO
iI iI
00
o o
CN CN
v> VO
<!" <!"
<r) m
Z
O
> . >H
4-1 5-1
H
PH
Cu QJ
M
O
d)
c e
nj o
x : 4-i
4-1
QJ
QJ
O
S <U
o
ti
itf
XI
4-1
QJ
cu
ti
O
4-1
QJ
O
S <
o QJ
C C
ctf
X!
4-1
QJ
CD
C C
ttf
O
4-1
QJ
O
4-i
si
4-1
QJ
S <
QJ
O
S <
Q)
c d
mo
x:
4-)
QJ
4-i
QJ
O
S <3
CU iI -<!4-1 i - l
.
ctf
-H
Cti
Pi
QJ
5^ a,
5H
m
o
CN
QJ
PH
B-S
moo
3 00
Hi
x)
H
PH
.
m
vo
13
i-l
O
i-l
M
I-l
M
iI
PH
X! O
CU
<N
^
co x :
x : - H ctf
X)
PH
1^.
4 - 1 ^ ,
.-I
o
fH
4-1
^
14-1 O iI
O
O
ctf
CO pej 1 3
QJ
QJ
ttf
ctf
O
x : 4-i
4-1 QJ
QJ
O
x : 4-i
4-1 QJ
QJ
O
S <
S <3
O CN
CJ CO
o
o
o
m
iI
O
5-4
QJ
4-1
Ctf
ctf
C/l
m m
x)
o <f
H
iI
O
QJ
4-1
nJ
Ctf
O
S-l
4J
!3 O
5^
4-1
!3
-H
c c
QJ
O
O
H
5-1 4-1
QJ
O
PH
nJ
QJ
= a
T3
I - l T-4
QJ 4-1
H
ctf
>H
H
O
m o
O co
< N CO
-H
PH
59
The concentrations of
major cation impurities (CaO, Fe?0 , A1?0 , MgO and total major cations)
that appear in Table 10 represent the weight percentage of these species
in product phosphoric acid containing 54 percent P90_ with all such
impurity concentrations having been obtained after one hour of dissociation
period investigated using a certain set of reaction conditions. The
total major cation impurity concentration in product phosphoric acid is
the sum of the impurity concentrations of the CaO, Fe 0 , Al 0 , and MgO
species.
60
61
The
The sulfuric
of about 1/8 to 3/4 in. The mixture was then heated for about 30 min
62
impurity in the product acid along with the filtration rate of the extracted
acid which resulted from the stagewise extraction of dried acidulate, which
was prepared from Florida phosphate concentrate I, with a solvent ratio of
2 pounds of methanol in each stage /lb of P,>0
in dried acidulate.
Table 12
63
13
QJ
nj
pu
MM
LP)
M-l O
M-l
O
CM O
Pi
4-1
W
H X>
QJ P4 H
4-i
13
nS
PL|
<u ^
5-J
CM
CM
CO
fi
o
H
QJ 4-1
4J Cd
4-i nj u
H H
4J
3 C
13
QJ - H
4-1 O
CD
O
C
Cti <a;
3
O
U
4-1
13
13
4-J
iI
4-1
X
W
ai
en
bO
H
tti
4-1
QJ
CO
>>
XI
13
H
O
13
0J
-H
U
Q
U
4-1
C
QJ
O
C
O
<
O
H
M-l
C i-l
H 3
co
QJ nS
^
4-> 1 3
T3
nj HH
c
>H
O QJ
<
4-1
nS
5-J LPi QJ
O O 4-1
XI
CM nS
ftpn
x:
CO
P*
O M-l CO
XJ O O
PH
X!
T3 PH
M-l C
O 3 ni
O 13
0
PM - H
4-1 O i - l
O C PM
3 nS
" ^ XJ g
O 4-1
0
U
QJ 5-J
PM g
M-l
H
fe
13
<t
<t
<t
VH
<t
vo
13
-H
O
3 <
f>
M-l
. O
0)
00 13
ni-H
4-1 O
CO <
vO
t>0
H
Q
fi
O
H
4-1
O Xl
O
d O -H
^
nj u
J-l iI
-H S
fn \
4-1
H
P
M-l
O
00
vo
<t
e
CD
M
QJ
13 0) MM
a; x : MM
H
^
Q;
U
<
vO
H 3
O
5-J
<
U
H
H
nJ
4-i
ctf cr" nJ
U co 5-J
CU 4-J
4-1 iI
H
p4 p i
m
O
*J
M
4J
O
13
QJ
O
5-J
PM
Cu
<t
CM
00
00
PH
oo
m
00
<t
<t
bO
O
H
C
4-1 - H
tf
5^
4-1
C
QJ
O
C
C_>
O
-X)
"H
O
<
LPi
O
4-1
CM O
PM 3
13
MM O
O PM
5-J
4-1
C
QJ
O
U
QJ
PM
CO
<t
X)
00
vO
vo
vO
MM
QJ
4-1
ti
VH
.
QJ
OJD
Ctf
+->
m
c ^
O
'Xi O U
i - l 3 QJ
QJ 13 PM
H O
>n VH
PMflJ
T3
H
4-1
<t
nS
oo
LPl
PH
CM
PM
QJ
4-1
QJ
(T)
Ctf < J
4J
O
H
PM
13
QJ
Ctf
X3
+->
4-1
fi
4-1
O
O
QJ MM
CO O
QJ
U
W
oo
,-M
4J - H
MM 4-1
O
<t
oo
cu
^ B
m
H
CM
PH - d
QJ
eu
PH
a, c
X)
5^ B
QJ - H
13
QJ C
XI rt
H
C
QJ
O
O
VH
^
CO 3
QJ
CMMM PM
ffi .-I
O
< M
C^l
oo
m
<t
LO
vO
D
CM
PM
rj
QJ
QJ
U
XI
64
M-l O
to
T3
C
3
CD
S-<
CD
P-i
CD
4-1
cd
x : -
4-1
H-O
? -rl
O
CD < J
4-)
cd CD
i-l ' d
CM
T3
H
O
<J
S-I
M-l
CM O
P-i
O CO
4-1 O
H X I
CD P H - H
4-1
4-1 ,-H" 4-1
1
4J
iI
H
I
C
O
a
pH
4-1
(fl
W)
4-i n d
H H
J-I O
MH
O
3 <d
a.
M
4-i
C
CD
O
W H
3
W
O
cd nd
p^ C
u
X
C
-H
00
a3
O
H
CD
id o
i-1 <1
c/)
nd
>> CD
, 0 -H
CD
S-I
4-)
-U P
H
o
<J
d
H
o
C
O
a
tli
x:
*d
ft
CO
O LOX!
H O PH
S-I
CM
o PD cd
x:
n3
a . M-I . H
CO O
J-I
PM
CD MH
>-N
O C
O
H O - d -rl1
4J
O
4-1
CD
CD
S-I
T3
vO
vO
VO
vO
CD
CD 0 0
4-1 Cd
Cd 4-1
SH CO
CM
vO
CM
C
SH
O
CD
H
PU
4-1
Cd CD
00
n e
4-1 H
00
rl
JCd
3 o cd s-i
- d <J ft 4J
O
CD C
S-i M-l S-I CD
PH O PH
O
CM I PH
PH
X)
H O
i-l
O 4-1
cd < J
4-1
o
H
cd
r-l
C
-H
3
-d
M-l 4-1
o
LO
P-i
h to
i-l 3 CD
CD ' O P-i
H
O
>H SH
P-icd
LO
T3
O
-H
CM
O
P-I
<:
o
o
x : nd <-i
PM a p4
MH O g
n3
C -H
4-1 - H
O 4-1
cd
<t! C
J-i
LT>
CD
4-1 O
J- 1
O
a
CNIO s-i
CD P H
3
CD
O
T J P-i
C MH
O
O
O
S-i
P-I
a
J-i
3 4J
CD nd a
OJO H
OJO
CO cd cd
--I iI
CM
Pn
P-i
CD CD
4-1 4-1
0)
O
nd
O
S-i
P-i
4-) 14-1
O.
B -u
-H
C
O
H
4-)
O
cd
nd
PH
d
0)
S-i
CD
m
MH
H
CD H
0 0 SH
MH
OJO
(J) 4 J N . 4 J
4-1 iI S-l iI
Cd H t d H
p4 PH \
PH
x : -a
H
<1"
Cd
CD
cd o" cd S-i
s-i c/i s-i < ;
CD
X)
00
4-1
CD
CO
CD
SH
00
iJ
C
CD
O
CD
00
CM
PH
Cd
XI -u
4-J C
o
O
MH
O
CO
a. c
CD H
T3
n e
T3
CD
C
H
4J
C
O
CD
<f'H
O
O
S-i S-i
zn 3 CD
CMM-I pn
xi
<
LO
D
CM
P-i
cd
C
CD
CD
SH
65
of sulfuric acid.
that percent i>90t. recovery from the rock remained somewhat constant
between 95-96% when the concentration of sulfuric acid was increased
from 98 to 104.50.
when the percent H SO, in sulfuric acid used was 106.75. This is
attributable to poor mixing of the rock and the acid in the acidulation
step thus rendering lesser amount of P90(- in rock water soluble.
Methanol Solvent.
product acid ?90
CO
pi
o
T-I
5-1
O
Si
4-1
O
en
CO
T3
O
Si
O
H
4J
cd
5-1
QJ 4J
5-1 Pi
QJ QJ
O
Pi
PM
CO O
T 3 PM
QJ U
4-1
cd CN
cd 4J
I-l
PJ
T 3 X3
3 QJ
H
4-1 nd 5-1
O T-I H
QJ
cd IS O 4-4
4-1
H
O
QJ
4-1 QJ O
T-I
5-1 Cd nd
O i1 3 4-1
Si
3 5-1
T3 CJ
T3
en T - I
O
QJ H
O
Si
Si
O
<:
a
o
<:
CM
<
T3
4-1
a)
H
5-J
T-I
5-1
T3
O
5-1
4-1
PM
.
QJ
a
4-1
O
T3
O
bO
4-1 CO
T-I
T-I
5-i
co
CN
QJ
QJ < 3
o
5-1
QJ
T-I
PH
CNTO
CM H
5-1
4-1 O
4-1 6 0
Cd Pi T 3
5-1 H
4-1
3
i1
CJ
T-I
m i d
4-1
Pi
QJ
p!
T-I
cd
.Pi
4J
QJ
4-1
O
3 T3
mnd *H
O
QJ
CN 5-1
PM PM PM
5-1 O
<
vo
oo
CN
ON
r^
m
r^-
o
r^-
00
C7N
r^
O
vo
oo
m
CN
oo
CN
<t-
CN
m
m
00
CT
vo
CO
pi
t - l 5-i O
cd O T-I
4-1 !-! 4-1
VO
r^r^-
oo
r^-
ON
r^-
>->
O
bO
4-i nd
T-I
T-I
5-t
3 <
Cu
6 w
r^<t-
o cd cd
H S O
r^m
m
m
CN
.J-
r^
O
ON
oo
oo
<t-
r^-
00
VO
CN
<3
4-i nd
a o
QJ
O
5-1
QJ
PM
5-1
CM
CN
QJ
PM
O
Cd
CJ
a e
o
o C NTO- I
CM <3 S
Si
cd
C7N
CJ
PH
CJ
r-^
oo
CN
ON
P4
a o 5-1
4-1
cd
o 4J ^.
iI T 3
C
c
o O o QJ
c
a)
oo
o
cd
PM
&, oCN
c <tO
m
oo
m
PQ
e
o
PM
CN
3 cd
DJ
cd i - l
4-1 2
CO CO
o o
<3
^o
6^-
CN
CN
m
CN
oo
o
o
a ^
a
o
m
m
m
o
H < f
>->
cd cd
IT
5-1
CN|
CM PM
i-l
bO 4-J
QJ
.P!
.Pi T 3
4-1 H
PJ
4-1 cd cd
O
H
cd
l-l
5-1
CO 4-1 T - I
QJ
4J
X
W QJ cd
T-I
4-1 5-1
4-1 QJ Cd 4J
cd CO i1 pi
5-1 T - I
3 QJ
4-1
nd O
C QJ T - I Pi
dJ bO
O
CJ
cd
C 4-1
O CO T 3
QJ
QJ 4-1
U
T-I
cd
5-i .Pi
4-J J-l Q
a.
T - I 4-1
CO
5-1
H Si
3
5-1 O
O T-I
r i 4-1
5-1
cd
QJ
5-1
CM
CN
CO
< !
QJ
4J
cd
Pi r H
Pi
H
3
QJ iI
T3
o cd
H
5-1 4-1
O
QJ O
CM
H
4-1
oo
CN
CM
m
CT.
00
m
oo
CO
ON
o
CN
< !
CN
CN
CN
<
Pi O
4-1 T-I . H
Pi
5-i nd
QJ
<f-p5 -H
O O 4-1 O
5-1 CO iI <
QJ
CN 3
PM EU CO
o
o
m
oo
C7N
ON
m
m
o
m
o
m
r^VO
67
the
concentration up to 104.50% H SO
The ^?^r
in acidulate.
68
0
vO
<t"
(0M , G 0 Z T V
0 D) PTV -jonpojij UTC soTcq^Tc^ndmi
C B
<t"
CM
<t"
<t"
CO
vO
<t-
CO
CO
UOT^BO
.ioCBft q^ueo^aj
o
C5
cci
<t"
CM
Jfl
CO
CO
CO
4J
(1)
p f o y }onpo.ia UT: o7 d q u s o a s j
CO
vO
v5
vO
CM
vO
vO
uct
'd
o
u
Pi
'd
<!
u
o
3
CO
*d
H
O * d 4J
*-) H H
PLI
O ^1
^1
_<
c
a,
H +J g
O M
O
<
CO
CU
H
'd
H
<!
a
H
a)
u
H
H
^1
14-1
i-l
CO
a.
LO
H
<t"
O
o CM
CO
CM
P-I
ffi
R-K
4J
in 3
-d
CMO O
*-l H
4J
4J
cci
ctf
o
PLI
P-I
14-1
'd
i-i
<u
>H
P!
H
*-l
m o
i-1
oCMtf
P-I
4J +J 4 J
a
a c
<D
a; a)
a
o
*-! <mt
O
i-1
crt
s
4J
cu
o
*-l
Pi
C H
CU n5
o o o 'd o
n n *-l H *-!
a; a) a) o a;
4J
Pi Pi p-i < j P i O
o
o
CO
CO
60
a)
69
was increased above 104.50, the increase in total major cation content
in the product acid was rather sharp.
content in the product acid on the basis of 54 percent P 9 0 q remained somewhat constant with increasing percent H~S0, in sulfuric acid up to a value
of 104.50 percent H_S0, in sulfuric acid. As the percent H9S0, in
sulfuric acid was increased, the impurity content increased sharply.
Acetone Solvent.
on product acid Po0_ yield, percent Po0_ in product acid, product acid
2.
AD
impurity concentration and filtration rate when acetone was used as the
extraction solvent is shown in Table 12.
With increasing concentration of sulfuric acid, the P90r yield
in the product phosphoric acid resulting from the stagewise extraction
with 2 pound of acetone in each stage per pound of acidulate P90r increased
The subsequent increase in concentration of sulfuric acid resulted in a
somewhat constant value of P90c. yield in the product acid.
The data presented in Tables 12 and 14 are also summarized in
Figure 4.
With increasing
70
<j-
VD
<j-
co
<j-
p-pV l o n p o j j UT
o
0O
vO
00
co
<t"
CM
^uaoaaj
UOT^BQ J O T T ^
CM
CM
o Z d" ^ u a o a a j
vD
vD
<t-
v>
CM
v>
d 4-J
a)
00
1
/
"v
ncentrati
is Extrac
< 0 d&
as a Function
d with Acetone
(0K e G 0 Z TV
0^0) PTV ^ ^ n p o j j UT saT^Tjnduij
r-f
00
H
O
<
O
nd
5-1
P-1
d
H
nd
H
<
4-J
O
un 3
CM
P-I
uw
d
CD
O
S-(
0)
P-i
4-J
H
5-i
4-J
H
5-i
d
o
H
4-J
H
4-J
cti
cd
}-(
LO
i-1
CM CtJ
P-i
jM
St
O
r-f
0 \
3
un
<t"
"~
O
O
i-l
0)
4-1
o
5-i
o
5-J
CD
P-1
0)
P-i
CO
P-i
<
0)
5-J
<D
P-i
Of
>>
p. o
e <n
v>
as
un
o CM
0)
j3
H
4-J
nd
o
etf H
5-i
4J
d
0)
O
d
O
<J
O
-H
5-i
o ^
I-l
md
CO
CM
P-I
d
H
<t-
i-i
O
CO CO
H
CM
>H fr!
LOS-S
CMUW
P-I O
0) P-i
^o
6^-
<t"
0^v\#^
1
o
o
nd
tf
4-J
X
d
5-i
O
CO
CM
4-J
0)
4-J
4-J i-M
H
3
5-i nd
3 H
4-J
CJ
CO
1>
<
O
H
5-1
r-t
a;
o
5-i
\ "
G- fr
6 M6
\*7
H
O
nd
r-f
<D
H
>H
nd
O
5-i
P-i
H
nd
nd
ies in Product Ac
nd
H
1
un
as
1
o
as
1
un
oo
o
oo
p - p v ^onpoJLj UT
o d J PIaTl
0)
5-i
1
3uaoj9<i
LO
cxO
H
71
co
d
4J
O
CO CM
1
T3
o
Si Si H
PM 4 J O
H
T3
cd
<
M-l
<D O
T3
3 TJ
J-l H
O
O
cd <D
4J
T3 cd
H r-H
O 3
<J T3 CD
CHC
PM
en
CNJ
CD
00
4J
o
3 T3
o m^o H
J-i O
O O
CD CM J-l <
ON
ON
ON
en
o
VO
as
o
o
vD
en
vo
ON
VO
m
en
co
vo
ON
ON
m
co
o
en
vD
ON
VO
VO
PM
PM
VD
vO
m
vD
vo
00
m
m
ON
VO
PM
CO
J-i
O
->
cd
O
-H
4J
cd
VO
CM
r-H
r-H
cn
CO
CO
>
4J T3
H H
J-l O
3 <JJ
toO
CO
&
^ - v
6
M
CM
vD
en
d o
CD J-l
O PM
J-l
CD
en
CM
CM
CD
Fn
PM
in
O
cd
CJ
m
o
d
CD
3 Q
4J
O
J-l
CD 4J
J-l
CD
M-l
M-l
II H
en
CM
PM
d
CD
o
J-l
CD
PM
d
H
r-H
cd
4J
O
H
C/3 r-H
CD
CM P
PM PS C/3
CO
o
00
en
ON
oo
CO
00
00
ON
-i
d
as
en
as
oo
CM
CM
en
o
m
r^.
vo
o
H
O
CM
CM
<
4J -H T H
d
JH T3
CD < t " 3 vH
O O M-l O
JH
CM
00
r*.
CM
CD
4J
Cd
d o
,>
cd
H
CTi
VO
VO
4J d
d -H
CD
CO CO
T3 CD
d 4J
3 cd
oo
cd
CJ
CMO
PH r-H
PU PM
ON
J-i
CD
e CO
3 m T3 o
M d
ex
M-l
6 oo d
o
H
M
d d
H o t 3 4J
- d PM CD cd
J-i J-l
d -H
O cd -
CD cd 4J
H 4J d Cb d
u d o (D CD
cd o 4J J-i o
U CJ <D PM d
4J
O
o
d r d <JJ CD CJ
PH
cd
T3
mO U >J-i
H
o
i n J-I
co
O <J
M-l
O
00
CM
toO
d -H
CD O
CD J-l
O M-l H
CD H
ON
<T
P^m
4J
H CO
J-l -H
3 co
a, cd
S PQ
M
^
o o
d <
o
o H
o
O
PM
<
>,P-i
-U
fn
H g ^ M-l
J-l <T O
ml
J-i
d
H
CM
00
00
cd
PH
- H si
O
O O H H
H < N^ J-l
J-l
'3
M-l
O T3
r-H
, d CD
CUH <D 3
CO U toOCO
O Q cd
4J T3
PM M-l m d
cd
o
4J
si
o d o M
3 o cd
T3 - H w CD
O 4J
4J
5-) O d cd
PM cd H J-l
4J
u
CD 4J CD d
, d X 4J CD
U W cd O
r-H d
d <D 3 o
H CO TJ c j
H H
co J5 O CD
d CD <JJ 4J
O W)
cd
H cd T3 si
4J 4J CD a,
cd oo H CO
J-I
J-i o
4J B Q .c
Pw
d o
d
o
o
J-i O
O .H
i-) 4J
<J
en
cr.
o
o
oo
as
o
en
en
o
in
72
concentrations of Fe 0
and Al 0
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
solvent.
73
used as the extraction solvent, the filtration rate was lower than
when acetone was the extraction solvent.
The process
for tank car quantities of wet process phosphoric and furnace grade
phosphoric acids containing 54 percent P 9 0 r are approximately $68 per
ton and $152 per ton respectively.
74
11 and 12 the sulfuric acid containing 98, 103.30, and 104.50 percent
H SO, when reacted with Florida phosphate concentrate and subsequently
extracted with either acetone or methanol gave the best P?0
in the product acid.
yield
impurity content of the product acid on the basis of 54 percent P90,was obtained when sulfuric acid containing 104.50 percent H SO, was used
for digesting the Florida phosphate concentrate and the acidulate thus
produced was subsequently extracted with either acetone or methanol. However, at this point, it should be mentioned that the choice of the type
of sulfuric acid would be dictated by the concentration of P90r in the
product acid desired.
75
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
relatively low boiling solvents which will facilitate solvent stripping
from the extracted filtrate with the use of low quality heat.
The data indicate that no more than 2 minutes of reaction time
is required when using sulfuric acid or fuming sulfuric acid.
The
ratios in the
of lower
76
pressure steam for fractionation and filter cake drying should result
when acetone is used.
per stage, methanol and acetone produce approximately the same filtrate
P?0
The total
yield,
77
CU
4-1
T3
Pi
^ cd
CU
cd
H
v - " CO
ii
. cd
CU H
<3 M 5-1
cd CU
T 3 4-) 4-)
CU CO Cd
H
g
.-I
3
T3
H
O
s-i x
O O o
cd H
M-l
O
CU
4-1
cd
PH
M-l
4-1 M3
X -H
PJ
CU
CO
H
>
CU
<J
T3
CU
-H
5-1
cd
MO
cd
+J
>
4-1 M3
Pi
o
H
CO
Pn
Pi
cd
5-1
4-1
x
<t-
B
o
5-1
M-l
O M-l
T3 T3
o
^
c
O
H
4-t
O
cu
S
4-1
Pi
CU
o
CN
Pn
o
CO
4-1
CO cd
"4-1 CU 4-1 C
O 4-) CJ CU
cd
CO I1
3 T3 3
T3 C T 3
O p H
5-1 O
P-i P-t
<
co
CN
O*
vO
C">
OJ
ro
&
.^
m
CO
r^
vO
.^
Pi
3
.^
CNl
o
r^
5-1
r^
vO
m
o
-cl-
ii
CO
5-1
in
CU
a,
C)
o*
ii
O
r^
m
a\
iI
.
ii
o>
o.
o.
<
o
cu
cu
CO
.
T3
00
r-i
CO
CN
CT>
ii
O
CO
CT>
Il
r-1
CN
VO
CN
CT>
CT>
ii
CN
Il
CO
i1
ii
il
Il
cn
<t-
CNl
i1
CU
5-1
CU
>
O
O
CU
S-i
CO
Il
cd
4-1
Pi
cu
vO
CNl
r^.
vO
m
<t-
vO
vO
vO
r^
r^
Il
r^
r^
vO
vO
vO
O
H
4-1
cd
Xi
a,
JJ
o
ro
o B
o H5-1
T3
H
O
CU
<d
P<
X
I1 H
o
H
vO
CT>
<1o
r^
m
o>
m
a\
it
it
cu
X
4-1
vO
CT>
CT>
Pi
H
CU 4-1
4-1
C
CNl
cd
cu
>-!
3
T3
H
O
O
5-1
CU
p.,
r^-
r^
ii
<3
ro
00
<t-
Il
r^
oo
CNl
CNl
i1
!5
cd
rf
Pi
ii
il
cd
cu
C
H
^-1
O
4-1
cd
U
4-1
U
C
cd cu
o
C
o
S5 O
M
H
cd
g
cd
H
5-1
Cd
4-1
CU
cd
cd
X
ti
CO
CO
I-l
Il
cd
T3
H
M
O
i1
T3 cd
H S
T3
H
5-1
O
il
il
Fn
Fn
Fn
5-1
O
>^
CU
4-1
a, X
o
X
P-I
4-1
M-l
O
CO
4-1 cd
H T3
H
O
^5
O
Pi
S-i
M-l
cu
4-1
CO
CU
&0
cd
4-1
cd
co
cu
5-1
S-l CU
O
PL,
M-l
CU
cu
4-1 - H
Cd 4-1
S-l
4-1
Pi O
O cd
H 4-1
4-1 Pi
cd
o
S-i O
4-1
il M-l
H
O
M-l
CO
cu pi
X -H
w B
r^
Il
o
O
Pi
CU Pi
co cd
cu X
CU
O
S-i
cu
a,
P-I
H
5-1
4-1
4-1
4-1 (J\
4-1
-d-.
il
X
H
5-1
CU
4-1
r^
m
vO
i1
cd
CNl
P-i
Pi
4-1
CO
PX
cd
<t'
r-
X.
cd
H
S-l
CU
4-1
Crt
<1 P-i
S
cd
H
o>
OJ
cd
<&
vO
cd
,P
.^
o
CN
ii
CN
P-I
Pi
.
a)
r^.
a\
^ o
CU 5 0
5-1 Pi
CU H
>
vO
00
T 3 4-1
I1 o
4-1
CU 3
Pi
r-1 T 3 <ti
a>
T3
O
5-i H
5-i
mp-i
O
CU
5-1 0 0
O P-I CT>
J3
"4-1 4-t
OJ
T3
CO
EC
CO i1
. \
rO
o o
o
CN
H C CU o
S-l 3 5-1 5-1
O O cd CU
.d P-. a, p<
P * ^ - cu
X C
P-. cd
<3
00
r-^
vO
4-1
O
Pi CN O 5-1
CU P-I
P
CU
T 3 P-i
o
Pi M-l O
5-1
P-i
> oCO
T3
H
O
<
.N
cu
^3
CO
vO
co
T3
o
H
Pi H
4-1 H
O
CU
CU
5-1
3 H
O
CNl
P-:
O
cd
t^, m cd
CU
Fn
CU
o
cd
00
ro
CU 5-1
O Pn
U
^3
P> <3
P<
B 4-i
H O
2
CO
CU
Pi O
-H H
5-1
CO
4-1 M3
H -H
5-1 O
5-1
CO 4-1
CU X
T3
5-1
bO
i>*
.N
CTi
CU
5-1
CU
4-)
cd I - l
<3
Pi
H
CX CO
CO
o
J3
ii
ii
CU
5-1
Fn
bO
cd cd
Pi JJ 4-)
H
4-)
T3
CU
CO
4-1
Pi -H
5-1
O
M-l
.^
m
cd
^3
[mental
CJ>
t-H
t-H
rd
Il
cu
H
>n
4-1
s re
more
4-)
CO
a)
I1
0.46
CU
'SB
I1
0.35 1
O
4-1
O
CNl pu
H
1 P-I
4-1
I1
CT^ M-l cd
cd
5-1
- H
5-1
CU CO O
4-1 CU fe 4-1
\
4-1
1 4-1
cd 5-i
i1
H
H cd M-l 5-1 X
\
^ p4 o 4-1
Fn
O CO
H ,3
4-1 t-3
X
CU M-l
4-1 M3 i1
Pi
5-1
0.62 1
CNl
S-l
CU 4-1
xB oPi
C WD
CN
CU T H
P-I
z.
cd
CJ
fi 3
^3
78
LO
CO CD
t )
5-1
a
o
H
CO
XI
4-1 r-l
C CD 0 0
O
PH
CN
a\
cd
PH
cd
CD P H
4-1
M-l
PH
PH
d
T3
rl
CtJ
4-1
i-i
5-1
4-1
il
r\
c r M-i
rl
4-1
Cd
5-1
4-1
i1
rl
LO
LO
cd
CD
5-1
<C
PH
d
>d
rl
T3 rl
3 O
5-i
CJ
<J CD
CD
rl
5-1
m
ii
4-1
>>
x:
o
x:
M-l
O
PH
o C
Xi
cd
H
vD
O
co
CN
C
d
5-1
r^-
i-H
cd
4-1
CD
CN
CN
vD
CN
LO
CN
CD
CD
CO
s-
& tJ
4J
C
CD
O
5-1
CD
'd
O
5-1
PH
'd
co
CN
CD
CN
nd
1-H
CD
rl
>-l
CN
>
O
O
CN
CO
O
n3
C!
O
-I
4-1
cd
5-1
4-1
Cl
CD
O
0
O
CJ
CD
5-1
CD
PH
PH
vD
C"
o>
r^-
oo
4J
co
5H
vO
vO
CD
r^-
r^vD
vO
oo
r^vD
VD
vD
4-1
cd
x:
Cu
CN
PH
Cd
4-1
O
H
o
x:
Cu
<f
co
r^CN
LO
5-1
CD
x;
CN
sf
vD
4-1
LO
co
CT*
cd
H
d
X)
rl
O
CD
O
r^-
CO
00
r^CN
oo
vO
r^LO
CD
bO
cd
M-l
4-1
CO
CD
4-1
5-1
cd (D
5H
CU
CD
ss
4-1
cd
U
4-1
i-i
H
M-l
LO
CD
oCN
XI
4-1
4J
O
cd
4J
5H
CD
PH
M-l
4-1
4-1
C
CO
(D
CO
i-l
nJ
C
CD
4-1
H
1-H
n3
4-1
cd
O
CD
O
5-1
!3
5H
d
d
o
o
H
5-1
4-1
rt
ctf
crt
d
H
d
H
5H
5H
1t
il
PH
PH
rl
5-1
4-1
cd
J>,
CD
6
3
1-H
co
rt
x)
H
5-1
O
il
PH
CD
4-1
Cd
>,
cd
i-H
x:
Cu
CO X ! r H
O 4-1 Cd
x : -H x i
P-. J3 -H
4-1 ^
M-l O
i-H
rH
o o oO
CO PH
1
-' d
1-H
CD
H
>^
LO
oCN
PH
CD
5-1
Cu
CD
5-"
4J
CD
O
5-1
CD
P-i
<T
PH
5-i
PH
CN
<!
s
1
CD
CD 4-1
ti
cd
rl
5-1
CD
4-1
x:
o
cd
CO
O CD
CNC <J PH
PH -H
4-1
CO
g
o
H
PH
)->
O
d
4-1
-d
" CJ
O Cd CU
5-1 TJ O
-H
CO
cd
co
PH
LOPH
5-1
M-l
cd
CO
CD
O
x:
4-1
(D
toO
cd
H
5-1
CD
4-1
'd
rl
CJ
<J
LO
O 4-1
CN O
PH
d
X)
M-l O
O 5-I
CD
5-1
1-H
CN
S3
H
O d
4-1 4-1 CD 4-1
O CD 5-1
d O cd CD
d <C cu O
CD 5-1
5-1 M-l 5-1 CD
PH
O P H P-i
r^-
LO
B <r
o
5-1 o
co
~^
C CD M-l
00
vO
vO
H
5-1
CD
Cu
3 <C
CD
x:
4-1
x : t 3 cd
P-I C >
d
co
CN
4-i nd
r l H
5-1 O
'd
cd
CN
5-1
CD
Cu
CO O
X ! 11 M-l
O cd
Cd r l d
cd w 5-1 CD
5-1
CD CO
4-1
X H CtJ
CD
W
5-1
CD
CD 4-1
CD
CO cd r l
r l r - l 4-1
cd CO
CD
CD "d
Cu
bO-H
toO
cd o CO cd
4-1
4-1 < J
CO
CO
t ) PH
>> CD
4 3 - H M-l
rl
5-1
4-1
d o
H
CO O
CD
O C
cd
<H -H T3 5-1
cd 4-1
O
L05-I X
H
O
w
5-1
CN
O P H CO CD
X!
d CD
CuM-l
5-1
CO O r l X!
5-1 H
O
CD
rl
4-1
O
LO
O
too
5-1
w a
vO
CO
4-1
CtJ
C co
O
co
co
/ - N
d W
Q
CO
cu
iw o c d
O cd Pi
H
CO
CO
o
LO
vO
< C
CD
o 6
rl rl
X! 5-1
T3 H 3
too
C
CO
CN
o
CO
co
4-1
cd CD X )
Xi
CO
-- C
o o
CD <C CJ
i-l
vO
LO
4-1
r l CO
4-1
^
Cd 5-1
5-1 }
4-1
^
-I
PH
CO toC
CD
4-1 r l
x : -
4-i
rl
oCN
cd
CO X !
5-1 4-1
CD
X > CD
P
rl
d
C
o
B
CD 4-1
x:
o
H C
79
P 0
acid along with the filtration rate of the extracted phosphoric acid
which resulted from the stagewise extraction of the acidulated mass, prepared from various phosphatic material, with methanol and acetone respectively.
15 and 16 are for each stage of those experimental runs made using not
more than 9 minutes of contact time per stage.
From the results given in Tables 15 and 16 it may be seen that
the P90c. yields of the acids produced varied from 95.04 percent to
96.73 percent when dried acidulate, prepared from various phosphatic
materials, was extracted with methanol.
80
It can be seen
that the choice of solvent dictated which major impurities were preferentially rejected from the product phosphoric acid.
When methanol
and
as the extraction solvent, the concentrations of CaO and MgO were generally
lower than when methanol was the extraction solvent.
The filtration rate of the extract while using acetone as the
extraction solvent was much higher than when using methanol.
The proposed new process has been shown to be capable of
producing phosphoric acid of high concentration without vacuum evaporation.
The process is adaptable to use of low grade as well as high grade
phosphate rocks, and of low grade phosphatic materials such as matrix
or waste materials.
81
CHAPTER IV
The flow
diagram is presented along with the total mass flow rates and the
compositions of the main flow streams for each process variation based
on a total production of 1000 tons per day of product P^O,..
It should be stated at this point that the processing conditions
used in the material balance for the flow sheet presented below are
based on data presently available and are not necessarily optimum.
The data need to be subjected to an extensive economic study in order
to establish true optimum processing conditions.
The list of assumptions used in calculating the material balance
are given here.
34 percent P20c' 50
percent CaO, 1.3 percent Fe20, 1.3 percent A l ^ , 0.3 percent MgO and
3.8 percent F.
82
<f .
H
<t
CO
P-I
35
CJO
C
4J
C -H
CN
CD
(JL|
rT
i 1
Q*
> a.
i-l
!-(
mmJ
I1
1
O
CO
^
4J
CO
CO
CO
CD
o
o
4J
1 1
4J
CD
on
>
i-1
P-I
<t C
CD
o
I-I
1 CaS
Solv
IMP
O
CO
O
H
4J
cd
I-I
T3
H
O
i-l
<3
4J
O
CD
U
H
Q
< !
CO
CD
CO
Ctj
O
CD
U
CD
4J
<f
CO
CJO
cd
5L
FQ
H
p*.
^
Q
C
O
P-i
res
CJ
H
4J
VO
>-i
O
O
P-i
CO
oc
co -cd
W
U
H
4J
cd
cd
J-i
4J
CD
X!
4J
4J
4J
i-l
c
CD
>
i-l
^1
O
M-l
fe
P-i
CO
<!<!
O
^l
CJO
CO
P-i
4->
2
H
cd
fe
cd
00
U
cu
on cd
W
O
P-i
H
Q
4J
<t
O
H
4J
CD
>
i-l
P-I
cd
CO
CO
11
CD
a
>
o
CO
CO
CD
CO
CD
aO
i-H
o
m
< j +J
CO
CD
bO
H
^
O
3
Q
I
4-1
CT.
C 'H
CD
4J
E
Solv
epara
cd
O
O
CO
CD
u
bO
H
CO
PM
T3
o
CD
4-1
cd
X!
CO
O
P-i
T3
H
O
<3
o 6
rl
3
i-l CD
3 .-I
M-l
O
i-l
3 U
CO
<3
o
H
J-l
O
.
4-1
O
a 3
CO
O
.
T3
O
H
PH
PH
83
P 0
ratio of 6.0 tons of methanol per ton of P90[-> being equally divided
Chemical analysis of
1.12 percent A1_0 , 0.35 percent MgO, 0.58 percent F and negligible
percent sulfate.
is 0.4 tons of methanol per ton of wet filter cake. When using acetone,
a solvent/dried acidulate P^O^ ratio of 6.0 tons of acetone per ton of
P 0,, begin equally divided among three stages, results in a 95 percent
filtrate P0._ yield during extraction.
2 5
phosphoric acid is 150 pounds of filtrate P90,. per hour per square foot.
Chemical analysis of the acid which results after fractionation of the
acetone is as follows:
Fe90 , 1.33 percent Al90 , 0.14 percent MgO, 0.98 percent F and negligible
percent sulfate.
the streams entering and leaving each of the major processing steps.
Each flow stream is labeled with a number to facilitate cross-reference
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
84
>^
T3
cu
O
^
Tj
O
5-1
PH
en 6
cu
01
O
^
CTJ
ttf
CU 0
pi
S-I - H
-U H3) -U
pi O
en co
CU S-i
O
O
&
<j-'H
J-l
4-)
0
a; co (/j - H
CU O 3
PM
CO CTJ 5-1
a-
a;
d -C
co T3 a;
n) C j l
S nj 4-J
T3
O
<:
S-i
(U
4-)
rH
-H
M-l
4J
cu
j-i
a> -i-i
c u 4->
-H
nj ^
ps a>
T3
O
00
5^
a
PM - H
4-)
a
O
-o00
<t
>-
;s
60
o tn iw
r\
o>
o>
o>
LO
00
00
00
r^.
LTl
en
r^.
r-l
4J
O
a
U
<t"
PM
<U O
co
CO 4-J ^ - N
- H r-l
CU rid
M CO
ffl U fJ
O
co
CO
ctf
o o r-i pi o pi a;
5-1 T 3
O -H
<f-
00
00
00
,c o ,c a; pi o
a, <j 4.) co cu o J-I
co
cu r-lco O> 0 r-l
a;
CO 0) *H
PH 5-I .
o 3o s4-) oLT|r-i
> M-l
>-, M-l T-l
4-1 r-l
5-1
(/>
a ^
g
M
O t l r-l
CNJT-I O
o
4-1
LO
CO
LO
co cu
4-1
a;
crj a o ^ M-i
CO
CO
j-i S
T-1
5 T3
PM ocrj
a) - H
O J-i
5-i O
o
o
(d
co
LO
LO
a) a) , c o
o cu 4-1 pu cu a) 4-1
1-3 4-1 CTJ
CO r - l
crj r-i a; O ,Q 5-i
M-I s-i 3 a; X H cu
o
o H3i
< ; 5-i a M
o
4-i
a
3
CU Pi
H
aa . H , c 5-i H
pi crj
4-1 O
O O
pi a) M-l
oO HLO a;O r-i
r-i
T j 4-1
-d
M
a;
cu
PM
-C
S-i crj -H
p^ X l 4-1 4-1
Cu O O
4-)
9
CO M-l
CO
O
TJ
a;
pi
4.) o
CNCU
S-l T 3
-H
o
r-l
UA
CO
p
O
H
>,
CVJ
P
<t-
00
LO
CO CU CU
CTJ 4 - 1 P M
LO
P3
a; co crj p! pi crj
JZl
PM
CO
CTJ 4-1
4-i xl H4-) oCU ' od a;
pi
O M-l
PM
M-l o
X
5-i
4-1 M-l
pi o
co pi cu
p! S-i
O
5-i 4-) < r
cu pi
CU O
d) O
4-)
CT1 CTJ iI r - l
-r-l
Ml)
>
CU
crj 4-) cu Tl - H O ,Q
p4 crj co
X co
&
O
r-l
h
r-l ,3
P! PS
Tj W
T-l
O Tj
S-I
O
CU
TJ 4-1
CU T j CU
CU r - l H3)
CO E
O
CU
< c c 3 ^e
CO
CO
CTJ
4-1
cu o
O
O
J-l
PM
O
4-)
<r
CU O O
5-1 C/3 O
-H
CNO
O
Pd r-l
CO
CO
O
CU
P3
CO
crj 5-i co
crj pi
cu
o
S-i H
4-) 4-)
C/3 CU
H
CO J-I
CO
O
CU CO
crj
U
T3
T3
T3
T3
O
T3
o cu
o p
S-i
CM
h
T3
cu
w
CU
T3
T3
60
crj
CU CU
5-1 X
CO
CTJ 4-) H
PH
CO
>^
T3
crj
cu cu
O
S-i
O
4-1
5-1 C/3
PM
^
w
p-l
85
<1"
CO
^
PM
CN
p-i
CF>
60
pi
PM
PM
<l-
un
CN
<1-
o
Pn
<1"
5 co
O C >,
r-l
Cfl
PM H
Q
CO
~ S-l
CO 0)
0)
nJ 4-i p-i
CO
<1"
eg
cd
CD O
J-l H
4-) 4-)
C/3
CO
CO
CD
O
O
S-i
P-i
Pu
H
S-l
O
CO
<U
Q
Pu
PL,
co E
CO Ctf
<D <U
O J-l
O 4-1
S-l C/3
P-i
T3 T3
O H
5-1 O
PM
T3
H
O
<
v_^
<d
>
cu o
O
T3
H
LT O
CN
CU
XJ
H
co
PM
o
H
3 XJ
4J
5-1
M-l 4J
O t1 H
H
3
5-1 CO
CO
O
CU
t1
5M
4J
PM
5-1
CU
CO
HJ
H3> H3>
O
00
H PM
4J
O M-l
3
H3>
5-1
a
o
PM H
4J
cu CO
J=:
F-M
4J
4J
X
4J
d
cu
3
cr*
cu
CO
,Q
H3> 3
5-1 H CO
O
M-l
H3>
<i
CO 4J
CU O
4J CU
co 5-1
&
F-M
H
Q
T3
CO CU
CO
o
cu 3
o T3
O
o
5-1 5-1
oo
I1
cu
t1
Xi
co
H
PH
CU
cu
5M
rt
c
u
5-1
o co
o
o
ii
cu
o
co
cu
5-1
4J
CO
C_J
CO
CO
CU
cu
00
o
o
5-1
c^
Cu
CU
4J
CO
r^
r^
<J-
m
CM
ii
<t-
<t-
CO
o
o
o
o
co
o
o
CO
CO
ti
CM
o>
CM
o
o
t1
a>
CM
r^
o
o
o
o
co
o
o
co
CO
00
00
o
<J-
<r
cr\
ii
o
o
ii
m
o
CM
228
r^
403
ON
r1
ii
I1
CT\
co
o o CM
co
co
co
co
r^
r^
^O
O
<J-
r^
r^
ti
CM
CM
I1
I1
CM
00
PM
CU
PM
<t-
<TN
<t-
<l-
<t-
ii
4J
d
CU
3 O
<J-
4-1 CO
H
4J
CO
c^
^o
CM
c^
I1
^o
CM
CTN
I1
c^
t1
^O
CM
^o
CM
C^
C^
<TN
CM
c^
o O
c_>
o
m
o
PH
co
C^
CM
i1
^O
CM
CM
t1
^o
CU
M
co
o
a
a
T3
M-l
c
co
o
4J
co d
cu CU
ti
a>
o
co
CM
^o
r^
r^
c^
^o
CM
CO
co
co
ii
ii
I1
co
m
m
O
in
CM
co
m
o
t1
CM
^O
CM
m
m
co
co
o
<T
co
ON
c^
CM
m
^o
CU
4-1
td d
cu o
CU
4J
CO
s
XJ
ii
prf
cu
>-
CO
*> U
CO CU CU
cti 4 J P M
co
co
co
r-l O
PM H
4J
i1
CO H
CU M-l
H
4-1 4J
H
CU
5M
CM
5M
/-v
CU
^
co
o
n
CU
CO 4-1 4-1
CO d
i-i
O
-H
i - )
O M-l
4->
CO
H
4->
&i
H
CO 5M
CO O
CU CO
o cu
o
o
5M
PM
CO
5M
4J
d
CU
o
d
o
o
cu
4-1
CTJ
X!
a
CO
co o
^o
O
<t-
I1
5-1
o
o
5-1 CO
a CtJ
o
5-1
PM
H3>
CO
CN3
X T3
a
CU
CO
H
CU
CO J C
CO 4-1
o
4J
tf
ts
o
CO
<J-co
>^ 4J
X>
PM
PM
a
co
5-1
CU
Cu
^o
4J
CO
r^
>
t1
CU
r1
O
>- x:
co
w H3>
r^
co
H3>
ctf o O O
H 5-1 5-1 o cu
,c
Cu 4J a
CO
a
|
CO O
d o to M-l cu T 3 CO
5-1
ii
co
>o
XJ
r^
CM
CU
4-1 tI
to <1
CU
MM
cr\
4-)
CU
ti
ti
d g
x> 4J
o
PM
CU
d o H
cu , G oo CU
o Cu H o
s 5-1
CO r1 co
cu o 0 0
X! ,G en a si CU M-l
4J
ctf
a
a c o
CO H g
cu
cu cu T 3 CO
o &
5-1 H3> CU d
T3
xt
PM CU CU XJ 3 6 o
4J 4J H
5-1 a 4J
ctf ctf
o co
^ 5-1
4J
ii
CO m
H 4J 3
. xcu! co co
5-1 d H3> m
.
3 cu H o 4J CU o
1 o O CN
5-1
&
6
<i PM 0 0 co CU
I-I a
,Q
d
o
c_> M-l 4J H
o o O
cu
3 3
o 4J
r^
CO
> o
o
<i
H
5-1
>
M-l
r1
CO
CU CO O
CO
CO
CO
cu o
d I1
4J
CU
I1
153
XI
H
4J
CU
403
d 4-)
cu C
154
4J
154
4J
O
CU
co
154
4J
co
154
CO
631
cu
WD
d
H
CO
4J
Solv ent
86
O
X!
co
CO
CO
cu
cu
O
O
5M
4J
5M CO
PM
H3>
H
O
<
O
H
5M
MM
I1
3
CO
s^
PM
00
CT.
II
CM
4-1
d
cu
3
ti
MM
MM
H
5M
O
4-1
CO
cu
CO
CO
4J
ctf
cu
g
CO
CO
ctf
4-1
d
cu
3
ti
t1
CU
4-1
MM
aJ
ii
cu
4-1
MM
5M
cu
aJ
3
H3>
H
<
H3l
CU
H
>
ri
CO
CO
CO
g
d
H
4J
o
CTJ
T3
H
O
<d
T3
CU
4J
O
aJ
SM
5M
4-1
4J
CO
Ti
cu
4-1
Ctf
H
4J
00
H
T3
H
O
<
X
W
X
PJ
PM
co
<t"
^O
r^
00
ON
5M
cu
CT3
5M
CTJ
H3l
H
O
<1
>-.
o
5M
CU
4J
tI
H
4-1
H
PM
5M
T3
CU
a
6
fl
4->
4J
r-J
I1
t1
II
CTJ
5M
87
00
te
PM
*
Pn f^
< !
T3
00
O
O
LO
to
00
rQ
en
O
ii o
py H
>>
nj
Q
en
> s-i
en cu cu
nJ - u P-i
S
rt
Pi
<D O
S-i -i-l
4-> 4-1
co Cu
l-l
en s-i
en
o
cu en
o
cu
o o
S-i
PH
m
oo
< !
T3
CD
a,
a,
H
en
en <ti
<u cu
o
5-i
O 4-)
s-i co
< !
88
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
The conclusions drawn from the results obtained in the further
study of the process for the production of low impurity phosphoric acid
by a method involving the dissociation in the presence of an organic
solvent of crude monocalcium phosphate prepared from wet process phosphoric
acid and phosphatic materials, are summarized as follows:
Effect of Repeated Treatment of Monocalcium Phosphate on Dissociation
Reaction.
methanol and acetone was studied by subjecting the insoluble residue from
a dissociation reaction to repeated treatment with fresh solvent.
From the
commercial grade phosphoric acid, and that this concentration was achieved
directly from the dissociation step after removal of the solvent and without further concentration.
90
process to produce high purity phosphoric acid from low grade phosphatic
materials was demonstrated by preparation of phosphoric acid from several
grades of Florida and North Carolina phosphate rocks, from Florida phosphate slimes, and from Florida phosphate matrix.
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
content was slightly higher.
It is concluded that the dissociation process is capable of producing
high purity phosphoric acid from any grade of phosphatic raw material,
even reject materials such as phosphate slimes.
Experiments were
91
mass is obtained when the acidulate is dried for 20-60 minutes at 250C
or held in an insulated container for 60 minutes.
Effect of Overall Contact Time on Stagewise Extraction of the Dried
Acidulate.
Seven
for the extraction of phosphoric acid from the dried acidulate with either
methanol or acetone.
from
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.
The impurity contents of the product phosphoric acids made from
Florida concentrate I are somewhat similar to that of the commerical
acid containing the same percent P90q*
Use of Low Grade Phosphatic Materials.
92
The compositions,
Recommendations
The following recommendations should be given consideration in
further studies of the two processes.
1. The feasibility of producing low impurity phosphoric acid
containing more than 54 percent P90,- directly after solvent separation
by dissociating crude monocalcium phosphate containing more than 47
percent P90,- in the presence of methanol and acetone should be investigated.
2. The feasibility of using a mixture of methanol and acetone for
dissociating monocalcium phosphate should be investigated.
There should
93
used to determine which of the sulfuric acids should be used for digesting
the phosphate concentrate I and to determine optimum process operating
conditions of a more refined nature.
94
APPENDIX A
CHEMICAL COMPOSITIONS AND PARTICLE SIZE DISTRIBUTION OF DRIED MONOCALCIUM
PHOSPHATE MATERIALS AND DRIED OR DENNED ACIDULATE
The experimental procedures outlined in Chapter II were used in
the preparation of crude monocalcium phosphate and acidulate containing
various amounts of free water.
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
to 23.0 weight percent P90,. respectively.
size
95
MM i
O i-H O
Cj H to CU 5-i
5-14-14-1 2 a) a)
CU W Ctf i-H 5-1 4-1
4-1 >> N Ou PH cj
Cj 5-1 -H
12
^
O H
i-H
CM
5-1
CU CD
4-1
cu
5-1 Cj
PM ! 3
3
H
r^.
LO
co
o
vO
i-H
VO
00
i-H
i-H
CO
<!
co
r^.
LO
vo
.
vO
CM
<!-
CO
<!-
CT>
CM
00
vO
CO
CT>
<!-
r^.
CO
O
o
o
CM
O
CO
<!r^.
i-H
CO
CM
o
<d
<u
H
5M
o
T3
C
cj
CU
4-1
Cj
Ou
CO
O
0JD
C
cu
o
u
cu
CO
LO
CO
r^.
co
CO
to
CO
LO
oo
00
vO
r^.
r^.
00
CM
CO
ON
PM
4-1
SI
CT>
CO
vO
LP>
4-1
r^.
CM
C^
c^
CM
cu
CO
PM
Ml
CO
CU
CM
00
vO
CO
vO
CM
CM
CO
vO
O
O
O0
VO
C^
CO
CO
CM
CO
i-H
PM
CM
H
O
i-H
Cj
O
O
c
o
C
O
H
4-1
H
co
o
CM
cj
CJ
CU
CU i-H
4-1
Cj 3
LO
5-1 i-H
O
4-1 O
CM
H
CO P H
co
CJ
CO
00
vO
LO
00
oo
CO
CO
vO
<!-
O
00
LO
<!-
00
CM
vO
CO
MO
LO
CO
vO
r^.
<!-
r^.
vO
00
vO
CO
i-H
r^.
i-H
i-H
OO
CM
i-H
i-H
VO
<f
CO
CM
CM
CM
-*
<!
<!-
<!
<!
<!
5M
r^.
o
o
cj
CM
4-1
O PM
CJ
CM
CM
C^
e
o
cu
CT>
LO
<!-
<!-
CM
CM
CM
o>
c^
CM
vo
<!-
OO
vD
vO
<i^
C^
CO
O
Ou
g
a
ctf
o
en
PM
CO
6
a)
.fl
CJ
,a
cj
c
O
H
4-1
O .
H
M
O
CO
cu
O
cj
H
5H
CU
4-1
Cj
cj
T)
H
5-1
O
i-H
cj
T)
H
PM
5H
5M
O
i-H
O
i-H
PM
,-~v
M
M
^w
MM
cu
MM
PM
N
O
v ^
5-1
<4H CD
4-1
PM
cj
C J 5H
s ^c
cu
cu o
T)
5H
C
O
CJ
o
5M
PM
4-1
Cj
CJ
5H
4-1
T)
CU
H
5H
c
cu
o
Ci
CJ
Fj
*d
iH
~N
M
M
M
o
'
5M ^
cu
PM
4-1
oj
CJ
5M
4-1
cu
cu o
T)
5H
cj
H3
H
cj
oj
T)
H
O
CJ
oj
Td
H
oj
Cj
*d
*d
H
5H
5M
5M
5M
5M
O
i-H
O
i-H
O
i-H
O
i-H
O
i-H
PM
PM
PM
^~\
& M>
PM
PM
6
O
5M
'
MM
cu
PM
4-1
Oj
CJ
5M
4-1
c
cu
nd
cu o
H
Ci
5M
CJ
5M
MM
^
>-^
^'
cu
e
o
PM
4-1
Cj
PM
CJ
5M
CJ
4-1
*d c
cu
cu o
Td
CJ
O
CJ
5M
5M
cu
5-1
UM
cu
i-H
^1
^1
cu
PM
5M
5M
<4M
MM
PM
CJ
PM
CJ
to
*d cu
cu
H
5M
&
3
i-H
CO
~\
M
^
g X,
Td -H
CU 5M
H 4-1
5M
oj
96
a
O
14-1
O .-1
cti -H
SH
a;
4-1
Cti
&
CO
4-1 4-1
CO Cti I1
t ^ CO &
SH
T-1
CJ
r-l
a; S-i
3 a; 4-1
a;
ii
<t-
Pn cti
CN
CO
CO
o>
ON
co
CN
vD
co
ii
o
o
00
S-l
&
S-l
a; a;
CU 4-1
S-l cti
ts
PH
rv
CN
ON
CO
O
O
CN
o
CN
PH
CO
a
CU
O
r^
en
SH
CU
PH
o>
vO
CN
CO
CN
o>
vO
ii
CO
r^
vO
CO
vD
r^
CO
00
CN
a;
en
CN
vO
CN
CN
CO
H
4-1
H
CO
CO
CN
o
cti
CN
r^
II
CJ
o>
CO
CN
VO
CN
0>
r^
CM
CN
O
CN
cti
CJ
4-1
co
VO
CN
P-i
CO
VO
r^
CO
co
co
VO
vo
m
CN
00
CN
co
ii
co
vO
CO
t^.
00
co
<t-
CN
CO
r^
<t-
co
ii
a;
<u ii
4-i , n
cti 3
S-i i - l
r^
m
O
CN]
CO P-|
CJ
a
a;
CN
CN
S-l . - I
m
CU ,>
4-1 3 D
Cti i - l P-iCN
m
co
rs o
00
vO
<tm
co
m
<r
co
H
4-1
i-i
cti
T3
H
S-i
O
i1
i1
PH
PH
CO
T3
H
S-i
O
i1
pH
Cti
T3
H
S-i
O
53
S-i
o
CO
<u
oCti
H
S-l
a;
4-1
6
o
S-l
LH
e
o
S-l
P-i
x-s
M
M
CJ
T3
-H
a)
s-i
4-1
S-i
cti
O S
X-N
Fj
g
o
S-i
o
S-i
LH
4-4 x\
CJ s^
Pn
CJ
M
M
PH M
T3 H
CU S-l
H 4->
S-i cti
o S
(n:
CO
>
M
LH
PH
CU
4-1
Cti
Cti
i1
i1
.
s
S-l
4-1
O
CJ
g
o
S-i
C
CU
CJ
O
CJ
CJ Cti
i-l
T 3 ii
CU
H
S-i
S-i cti
CJ
Q S
B
o
S-l
CJ
cti
C
H
T 3 i1
CU O
H
S-i
S-i cti
CJ
p^
P-I
CJ
CU
4-1
Cti
-C
PH
F;
^J
o
o
S-l o
LH
T3
CU
H
S-i
i 6^
CO I1
LM - C
CJ
PH
V ^
T3 H
CU S-l
H 4->
S-i Cti
LH
a
CU
o>
VO
H
O
CU
4-1
S-l
4-1
CN
4-1
r-l
a
o
CN
dal
*0
cti
H
vD
(I)
O
CJ
CN
vD
ii
H
U
c^
PH
CO
CN
4-1
T3
CU
m
r^
&
CO
^
P-I
co
o>
CU
4-1 LH T 3
Cti O
c
cti
i1
3 C
T3
o X
r-l H o
O 4-1 o
<: iCti1
PH
3 cu
T3
CU T 3
r-l H
S-i O
<r
4-1 O
Cti CO
,
CN
o < &ffi
97
m i a
o .-i o
rt -i-i co <u
J-I 4-1 4-1 3
CD
CD CO Cti iI J-I
4-1 >-, N a, Pn
CTS SI -iI
^
O --I
CD
CD
J-I
J-I
CD
4-)
rt
CD
4-)
rt
CN
CN
ro
rn
CN
oo
<N
CU
fe
J
ro
*d
O
O
ro
ro
64
m
cd O
4-1
<N
O P-t
CD
4->
Cd
J-i
4-1
i-t
<N
i I
J3
^
LP)
i-l O
O
<N
W PL,
vO
o c
CD
CD ,-Q
LO
4-1 3
O
CN
cd
5
o cn
CN
00
<N
b" co
J-i o s-s
IH
00
cx, a-<
CD
4-1 M-4 T)
cd o
cd
d
3 a
O
o ^ i
.-I >r4 O
a 4-I o
<3 cd p i
d 3
o
<f
Q) T ) J-1 O
-r* -IC Ctf C/D
J-I
a j:
<N
o <d a
JC
i ro
O co
J-I O CO
m si o
CU , - 1
CD
4-i m *-d
cd O C
i-l
cc!
3
d
o
o ^ ;
i-l 'rA O
a 4-i o
< ! cd p^!
ii
d 3
n
<
CD T} 4-1 O
i-l i-l Ctl C/3
g
i Lh
o co
J-I o <r
m jn
o
g
O
J-l
> w
4-) M-4 n j
CD
4-i m
m o d
m o d
cd
=3
G
O Jsi
r-i T - I a
a 4-i o
<
03 PS
H3
- d d. (0
<t
CD n3 4-) o
-ii -ii uj en
J-I a si
CN
o < aw
i rco
O ^D
o
PH -
II
3
d
d o
I-I ,-!
a 4->
<J cd
T)
d
a) i d
-ii -
i -c
J-I a
Q
<j
n3
cd
^5
a
o
p3
fl)
4J o
cd C/D
jn
ca . jx;
98
00
<J-
m
CM
oo
LO
LO
LO
T3
<J-
>.
<j-
LO
LO
<t-
LO
00
T3
X)
<J-
<j-
vo
CM
LO
LO
LO
<t
<t-
<J-
vO
CO
LO
LO
oo
00
00
c^
CM
LO
oo
oo
<t
<t
CM
00
PM
<t-
CM
LO
<tLO
LO
oo
<J-
T3
LO
LO
Q
CM
tu a
s <u
MM
<D
U
O
(73
00
<J-
<J-
00
vO
<t
CM
00
00
LO
C1J
CX
0 0 T3
nj U
4-i o3
a x)
P-i
o
o
00
0) C
O 03
5-1 -U
QJ
PM
C/3
x:
W)
T3
CM
X:
PM
Hd
T3
H3)
id
H3)
nd
nd
nd
nd
X)
nd
o
PM
PM
PM
PM
a)
PM
PM
PM
PM
PM
QJ
4-1
03
5-1
PM
O
PM
PM
PM
PM
PM
(U
nd
T3
T3
nd
T3
T3
CU
H
O
C
O
O
PM
PM
PM
PM
(1)
4-1
03
5M
CJ
5M
S + J
S4->
T3
CU
<D
O
(1)
<u
a
n
T3
Q)
H3)
<u
5M
u o
o o
a
c
5-i
MM
o o
M-I
a)
M-I
PM
4-1
03
4-1
P-i o3
O 5-1
s y
M-I <U
4-1
P M 03
O 5-1
MM
Hd (1)
(D O
H JH
5-1 O
O
O
s-y
PH
5M
MM
MM
QJ
PM
4-1
03
y ^
S
nd
cu
0)
5M
99
<t-
o
vO
vO
T3
<t-
o
P4
*
m
CD
4-1
oj
CD
M-l 5-J
O O
CO
CD
5 0 X
Cti 5-i
u cti
C X I 00
<t"
<t"
<t"
CO
m
o
o
cu d
o cti
u u
O
VO
vo
vo
Q) CO
p^
<t"
vo
o
60
<t"
-*
vO
<t-
<t"
CO
CO
CO
u
<t-
< *
o
tf
<f
o o
H CO
4-1 CM
cti tn
X) i-l
H
.
O CO
cu
xt
M-l
^
O
a>
M-l
PM
a)
u
Cti
y ^
S
X)
JJ
CU
cu
5-1 O
ft U
6 ^
o o
VJ
IW
P-i
O
O
p>
<U
4J
cti
xt
<to
u co
Cti
CNJ
JX!
H 00
O CT\
cti O
CO
c
o tn
cti O
ii e n
ii i n
T3 m
H O
xi
<}
o X
cti m
I-I
CD CO
H
O
5-t x :
ft P-i
4-) p>
cti
iI
Q)
3 4->
X) Cti
I-I x :
O Pu
< en
o
X) x!
ftcu p.,
o
r--
T3 vO
H O
<; cr\
XJ
6 S
O cti
u
M-l ,id
O
0) O
4J ftf
Cti
O cti
5-J
M-l ,id
o
cu o
JJ p>
cti
iI
0)
3 4-
X) cti
T4 X!
O Pu
<; en
o
X)
d)
r-l
5-J
ft
XJ
iI
Q)
3 4J
X) cti
H x !
o cu
<J en
PH
M-l
O
X) x !
0) PM
H
5-1 <4-l
ft
s S
M-l
CI)
M
o
O
u &
cti
II
d)
3 -i-1
X) cti
H x !
o cu
<J en
O
X) x !
CU CM
H
5-1 <4-l
ft
O
5-i
M-l
cti
^
O
cu
U
cti
iI
3
X)
H
O
pi
CD
4-1
Cti
X!
Cu
<J en
o
-a
x:
CU PH
H
5-1 <4-l
ft
100
APPENDIX B
EXPERIMENTAL FILTRATE P90
The crude
slurry sample until the top portion of the cake appeared dry and after
analyzing the resulting filtrate P0., the filtration rate in units of
pounds of filtrate P90,- per hour per square foot of filtration area was
then calculated.
101
T 3 r1
r-l O
o
M-l
CU CU O
P
P
cd cd p
d
P4 5-( P M
O
H
p
d
. - i cr P
O -r-l co cd
H PM \
5-i
p
5-1 P
cd M-i 5 5 r - l
-H
5-i
O \
P
LOPM
i1
CO O
CM
H .Q
PL4 r - l P-i
O
O
cd 5-1
.d
o P CD
r-l CU P
5-1 g
cd
0
X
Xi . d
G.
D, P
cn
CO H
o
0
-d
XI
a.
<;
PH
6
d
H
O
4 J <1
r-l
-d
cd cd CU
5-1 o
5-1
P o
cd
t1
d a.
r-l
o a;
Pn g 5-1
"d
cu
d Td
cd 2
d
o
5-1
U
H M-l
P O
cci
5-1
P
a;
LO
LO
5-1
CO
Cu
ii
-d^
ti
cu
r-l
cu
CO
H
CU
X
H
>* H
d
o
H
P
cd
H
5-1
CCi
>
a;
H
>H
d cd
a; 5-1
d d
a; cd
u
CU d
5-1 M-l
M-l O
H
O
<
P
O
d
m-d
d
o
o
cd
a;
5-1
H
p
CU
,>
cd
tl
i
d
o
d
cu
o
bZ
O H
5-i cd
P-i
P
CO
<;
tl
a;
PM
ocd
o
cr\
ti
CM
CM
CO
vO
O
tl
tl
tl
00
vO
tl
CTN
LO
CM
KD
r-
CM
CO
<t
tl
tl
- d
cu a;
CM
tl
cd 5-<
m.
CO
< t
CO
CO
CO
LO
CM
LO
LO
r-
o.
bO
-P
CO
^D
\0
CO
(D
P-i
*> cn
cu
5-i
6 2O
H
crj E-i
CU
PSJ
ii
P
cd * d
d -P <u
cu o -P
>
H o
tl
cd
O M-l a;
CO
O u
d P-I
M-l X ) P
o
o d _ g
3 d
O
o
CO
^D
r-l
co
*d
P-I
d
3
o
^
a;
P-i
P-I
PH
LO
CM
ti
cd
p
tl
o.
O
CM 5-1 d
P-I P-I H
H
CM
cd
CO
5-i
H M-l
P M M-l H
H P
g
o
Td
r-l
a;
a.
cn 6
o cu
>
d
H x )
N-' 5-1
p
LO
cu II I1
H
CMbO
cd CO M-l
P-i
-p
M-l CO P * d
CU H P
tJO P
cd cd d
P
ctf O
H
CO
p
P
P-i
d
cu
a; CO
o cd x i cd
d H d
o o 5-1
u o O CU
CO
00
O
CM
5-1
d
o g
en
<t
r^>
d o d
cu d -H
o -d d
H
-P
> >
r^>
bO
i1
p
H U
5-<
5-<
a;
d T 3 P-l
r-l
CO
O <f
CM
r-H <d LO
P
P-I
V
-p H
H O
5-1
^D
5-1
i1
CO
^D
CO
r^>
a.
B
a.
>.
5-1
CO
o CM
>.
5-1
tl
ti
CO
CO
00
CM
in
O
P-i
PH
PfiS
5-i
<
cu
P
cd
5-1 cd nd
O . d r-l
M-l Cu 5-1
CO o
QJ O I1
P v d Pn
cd
cd
cu
d
(U
P-i
u d p
y
d -H o g
a;
cd
O
LOCU
5-1
CU
CMd
P-! P-I p
u o
^D
CO
tl
CO
o
o
r1
CD
4J
CD
4J
U-l
O
Ctf Ctf
u
d
5-1 Pn O
4J
H
C
r - l CT 4-1
O
- H C/D ttj
H
f^ \
5-1
4J
5-1 4J
Ctf M-l ffl t-I
>H
5-1 O \
4J
inp^
iI CO
H ,3
CM
P4 (-3 P-i
P^
Ctf
CD
U
<
CO CO CO CM
CM CTN 0 0 r^>
0 0 0 0 ^ O
CO CM CM CO
T-I
VO
T-I
TI
T-I
o
o
r^>
cr.
T-I
CO vO 0 0
T-H
O
CO CO CO CO
o o
LT
W)
<N
P-I
d
H
> >
t
d
4J
CO
o CM
CD
4J
H CJ
5-1
2 n3
H
o 5-1
o
a,
B
H
CD
Pi
r^>
CM VO
in
T-I
T-I
T-I
o o
CD D
O T3
5-1 O
CD 5-1
P-i P-i
m
T-I
CO
t-l
00
O
O r-
T - l
T - l
o o oo
o o o o
VO r^ < t c^
CM CO CM CM
V O O ^ O 00
CO CO CM CM
0 0 t - I CM T - I
CM CO CM CO
o o
O O
o o
<J\ CO CM
CTN
T-I
o T-I T-I
o o o
T-I
<3
o CM
CD
4-1
< t CM
T - I T - I T-I
O O
CO
o <f
< m
4J
T-I
Pn
d
H
d o
H ctf
M
ttj
4J
00
O
T-I
CM
oo r^> CM CO
T-I
T-I
o o
o o
o o oo
LO < j - CO
<f
CO O
T-I
Tl
T-I
Tl
Tl T - I
T1
T-I
T-I
<f
T - l
T - l
Tl O^ - s f
t-l
O T-l
00
T - l
o o o o
o o oo
o o o o
CO CO
c^
0 0 < j " VO i n
CTN CM T - I v O
VO CO CM 0 0
00
<j-
r^> oo
0 0 C^
CM CM CM CM
CO C ^
O C^
CM CM CO CM
0 0 CTN
CM CM CO CO
m O
m
r^>
O
O
m
o m
CM i n r^
O
O
T-I
o o o
T-I
d
H
H3)
T-I
CD
H
>n
T3
H
O
<;
4->
4J
O
W) O
ttj
4J
LOT3
C/D
<r
t - l CM i->
CO CO CO
CD CD
5-1
CD
P-i
o o
CM 5-1 d
Pi
Pi H
CD
H
4-J
O H
CO
5-1
rt H
td
e sO
CD
CM
m
o
m mo m
o
r- O
CM
o o
Pi
i-l
u
d
CD
T-I
O
C/D
cd T 3
4-i CD
O 4J
H O
Ctj
M-l CD
O 5-1
M-i
<-d
>
o
CO
T3
d
2 d
O
CM
d P-I
!= O
vO
CTi
T-I
VO
T-l
r^>.
00
P I
LO
d
3
CD
oCNJ
P-i P-i Pn
T3
CD
fl 4 J f l |
H CJ O
s
5-1 OLO 5-1
CD
CD CM d
P-I P-I :=>
VO
CO
vO
00
VO
OO
CO
r-*
103
The
The unreacted
104
rH
*& O
M
O
a o
o rt s-i
<;
O
H
H
O
J2
j PL,
d
co
P-i
jd
4-1 CU
CU 4-1
rt
XJ
i
P<
4-1 CO
TH
cu O
J3 . rt
4-1
a.
M-l
<D CD O
4-14-1
Jd
CT5 ctf 4-i O
Pn S-i pn -H
4-1
4-1
Jd <-H cr* ctf rt
O - H en s-i cu
H pn s ^ 4-1 5-1
4_i
>-i ^i -=d
5-1
O id -p4
Ctf M-l
H
4-1
LP)
ii co O
H , 0 CM
Pn J P-i
rt nd
^
X!
mo
o | &o
-H
a. >-i
CNg
P-I
M-l
CO O
O i-l
CD Si Pn
4-1 P-,
% r*
S
I p
^
4-1
H
5-1
3 -
p: e o
3 5-"
fd - H M-l
O
O
H i - l nd
4-1 nl CU
rt o 5-i
5-1
4->
i-l
H
P4
O
CJ
O
g
rt
P<U
5-1
P.
CU
CJ 3
&
rt S-i 5-1
U
_
3
P-i
CJ
i- O
ct!
jd CO
o
O M-l
iri
5-i
H O
O g
4-> - H
in
Jd 4-1 CU
cu cti
o-H
fd O
o o
o co
>^
5-1
4-1
P
Or
nd co
3 n)
5-i
o
cu
co CU
-H
CU Jd
Q
CO H
-H
IS n 6
CU O CU
- H 4-J
Ctf 4-1
4-> ctf fd
en p4 o
-i-l
CJ 4-1 4-1
-H a nJ
CU
LP) CU
5-1
> 4-1
60 i-( i-(
CM CtJ O - H
PL, + j en M-i
en
M-i
4-i nd
o x) a
C a) rt
fd O
O O
i-l CU
4-1 e n
Ctl
5-i
CU Jd
M-l O
M-l H
H 4-1
CO VO vO
vo ON o is
<f is co m
CM CM C^J CM
CM CM CO CM
CM CM CM CM
<f ON vO <f
vO LO vO vO
00 CM is (^
oo oo m is
m m m m
<}- 1-1
uo vo in in
O O CD O
o o o o
o o o o
o o
CM CM r-i TI
O CM (^ ON
CM <} iI LO
CM
CM
CO vO <f O
ON CO
o o o
o o o
O O
<D
o o o o
VO 00 in CTi
ON 00 is CO
IS LO
r-l iI
o o o o
o o o o
o o o
<f 00 CM
O O
o o
V
is o> o
4-1 4-1 6 P4
CJ O Jd
cu 3 -H
O X) C
5-1 O H o
CU S-i rt
PM PM 4-1
o o o
o o o
4-1
- CJ
cu cu
H 4-1 60
>^ O nj
P 4-1
innd en
O
O
CM5-I Jd
P-i P-i -H
O
5-1
CU
P-i
H
~ CO
4-1 CU 5-1
O g
3
rt'H
O
<IJ H fC
Pi
vO ON CO O
i n <i- i n i n
o o o o
o o o o
o o o
vo
0 0 O il CO
ON i s oo
<}<}<}<}
m o in o
CM UO is O
O O O i-l
00 CO CO LO
00 iI ON
o o o o
<f co
o o o o
o o
o> ii ( o
CM co <t m
CM is O CO
fs fs CO CO
CM ON ON CM
<f CM
m io
in in
vO vO vO vO
LO
LO
in
m o m o
CM
m o m o
m is o
CM
o o o i-i
o o o i-i
in is o
m o m o
m is o
CM
o o o .-I
o o
<f
CO O H
nd P-i
jd
m
3
5-1 O
O
PM
CU C M
P-I P-I
H g Q O
5-i O
ctf
rt 5-1 4-1 CU
> M-i nj 5-i
CM
nd
4-1 C
C -H
4J
O P-i
cu
a
cu
d o
mcu X
U O
5-i
0) CM fd
P-i P-i J3
<}00
CO
m o
CM
vO
C
o
P C S
en o s-i
M-i nd J3 P-i
4-i id nd
C 4-1 CU
CU O 4-1
> H
O
i-l
itf
O M-l CU
is CO
i s m o CM
iI CM CM CM
ON VO i s O
O O O i-l
cu
OJO
^
X)
ii
CU
H
>-i
<l)
O
5-1
CU
d ^ i
H
ON
m vo vo uo
o o o o
vo in o> co
a.
M <J m
H X )
H
T3 O
-H <
5-i
3
4J
P>
C
O
O
O CM vO CO
CO CO CM CM
00
in
105
CD CD O
U 4-)
cd crj 4J
Pi
fe
'H
4J
r-l
U^
O -rl W
H f n \
4J
J-l
4J
CVj
^
4J
r-l
<
u o
<f m
CNJ CNJ
r-l
CO O
r-l , T l CNJ
[ K i-l FM
mo
o | bo
c^
r ^ C l <U
4-1 O O
H O
M
J-i
CD
3 - d P-<
0.H
6 O <f
M
<
m
M
G\
m oo
o o
J <u
4-1 4J
<f m
Pn
fi o C
CD 3 -H
OTJ
C
cj>
J-l O -H
CD U cvj
Pn P-I 4-1
H " d
H
T3 O
r-l <T! 4-1
CD
CD (U
r-l
>H
4-1
O
6 0 CD
crj
O
4-1 fc
LTTO C/3
O
cMJ-i
PU P^
-H
CD
g
-H
E-i
J-l
3
O
td
4-> crj ^ d
(=! 4J <u
CD O 4-)
> E H
O
r-l
CTj
O M-i CD
co O J-i P-i
Pi O
H f l p g
o c
co O -H
" d P-I
3
O
P-I
4-1
m
J-i
CD CNJ
P-I P-I
K>
CD
P-I
CO
H
4-1
O
crj
CD
Pi
CNJ CNJ
V>
4-1 P-i
C H O O
CD
CVj S
o
incD
J-i O J-i
QJ
csiq!
P^ P-i p
m o
r^ o
O
r-l
106
<u <u o
T)
H
4-14-1
Ct) Ct) 4-1
a) o
d o
o u
P^
4-1
o jn
O - H CO 4-1
5-) UCU
H Fn
nl
M-I
S-) O
4->
4-1
4-)
CNg
P-I
>* d cu
PH
Pi
H r - l *"d
4-1 Oj CU
FH
crj O 5-1
a,
O
13
a
2
O
U
u
g
rt
>>
a
5-1
CU
U
5^
O
r-l
4-1
ctf
5-1
4-)
d
CU
O
d
Oo
4-1 CO
O
^N
PH U
d O o
O g
O
-H
in
4-) CU
rt 13 co
- H p crj
O 5-1
co
o o CU
4-1
CU
PM
5-1
J^-H
x: 3
4-1 O
H T J
H
nd O
r-l <
CU
H 4-)
^
O
3
O s f C ^ H
< f O H CM
CNJ CNJ CNJ C N
<f o a> i n
CO *"t r-l ON
O r-l r-l r-l
CTv iI < f 0 0
O r-l r-l il
o o o o
sf n vo m
CN r - l
CN CN
& CFn
5-1
PW
crj
4J
4J
CU d
t>0 CU
(U O
4-1 S-l
Is-*
iI iI O
o o o o
<fCNCN<i-
r - I O O m
CN CN CO CO
CO CO CO CN
CN CO CN CN
CN CN
o o o o
o o o o
o o o
OS CO r-l CNJ
O O r-l r-l
H vO N CM
r-l O O r-l
coco o <r
r-l i-l
r-l
o o o o
o o o o
o o o o
o o o o
ii o
CN Os CO O
iI O r-< iI
*cf r o CA CN
r-l
f* 0 0 CN CO
O
O il il
o o o o
o o
o o o o
o
o
o
o
H
H
vo
ii
CN
CN
CM O i H
Os vO iI <J-
CNJ
ro
N
H
CNJ
CNJ
r-*
VO CM
CM < i "
o o
r-l
r-i r-<j- co
il il O
^ O O M O
<i- r*- a- oo
ro <f vo i n
ON
oo
il CN
i n Is-
CM CM CM CM
CN CN CN CN
CO CO CO CO
m o m o
CM m r- o
CN
m o m o
m r- o
CN
in o in o
m r- o
CN
o
m
o o o r-i
o o o I-I
o o o r-i
o o o r-i
m n 3 en cu
O
O
P-i
CN 5-I
d
PL, P-l T H
4J
5-1 CU
O
r-l
d oo
ex,-i-i
O H O
crj EH a
CU
a o a
bO H 4J
> Ct) 4 - 1
n d 4-) cvj
d
r - l CO Ptf O
CU
H
'i-l
d 4J 4J
> H -r-l d
crj
CU U
i n c u > 4-i
W ) iI ii
CNcrJ O T4
P-l 4-1 CO 4-1
CO
4-1
4-1 T j
o nd d d
d cu oj
d o 5-1
o o cu d
H CU 4-1 O
4 J CO * H -r-l
CVj
- r l 4J
r-l
S-)
CTj
O
U
CTj
4 J CU
>
<J-
4-i
crj 5-i
co
CU 5-1
M S 3
ee co e
M
4-1
CNJ
O l j
fl
U O H CJ
CU
o <f
<; m
d o d
cu 3 H
5-1
*"d
4-i
d
iI
Ctj
H
CO
o CNJ
4-1 o
a
H O S-)
5-1
CU
3 nd PH
a, -H
tf _ g
ffl O
B 5-1
d -H u-i
o o
CN
ii < f o
mo
OlW)
CTj
CO O
O i-l
a; . a
O CM vO O
r o <f i n vO
il CO O
H ,3 CNJ
f H | J PM
cvj nd
5-i X ! - H
o a , 5-1
4-1
o r- CNJ m
i n <f vo vo
-H
Fn
CO
a-H o
w .a
o
a,
x ! cu
P-l
4-1
d r-< t r cd cvj
CU CU
O O 4-1
H <J CTj
5-1
J=!
. d
d
O
S-l Fn - H
m o m o
CN
i n t-~-
Pi
4-1
d
CU
CTj *T3
4 J C1J
O 4-1
> H O
r-l
CTj
O 4-4 CU
CO O 5-)
00
d PM
Tj D
U
CO
CO O H
T j P-l
d
d
o
P-i
m
5-i o
cu C M
CH
CH
O
TJ
cu
4-1 d
G -rl
cu
O
U
cu
4J
O P-t
crj c j
m cu S
O
5-1
CN d
P-i P-i F3
CN
n Rate,
Itrate
q Ft of
ation
107
4-1
I-I
H y j
fe
M-4
CJ
cd
QJ
00
S-i S-i
4-1
Fil
rat
o
H
i-l
CO r-- cN
O
i-H
CN CN CN
CN
i1
i-l
CO
i-l
rQ
1-4
>-. od
CN
QJ
O rH
13
H
O
<
ent
uct
o
S-i
<u
H
4-)
O
U
< f.
CN
QJ
p-i
n3
i-H
<u
H
>-
o O
CO CT\
CN I1
vO vO CN CN
CN CN CN CN
o o
O. O
o o
ro
<t O
m
d
CN
QJ
fe
I-l
I-l
I1
I1
o o
CN CT\ CO
O
i-l
i-l
o
O o o o
i-l
13
d
O H
S-i cd
P-i 4-)
O
cd
I-l
CN
i1
o> o
CO CN
I-l I-l
I-l
vO I1
CO I1
CO
r--
r o < f
m o
r-- o
m
o m o
CN m
r-- o
o . O i-J
I-l
o o
o o o o
13
H
O
o
3
LDT3
O
Per
puri
4-1
o m
o i-H i-H
O o o o
i-l
ro
d o
NS
4-1
i f O
00
P-i
QJ
CN
P-i
3
d
C3>
o pa
m
o
fe
n3
r--
CO
^-s
vO
CN CN
o O
<d
00 QJ
cd a
4-1
C/J
^
QJ
r--
CN
CT\ O
0>
i-l
P-I
CNS-J d
P-I P-I H
^w
QJ
ds of Solvent
Pound of Total Reac
in Unreacted
Ti
MCP
Ho
S 3*-!
I1
m
o CN
ent Total P
o
5-J
QJ
p-i
acted
d
3
9.21
H
4-)
Hm o j
5-1 o
V4
QJ
cNd
P-l p-i
E>
p-i
u
S
29.36
X>
cd
H
i-l
108
QJ
4-1
rt
n d 1-1
H
O
CJ d
< ; rc5
jd
CJ 4-)
H
Q)
5^ S
o
,d
jd
o
O
J:
crw
CM N
^D O i
CM CM CM CM
<u
d
4-J H 3
Ct) - H
Si
U
M-I
a. o
m
J-1
tO i-1
O h
,d
PL,
5-I
<N2l
>^ d cu
4J O
H CJ
o -H
o nd
4-)
cu
ct) ct) 5-i
4-i
O
S
S~\
CJ
o
LO
H3>
H
i-i
<
CU
rl
J-l
4J
>H
O
d
LPTd
in
aj
a;
4-)
4-i
Ct)
p4
d
O
-H
4-14-1
d
ctj
>
4->
CU
5M
CO i - l iI
O
H
P
CMbO O - H
Ctf CO MM
4J
M-4 CO 4-1 <Tj
0 0
*& CU rd
5-1 5-i
o H a) d
H
rl
4-> H
ctJ
5-1
H O
ctf 5M
>
MM
m
CM
4-)
M-i
O
M-l T - I
- H 4J
P
CJ
ctf
4-) CD
ct) 5-1
pL,
4-)
d
CU QJ
M O
cd 5M
4J QJ
CO P M
n)
" C0
CU 5 M
g
d
rd
tlj H d
4-1 CU
O 4-1
> ^
1-1
O
CO
tlj
MM CU
O 5M
MM
-Tl p
d
o
co
H3>
d
d
O
PM
PM
d
d d
O
-H
PM
5M
CU
PM
4-1 d
d -H
QJ
m
o
CM
PM
T3
CU
4J
CJ P M
Ctf C J
mcu
5M
QJ
CMd
PM
P
PM
vo
o>
vo
vo m N
o o o o
N
pM
in m in vo
o o o
o
o o o o
V
CO O i
co 0 0
CM
<f
M
00
r^ro
<J\
ro
CO CM
r o <J-
I-1
r-i
CM
i-l
00
o
0>
O
0 0 CTi iI
CM CM 0 O
O
CM
CO
O
PM
4-1
d
CU
r-
-H
CU
PM
O
O ^>
CM CM i-H
CMJM
PM PM
d
4J
n)
5-1
CU
js
- W3
T 3 Ct)
i - l 4-1
CU CO
H
>^ d
H
o <!
<tj m
PM
a. w CU
g .H to e
HM
O <T3) d
J-l O - H
QJ J-l tlj CJ
in
t ^ to si
4-1 - H H
H f i ^
5-1
d 0 )
\D
i-l
iI vO CM
PM
d o d
cu d - H
cu
CI)
Tl
4J
CU 4-1 T 3
tfl
CJ ctf d
ctf
d < H 5-1
O
CJ CJ
0)
CJ
CO
CU
PM
o o
a>
T3) <U t ^
d ^ d 5-i
ct) ^
5-i
5-i
d
d u
I-I
I-l M-l
4-> O
ct)
5-1 d
O
5-1
5-1
CJ Ct)
o
a.
d
<u
O 5-1
h S
0>
<j- m in m
o o o o
<j- in m in
PM
PM
m i-i i)
LPO
O l W)
5-1
u
i-i
H
vo oo
CM CM
A A A A
a.
*d
PM
r^. o o
CM CM
A A A A
LTIfn
4J
i-1
tfl
O
H ,13
(N
h
h J CM
a.
w
si
-i-i
fin
O H CO tlj
H Pq \
5-1
4J
5-1 4-)
5-1 M-l
tlj
O [r! i - l
cu
4J
tlj
PM
5M
a-u
QJ O
4-)
d
4-)
d
5-1 fo O
4-)
-H
5M
m o m o
in N o
o o o I-I
CM
m o m
m N
CM
O
o
o
i-i
109
CD CD
d
o
cd -P
5-1 P M
d
H
O
<J
o
<D O
d
5-i
O
U <D
o
m JJ
H
O
cd
5-1 <
^
o
a.
i i
to
CL -U O
tll-H
PL
cr
co
\
M
pd
H
-P
cd
5-4
-P
d
^
oo
M
CO <M < f
<r
n o
o> vo
O
o>
O
N
O
i-l r H
ro
i-l
00
o
0 0 N CM
o
i i
CM 0 > 0 0 iI
iI O
O <I
iI iI
o o o
o o
d
o
CNJ
i-i
<H
4J
-P
CNJ
a;
b|PM
y dH
<D 3
o -d d
5-4 O H
CD 5-4 cd
PL. P-I P
y ^ \
^
&
o <f co m
(N
CM M
<N
vt
o o
CM v O H
N
CM CM C\I CM
O
< t - CM v O
CM CM CM CM
ii m o
CM
CM CM CM CM
CM O
i-l
i-l
co
O
PL) o
O 'D
S o
m
QJ
>d 03
d cd
co
O
P
H
O
5-i
3
-d
PL -H
H
Pi
o
o
CD
o
03 CD U
P^ w , d 3
.LJ . H
H U
H O
^ cd
5-i
3 CD
a)
PL 03
- H 03
M
&
O a>
CD > H u
- b0 -U
T 3 cd cd d
r-l -P Pd o
H
CD e n
H
-U u
!x
d
d cd
H CD 5-i
m
> +J
o
a; I-I I - I
C M W ) O H
pl-i Cd CO M-l
+J
L H CO - U T3
o
d d
d
a; cd
d
>-i j-4
O H <U d
H , d M-l o
U H M-l H
cd
- H LJ
H g
O O
5-i
5
cd
cd 5-i -u a;
>
M-l
cd U
H O \
i-l O
CON
i-l
O
CTi 0 0 CM iI
O
O
i' i-l
cn co
CM
i-l i-l
a%
O
O
I-I
^>
O
r^
O
vO
(D> m
CO
o o
o
o
o o
o o
o
o
vO
i-l
0 0 v) O
CM CO < f
o o o
(N
i-l
vO
O
00
O
vO
O
O
i-l
C3> iI
O
i-l
o o o
o o
o ^o o
O
i-l
d
d
I-I
H
o
<;
-P
<D
H
-P
CD
CJO CD
0 0 r^
VO N
iI O
00 CJN
o o o
vO
vO 0 0 O N
CM CM CM
CM
CM < f
r ^ CO
co v t m vo
CM CM CM
CM
>-) o cd o
3
L|
u r d co a;
o o
P-I
CNJ5-I
d
P-) PL) " H
O
03
H
CD 5-1
M 6 3
O -H
O
n! H f f i
CD
P4
u
ri-d
-LJ <u
<D
>
i-i
O
co
o 3
d
03 O
" d PL)
PL)
4J
m o m o
CM m r-. o
in o m o
CM i n
r^
o o o I-I
o o o I-I
i-i
II
CM
00
I-l
<f
vO
r^.
co
co
co
co
CM
CM
CM
CM
CM
p^.
CM
m o m o
eg
O
in
O
r^
O
O
i-l
m o m o
CM m r^ o
-I-J
O
cd
M-l CU
O 5-i
d P-I
M-l > d ^ > O
MD
CO
II
5-i
O
CU PL)
CNJ
PL)
rd
cd
H
CO
PM
d
o
o
T1
CN O
I-I
mo
OlM
cMg
6 ^
CD
<( i n vo vo
CM
PL)
d
3 M-I
O H
H
O "d
U i - l CD
cd cd 5-i
J-J o
cd
+J O
PL
r-i
d
<u
H O
J-l
p^ ;
PL
vO
<N
<t
<y cd
+J
^
5-J Cd H
O J3
U
M-l CX O
03 r-t
QJ O Pn
u , d
cd Pu
g
pt!
6
>>
u
J-i
3
I-I
w
KD CO
i n <( vo oo
LTfi^
^
PM
-d
<D
d 'd
cd 3
5-i
d o
o
H M-l
4J O
Cd
5-i d
LJ O
d -H
<D -P
o
cd
N r^ \ o
ro
00
0 0 O H
H H
N
N
T3
a;
4 J PL)
d -H o o
<u
cd ^
o ma;
5^ o
5-4
CD < M d
PL-l P-l D
110
P 0 r with 6.30 and 7.06 pounds of methanol per pound of total P^O,.
2 5
2 5
in unreacted MCP in successive stages, while the unreacted monocalcium
phosphate P^O
The filtration
concentration and
Ill
MH
>
X > r-H
H
O
<
O
H
CU
4-1
CtJ
P^
CtJ
4-1
d
o
H
CtJ
,d
CU
4-1 4-i
CU CtJ
J2
4-1
ctJ
5-1
4-1
n
o
a
X ! J-1 co
a-
o
CO T - I J 2
O
CU
4-1
r-H
U h
SH
>w!U
O \
r-H
vD
O
CM CM CM
LOO
CO
r-H
i-H
ol&p
Ns!
5H
00
<r
r-H CO
CM CM CM
<r
CM
i-H
i-H
c^
CO 0 0
CM r-H
o
CM
00
i-H
r-H
r-H
CM CM CM
<r
r-H
CM 0 0 v D
r-H r-H i - H
i-H
rH
CM
r-H
ON
r-H
r-H
r
o
LO
O
r oo
o o
CO 0 0
r-H
ON
oo
ON
o
o
o
o
vD
O
ON
<!-
w <^
r-H
LO'rH
w o h
,n CM
rH
pH t-H"
PH
4-1
O
rH
tr" ' H
H CD 4-1 crj
P H ""^
CtJ Q)
PH
XI
CtJ
4-1 X I
5-1 CtJ H
O
j 2 5-1
O
M-I
r-H
PM
CU O
4-1 XI
PH
CU
a.
w
CtJ PL,
PH
g
d 5
H M-l
4-1 O
CtJ
5H d
4-1 O
d
-H
CU 4-1
O
ctJ
4-1
CO
O
CM
r^, Pi CU
4-1 O
O rH
H U H
5H
CU
3 X I PH
6
o
5-1
M-l
a TH
B <o <lLO
4-1
>^ .
/-\
C
H
CO
CtJ
PH
o
S
CU
CU
x> 5-i
3 4-1
3
CtJ
5-i
CU
'
X)
r-H
cu
>
c/)
4J
o 4-) d
CU
d co 5-i
^o
o
r^
CM
CU
r-H
J=>
ctJ
H
5H
co
CM
CU
PH
PH
PH
XI
H
O
<
G
- H CtJ
ctJ O
4-1
4-1
cu d
CMSH
PM
O
H
4-1
O
O
5-i CU CtJ
H - H M-l CU
4- P H M-l r-l
H
CtJ
H
6 Q
5-i
5
CtJ 5-1 4-i
>
M-l CtJ 5-i
C/3
X>
O
CU
PH
O
rl
i-H
CM v D
r-H
LO
r-H
o o
00
CO
r^.
i-H
O
CM
o o
ON
r^.
o
ON
r-H
CO r-H
r-H
O
vO
O
ON
r r-H
o
o
r
o
O
r-H
i-H
i-H
00
LO
O
r r-o o
o o
o o
ON
00
LO
vD
LO
r-H
vD
00
O
vD
00
LO
ON
<r
CO
CO
LO LO LO
o o
o o
CO LO
i-H
r-H
ON
<!- r
o
ON
<r
ON
ON
00 ON O
CM CNl CO
O
CO
<!-
00
LO
vD
r-H
CM CM
LO r-H
ON
o o
co
00
r o
vD
CO
r^oo
v D CTN
CO
CO CO CO CO
4-1 1
o -a !x!
o
LO
CM LO
O
ctJ H
CU
CO CO
dr
CO CO CO CO
<r
LO o
r^ o
LO O
CM LO
LO o
r^. o
LO
CM LO
I^N
o
o
LO
O LO O
CM LO r^. O
o o
i-H
i-H
i-H
LO
o o
i1
CtJ X )
4-1 CU
CU O 4-1
H
O
r-H
CtJ
O MH CU
O
5H
t/3
>
a
3
PH
^)
ON
r-H
PH
d
o
3 d S
r-H
CM
LO
r-H
i-H
vO
oo
c^
O
O
o
o
r
o
o
r
o
o
<!-
<!-
-H
PH
JH
CU
PH
un
O
CM
PH
r-H
4-J
X)
CU
4-1
O
CtJ
LOCU
C
H
o
5H
5H
CM
PH
t)
CU
CU
PH
r-H dr
CM LO
<r
4-1
<r <t
PH 1
CO
Xl
CO
rl
MH X )
O
0 0 CT\ CO O
v D vo
r
ON
<t <!-
o o
CNl CO CO
CO CO CO CO
<r
"
(U
Tota
d d
M-l
5H
CU
H 4-) bO CU
O
ctJ O
r^
3
4-1 }H
L O X l CO CU
O
PH
O
. d
e -H o
CtJ
4-1 - H H
H
O N
CU
4-1
5-i
3
CU
Pu CO
CO O
rH
M
JS
CU H 4-1
- bO 4-i CtJ
Xl
ctJ CtJ 5-1
i-H 4-1 P$ 4-1
r-l
CU t / 3
4-1 H
H
M-l
H
CU
LO
Xl
I1
cMbO O CtJ
4-1
4-1
CNJ 0 0
G
o d
CU P H
d 'H 5-i
o a g
u o
co CU
t^. co Xl
P H
<
5-i
5-i U
o
r - H LO
CO LO
i-H
G
H
Pn S
d
O
O
vD
r-H
o o
PH
O -H
H
O X)
4-1 r-H CU
CtJ CtJ 5-1
5-1 O CtJ
4-1 O CL
rH
C CU
H
O 5-1
CL
X l CU
d 13
CtJ 3
5-i
PH
O
S
r
<T
r-N
<f
i-H
112
*0
H
J*
O
(D O
0
U
O (1) O
4-1 4-1
cd cd 4-i pj
PH
5-1 f n O
4->
TH
p; iI c r 4-i cd
O - H W Cd JU
H PH
U 4-1 <J
4-1
cd MH pej I-H
5-1 O "--. -H
4-1
mpn
iI en o
H ^3
CM
PH t-J PH
a
< o
<u
o -p
O) 4-1
H
o cd
5-1 <J
jr!
a,
J=! . C
en
a. -M o
en T-i
o
*c
x!
LOO
0 | W)
CMS
CD cd
4-1 1 3
5-1 Cd v - l
O X ! 5H
PH
M-I
PH
Pi
r-l
CO iI
(IJ O
4-i j d
cd PH
pd
> , Pi
4-1 O
H O
5-1
e
o
e n
a- -!
pi 3 MH
CtJ
O H a
H O T <u
}
4-) ii <u
5-1
cd
cd
5-(
MH S
aM o
4-) CJ
O
T3
-
f i 5-1
pi -O
H
O 5-1
cd p)
5-1
Pi u
o
hi <5
Pi
H T3
r-l
T3 O
r-l <lj
4-1
T3
a a
4-i <u
pi w S-i
o 5-I a)
r4 - H MH
4-1 Pn MH
cd
T-I
nj
m r-~ m m
o o o o
m m N co
o o o o
M n m i n
o o o
o o o
V
o o o
V
o o o
V
<f
c o < t <j-
CO r^
O H
iI r-l
co <t as o
o in oo >-i
c o <! < f
<! c o < f
CM CO CO vO
N Pv CO N
m in N oo
o o o o
o o o o
V
r-l in ON CO
<t
o o o o
o o o o
CM CTi
VO \ D C ) (Ti
CO CM CO CM
O f O H s f
c o c o CO CO
CO vO r-l O
CO CM CO CO
o o o o
o o o o
o o o o
VD !?> 00 Oi
o> o> oo vo
oo oo N m
o o o o
o o o o
> 4 J
CI) PJ
4J M d)
H
o
cd o
^ 4-1 5-1
m f l cxi CD
o o
PH
CM 5-1 pi
PH PH -H
vO CTi
O
O
o o o o
0 0
r - l CX) IT)
O N O N CO
CM CM CM CO
CO c o CO CO
o o o o
o o o o
>X) *X> 00 00
<t in vo r-~
<! v t <! <!
CO CO CO CO
o o o o
o o o o
00 i-l 00 CO
00 iI r-l CM
ir> vO vO vO
co CO CO CO
m o m o
in r- o
m o m o
m o m o
CM
CM
in r- o
O O O r-l
O O r-l
O O O r-l
CM
CM
oo
r-^
m r-~ o
pd
5H
Tj
pi
*=> S
to
CM
oo
Pi CO O
H
T3 P H
m
Pi
CM
PH
PH
PH
H g Q
5-1 O
Cd 5-1 4-1
>
M - l td
00
CM
T3
CD
4-1
O PH
cd u
rd
H
m aj
O
5H
CM Pi
PH PH
p
ON
CO CO co CO
cd T 3
4-i aj
4-1
O
cd
CD
<4H
O
CO vO
a> CM in m
m vo ^o vo
CM
m o m o
CM i n
a) H
Prf
O ^O
oo co
m co co CM
o o o o
<t
CU O -H
CMbO co MH
vO O
rv r-.
PH
<t
m
bJC
Pi
H
CD ^ Pi
5-1
O H
cd
a)
5-i
PH P H 4J
iI
O CM CO 0>
00 t^. 00 CO
ON 0 0
CD
PH
aj
MH CO
o
u
4-1 4-1
Cfl
H 14-1
4-1 0 PH U
CJ o
cd
S o
5-1
m
4-) o
<D
H
f3
a) 4-1 T 3 W
cd
o cd
0 H
O O
CD
u O
U
W
! > . cn
4-1
4-1 -H
Cd
H Q
5-1
5-1
CD
pi 0)
P
a, w
S H
M
4-1
a)
- bo
Pi
X ) cd
O
r-1 4-1
H
<u co
4-1
cd
H
JH
Pi
5H
H
4-1
O
4-1
Pi
CO
CO ON
o o> co o
o
o
r-*
o
o
o
o
t^-
O
O
r-l
113
14_|
cu cu o
4J
TJ
H
O
O
O
d
O
Cd J-l
cd cd 4J
p i j-4 pn
CD
4J
^ g
cs
M
xi
o si cu
x i 4_i co
& H O
J-i
iI CO
i-l XI
cd
CU
J-4
<J
oi
P-i
4J
CO X
uno
O j bO
Cd
cd T3
PL,
co o
O r-4
(1) XI Pn
PL,
cd
& & o
d -H m
o o
rl H T)
&
^~N
LO
d 4J cu
CU Cd T3 W
o - H 3 td
O
w J-4 0)
d CO
o
0) J-l
>o > To < o
3
4-1 Q
H
H
^
J-l CU
3
CO
O-. "i-l
6
M
I*
>H - H
4J
<
4-1
4J
CMJ-4
PL, PL,
4J
Cd
J-4
CU
Cu
LO
*H
4J
cd
CU
>
J-l
4J
-r4
r^ ii x> x>
<f
i-l
CO X )
i-l i-l
CTi
O
0 0 0 0 C^ iI
r^ r^ CM
4J
d
CU
> H
o o o
C^ CTi CO
O
O
O
H
i-l
o o o
II II II
o o o
II
i-l
II
II II II
<f
CO
CO
T3
d
T4
PH
o o
r-. oo
LO
r^
r^ LO
I-I
i-4
i-l
o o o
o o
"X) CTi iI
O
O i-l
X
O
VD O i N
VD
vD h
o o o
LO x
o o
x
o
r^
o
o o
o o
<f
CM
o o
o o
oo co r^ oo
LO X
o o
o o
LO X
CO < f
LO LO < f LO
LO iI
LO LO LO LO
X 00
o o o
o o o o
o o o o
o o o o
o o
OOCOsf
X ) r ^ ii
O
o
H CO CM CTi
iI CM CO <f
X 00 CO CO
CO <J" X LO
iI X
00 LO
i-l CO CM <f
CO <f
CM CM
LO LO LO LO
i. r i r^~
00 CO
LO
LO O LO O
CM LO r^ o
O O O iI
LO O LO O
CM LO r^ o
O O O r-4
LO O
LO O
CM LO
iI
iI
LO O
CM
LO r^
.-I
LO
CM LO r^ o
O O O i-l
ix!
o o
O
PH
CO
PH
LO
00
LO
CU
CM
PL, PL,
=Q
J-4
Cd J-l
>
<4-l
LO
CM CO
d
P
O
-H
4-1
II II II
Cd "XJ
4-1 CU
O 4-1
Tj
d d
cu cd
J-i
cu d
II
cu
H
CU 4-1
4J
cd CO "4-1
H
LO CM
iI iI iI CM
Pi
bO iI iI
4-1 H 3
cd H
CNlCd O H
PL, CO
4J CO 4-4
o TJ
d
d o
o o
J-4
u g
cd
CU
J-l
14-1
Pn
Cd
4J
" C O
"4-1
O
bO
CU
i-i
O
CO
LP) CU
iI
CM
d
-H
O
H
CU
4-1
- Cd 4-1
xj 4-i cd d
i-i co p i o
CU
H
CN1
H T3
H
n3 O
4-i
rH <1 d
cu
cu cu
H 4-1 toO O
> H O cd J-i
3 4-1 CU
m t j co p.,
o
o
to B
CU O
bO - H
iI CM X )
CM CM i(
PH
CU J-4
PL, P i
4-1
PL, C J
cd d c_j o
J-I o g LO
4-1 T 4
O
Jj
CU
d o d
CU 3 - H
CU
cu
O-O
fJ
J-4 O H CJ
d
3
cd J-4 J-4
CJ
rH
O m co
l-l
>, d
4J O
H U
J-4
3
T3
Cu > H
e o <f
4J Cd CU
cd o J-4
Pn
a
J-4 cu
o cd
&
1 3u Td3
r-4
0 0 O N CM iI
il iI CM CM
mfn
J-4 X ! T 4
O & J-l
4-1
iI
CN CM iI
O
C
PH
xi
rH O oo r^
Pn yA PL,
co si
O
d
o
4J
T4
d i-<
c r 4J
O T 4 CO Cd
H Pn ~--~ J-4
4-1
J-4 4-1
Cd M-4 pXj i - l
<: x:
4J
O
4J
cd
4 J CU
Cd J-4
H
4-1
T3
CD
d
J-l O
CU
CM
CO
co
CO
4J
d - H o PL,
cu
cd C J
O
LOCU g
PH
CO
J^
CMC
PL, pD
<J-
<f
114
M-l
CU CU O
4-1 4-1
CTJ rt 4 J
Cd U fc O
4-1
-H
C H
cru
o - H en ni
H f
4-1
\
5-1
H
4-1
<N
y3 N o
a-* r^ o
rt u-i pd .-i
5-1 O \
H
4J
LTfc
iI
CO O
H ,)
CN
p-i t - l CU
ino
O bO
>-. d cu
4-1
-I
5-1
3
CU
O
O
O
S-i
CU
P-i
nd
'H
n
iI
Oi
O
N
o
tI iI
o o o
ro
tI
cri i n L O L O
o o o
m oo m vo
o o o
o
o o o
o <r
< m
o o o
4J
4-1
o o o
6C Pn
CU
-H
ofl
5-1 O
CU S-i
P-i P-i
-H U
rt
4J
-d
H
O
<
4J
CU
CU
H
>-l
OJ
tI tI
r^ vo
o
o
a o a
T3
i-i
CT\
4-1
O
3
CN
LO
VO
LO
O
LO
CO LO
<f
o o o
00
LO
CN CN O
^O
6 0 CU
CT3 O
4-1 5-1
vO <} <N
<T <T <T
O
o
vO
CO
O
oo r^ oo oo
CN iI
00 00
< f CO
C7\
O
CO 0 0
00
00
CO CO CO CTi
L^rd co cu
O
O
CNJ5-I
P-i P-i
a
-H
P-i
4-1
CU
LO
LO O
LO
r^
CNJ
m r^-
O & 3
.-I
CtJ - r - l
cu
Pi
4J
5-1
O
nj
a
4J
CU O
>
H
t-l
O M-l
T3
CU
4J
O
flj
w o o
5-1
4-i t i a
O a t3 P-i
w o a s
T3 d( 'rl
a
LO
3
O
P-i
S-i
JJ
P-i
p-i
Jd
CU
4J
H
4J
O
M
t)
a H o
P-I
CU
tti
O
LOCU
S-i O
5-1
CU
CNd
P-i P-i 3
O
S
<i-
.-I
m o m
CM lO N
r-l
115
T)
H
O
<
O
H
M
O
jd
(O,
CO
(U O
C O
O 5-i
*J
CU CU
O 4-1
< ; nj
jd
ft
-u co
!- O
jd
CU
M-l
QJ O
4-t
4-t
CIS
J-l
4-1
id i - i
O -i-l
rl h
4J
Cti M-l
5-i O
4J
iI co
rl , Q
PH i-J
4J
id
O
-H
c r 4J
CO Ctj
\
5J
5-14-1
K
r-l
PH
LOD
O l M
CNg
P-I
flj
nd
5-1 J d -H
a n
CO O
O i-l
CU J d PH
4-> P-i
CTJ
g
<t
^o
en
r^-
00O<t^
in \o \o ^o
>-, d <x>
4-> O O
H U 5-1
5-1
<X>
3 - d P-I
a, *H
C -H M-l
O O
H H
'd
B o <t
H-l
4J
id
CU
O
5-1
a)
P-I
u ctj a;
PH
CTJ O 5-1
a,
o nj
1M
) T>
th
a d
d 5-1
u
a,
i -CT3
l 5i
O CU5I
U
C
O
H
4J
CTJ
5-1
M-l
O
3
<-!
CO
4-1 -i-l
LT>
a -u a) '
a) nj ' d co
O
O
O
^
u
H
S-i
^N
C_)
C O o
O g
O
PH
'rl ^
O 5-1
co
CO
O 0)
O
^ .
Q H
^
a)
12
CU
5-i
3
4J
ctf
5-i
Tj
CU
H
4J
>H
O
dLOTd
d- to
a)
a, 'r-i . a,
e & co e
f1 0)
60
flj
Tl U
<i cn
0)
H Cj
> H -H
O 0)
-H -U
4J
t C
Pi O
-H
U 4J
(d 0j
0) 5-1
mcj
>
u
O
00 iI iI
N f l j O -rl
PH 4-1 CO M-l
en
M-l
4J "Q
o Md d
d
d
cu oj
id O 5-1
o o o
c
5-1 C
OD M-l nj
H
O
CX3 CO
J-l M-l
4-> >r-i
0)
4-1
>ctf M-l -H
n3 JJ
5-1
H
en
e o y
4-J
C
CU
r-i
\o
\o m
r^-
oo en
\o \o
CN 00
in vo m m
o o o o
m ^o ^o in
o o o o
in m ^o m
o o o o
m m
o o
o o o
o o o
o o o
V
o o o
in
in
oo <! ^o \o
en <t* en CN
v> O ^O 00
en < t en CN
r N oo oo c o
CN en c n c n
<t en
o o o
o o o
o o o
o o o
r^-
oo T~I en CN
CN N N CO
c^ CN < t
CN CN CN
en
cn
o o o
o o o
ii
<j- <t en en
v> cr o
CN CNJ en
o o
CNJ
in m r^. oo
o o o o
o o o
CNJ ^ 1
<t
4J
CU CU
50 O
etf 5H
4J a)
CO PH
i-H
<t m
v>
o
V
o
V
m oo en
en CN CN CN
CN
o o o
CN
PH
\o m
o o
in v> r^> ^o
o o o o
o o o o
V V
oo cr\ ^o
1^- CO O
r^O
v> en r^- CN
oo o c n C N
IN
c^j en c n
en <t en <t
in m in m
v) \0
m o m o
m o m o
in o >n o
CN m IN o
m
CN
o o o
o o o
v> r^fN
ON CN
0 0 CO
\o oo
CU
5-1
O -H
ctf ^-t
CU
Pi
O
ffi
in o m o
CNJ
r^.
.-i
CN
IN
CD
o -
IN
o o o
I-I
CN
I-I
Ct5 ' T d
4-J CU
O 4-1
Ct5
M-l <U
O
5-4
C30
CN
^o
en
en
en
en
<t
in
<h
d -C g
01 O - r l
nd PH
id
-H
M-l nd > PH
0
5d
O
PH
rN
\o \> m in
CN
d
3
oo m r^- m
o o o o
o o o o
V
> H O
iI
O
CO
CNJ 5-1
PH
<J LO
Fn
4J w:
o
d
d - H
Td 5d
O -H o
5-i crj
PH 4J
nd
H
O
-> <J
CN
in KD in m
o o o o
M-l
Pi g 5
3 5-1
oo a^ en CN
v) \o KO r^-
PH
a,
4J
CTJ
IN
\o
mpH
O
C
Jd CU
PL,
o
MD
m
5-i O
CU CNJ
PH
PH
nd
<u
4-J Jd 4-1 P-i
C -H O O
CU
03 S
O
LO CU
5-1 O
5-1
CU
CMC
PH PH dJ
-ct
<t-
116
LW
QJ
4J
aJ rt
4J
QJ
4J
pil
C
O
H
4-)
rt
S-l
S-i
4J
r-t
-H
4-)
i1
H
PH
O
H
cr 4 J
CO cd
S-l
PH \
S-l 4 J
ffi i1
H
O
W
,Q
(-1
PH
CM
a i1
S-i <J3
0)
<t o
LO
4-1
4-1
O
w:
c
o
c
H
rt
a
O
u
o
en
T3
r-H
QJ
H
-d
<u
S-l
P-i
PH
a
H
<3
S-l
T3
H
O
<]
4-1
PM
PM
cfl
4-1
bO
(73
MH
O
S-l
QJ
o o
V V
o
V
LO
LO
O
^>
O
o o
V V
o>
l^
CO CO i^
cr.
en en en en
o L O CO r< t en en CM
r-^.
en
CM CM
Td
CM
^ D o>
CM CM
CM CO S t v O
CM CM CM CM
CM v O LO rCM CM CM CM
LO
O
co
v> LO
O
o
O
LO LO LO LO
LO
o o o o
3
o
ffi
PH
CO
o o
V
en
c^
CM s t
r- 0 0
c^
CO
^D
v>
r- r-
t-~. l^
CO
CO
LO
c^
CD
o>
o>
I1 en I1
I1 ii CM
o I1 en S t
I1 CM CM en
r-
CO CO CO
CO CO
co co
o
r- o
LO o
LO
CM LO r-
LO o
CM LO
LO
o
o
LO o
LO O
CM LO r~. O
r-H
i(
r-H
i1
CM
CM
r-H
C ^.
I1
aa
CM
CM
i1
i1
CM
PH PH
vO
nd
cu
LO v>
o
4-1
en
CM en r- s t
CM CM CM CM
LO
CTN
a -uO
ttf
LOO)
SH O
SH
QJ
CMC
PH PH !=)
o
r^-- o
SH
rt
<u
Da
O
P-i
^D
o o
en en
LO
S-l
u
o <u
PH
LO LO LO LO
PH
> W
o 3a
a
3
LO LO
ii
nJ T 3
4-1 CD
O 4-)
O
> H
W
Tj
v> ^ D
O
O
MH
i1 r-H en
LO LO s t
en
LO
i1
O
(73
r~.
<t
CM o>
LO LO LO
4J
*>C
<u
<u
H
4-1 <U
O
aj H
<U H
Pfi3
4J
C
QJ
en
PH
rd
H
I1 CO CM
LO s t LO
en
o CM S-l
o
v> LO
o O
PH
>- o 4rtJ
ITTd
^D
en
O
0)
a
<u
H
4J
bO
CMS
T3
H
O
QJ
mo
4-1
1
^ a
o
fr
o> iI
LO ^ D
PH
<:
P-i
CD
S-i
~-"-^
ITPM
o CM
4-)
H
S-l
rt
PH
co
ti-,
en
LO
St
LO
St
VO
en
LO
St
I1
117
Tables 31 and 32 show the P90,- yields, the major cation impurity
(CaO, Fe 0 , Al 0 , and MgO) concentrations in product phosphoric acid
containing 54 percent total P?0_ resulting from the third stage of the
stagewise dissociation of unreacted monocalcium phosphate from the
second stage using methanol and acetone respectively.
The filtration
along with the dissociation reaction time for each experiment. The
unreacted monocalcium phosphate P?0
118
CU CU
4-14-1
-dn
rH
O
O
5-1
P^
<;
p|
5-1 PM -rH
4-1
4-1
cr" nJ ctj
I-I
O 'rH CO 5-1 CU
4-1 S-l
rH PM
4-1
5-1 rI
X ! CU
O 4-1 4-1
rH CU Oj
nJ
u g x!
O
Xi X!
Pu 4-1
to T H
O
X!
Pu cu
4-1
S-l CtJ
O X!
M-i p u
W
nJ nJ 4-i o
PL,
W
O
x!
pu
M-I
S-l
4-1
iI
LOO
O l M
Csg
g
T) (0
n 13
nJ 3
'H
CU
^ W)
13
ctj
i - i 4-i
CU CO
H
>-< a
H
^
O
ON
O 00 CO
ii o ii
CO
00
Oi
o o o o
o o o o
m m m
o o o
m
o
o\ <j- m
o o o
m
o
m
o
m
o
o o
V V
o
V
o
V
o
V
rO
CNj
iI
M-I
T)
a a
T) CJ rti
a s-i s-i
O "rH CU P
H x : M-I o
M-I . H
- H 4-1
V V
o
V
4-1
CU 3
O 13
S-l O
v> co oo a>
co <i- co co
n o> vo <t
co co co <l-
o o o o
o o o o
C7> iI
CTI ii
a> o r- co
<t vo m m
o
o
o m
i n r-
o
o
CNJ
CM
o m
m r-
o o o r-i
ii
'H
Pu
4-1
p:
CU CU
O
3
CtJ S-l
4-1 CU
CNJ O
CNJ 0 0
a> a>
m in m
o o o
o o
o
^O
V V V
CNJ
o o o I-I
i n i 3 co Pu
o
cNS-i
P-i Pu
H
4-1
en
T-I
m m m v>
o o o
o
M PM
rH 4-i oo a
>u
O CU
" H 4-1
4-1
ctj
a
pi!
o
P-i nJ co
S-l 6
rO
VD oo ON m
p o p :
H 13
H
13
O
<-i <
CU
PL,
4-1
MH Cfl 4J
4-1 H
CtJ
O
il
CNJ
PU
cu s-i nJ
4-14-1
a
nj
CU S-l
>
4J
m
O
CU iI iI
CNloO O H
S-l
CU
Pu
nJ
o o
S-i P g O
4-) o
m
f l - H CJ
CJ U - C B
ctj
oo aj
o 3 cu
pi -w
H cu
s-i s-i
^o w
x
:
3
a o 4-1
4J -rH H
H
Q
nJ
II
rH U
S-i
3 13
Pu H
4-1
Pu
>i
5-i
S-i
S-I
3
CU
PU W
a)
a
Pu
CU
S-l
5-1
3
C U
i-l
O
cn
rH M_|
4-1 O P-i
N fi
4-) o
6 o <r
<; m
CD
nJ ctj 5-i
s-i a nj
PM
II II CNJ
Pu
-rH
O
P
O
\o i n co vo
aj
13
-rH
S-i
O
iI
H a i d
4-1
i-l
rH
CNJ
4-1 iI
iI iI CNJ
h J f t
nJ p-i B
P4
O
P: 3 <w
O
c^ r^-
r-l
rH X I
cu o PM
t r ! -rH
p:
H
W
CU S-l
Ctf-rl
m o m
CNJ m r-
a> F U ps
P=S
4-1 CtJ
P
4J
CU O
>
^
r-l
O M-I
CO O
13
CU
4-1
O
CtJ
(U
S-i
M-I U
O P
3
W
13
p
3
O
P-;
O
Pu
Pu
O
CJ g
<l-
v-l
m
S-i O
CU
CNJ
Pu Pu
CtJ
13
CU
4-1
O Pu
CtJ O
incu g
S-l O
S-l
CU
CNP
Pu Pu
p
<l-
<l-
<l-
o
o
I-I
119
<u <u
4J
*d
4J
Pi
o
cd cd 4-1
H
O
0)
C
o
<:
4J
pi
O
4=1 4=i
4J
^ cr cd
4J
5-1 i1
O -H CO
H Pu ^^
<U
CU 4J
O cd
< 4=i
H
5-1
S-i PH
4J
S-i
4J
Cd <+-( EC H
a,
TO
5-1
Pn
o
a,
TO H 4=i
o
a,
jr;
i1 TO
H 4=1
Pn H J
x)
cd H
&
en
iro
O Cl N60
E
5-i
I1
cd
P-i
P=!
C p
>-.
4J
5-1
<4-(
H
5-i
H
O
4J i1
cd cd
o
o
Pi
5-J
4J
i1
*d
a.
X)
cu
C X)
cd 3
5-i
CM
CJ>
<+-(
cd
5-i
4J
4J
LT>
TO
cd
0)
5-i
H
>-t
<U
TO
& H
TO
ii
& O
<U H
r.
60 4J
X ) cd cd
P4
4J
O
oCM o5-1
P...
o
H
cd
cu
4J
cd
P=!
5-i
I-l
I1
4J Cd
4J
<4-(
<u CO
LP
CM
PM
CU
> *d
CU i1 Pi
60 O
cd
cd CO
U
U-J CO 4J
O
C
*d CU
qj
O
H
4J
Pi u u O
O H cu cd
H 4=i <4-( a;
4J H <4-( 5-i
H
cd
H
g Q M
5-J
cd
>
5-1 4J
<4-( cd
4J
4J
cu o
> H
ii
O "+-(
CO O
u-i
O
TO
'd
Pi
m
o
o
co
r^. vO CN r^.
CM CM co CM
CN O
i-H ii
co CO CO co
o o o
m
o
o
V
m vo vO
o O o
o
V
o o
c^ (^ 00
co CN CM CM
< !
m m vO
o o o o
o o o o
V V
vO
o
< !
o o
ocd
o
< !
st
O o
CN CN CM CN
O
o o
1
m
o
CN vO CO m
CN CM CM CM
ro
|
43
cd
H
TO
53 5-i
e p!O
3
H ffl
m
o
o
1
o
1
m m
o o
o o
O
PH
CO CO
o
CN CN CN
c^ C^ CO c^
m vO vO
< !
I1 i1
il
i1
il
m O LT)
CN LO r^.
o
o
r-.
o
o
o o o
ii
CD
Il
m
o m o
CN m r^. o
o o o Il
00
I1
o
m
o o
CN
4J
cd
cu
5-i
00
pi
I1
P3 PH
CJ>
C
*T3
CN i1 vO r^vO vo m m
'd
cu
PI
.
< !
m
o CN
P-i
PH
P..I
CN
i1
Il
CM
vO
o
o
5-i
Pi H
CU
CU
4J
O PH
cd O
o mcu
u
u
cu ocMqi
PM
P-i
ii
II
Il
Pi
5^
cu
4J
CM co C^ vO
CM CM CM CM
CM
00 00
co CM co
3
o
i n uo
o
o
CN
4J
*>
0) QJ
60 O
cd 5-i
CJ
H
4J
Pi
4J
O H
P-i
3 4J cu
i r r d CO PM
PM
m
o
o
ii co CM
CO CO CO
'd
<;
cu
CO
t-i
4J
S &
o cd 3 3
CJ H 5-i 4J
cd
o O O 5-i
o o
TO a; a;
>-. TO X. a,
4J H H
e
H Q
0)
^^ 4J
5-J
M P4
a; 5-i cd
'd
O
Pi H a;
CU 4J *d
I1
5-i
PH
vD
PM
C O Pi
a; 3 H
o T3 Pi
o
3 o
4J
o
o
< !
S-i
iI
TO
O i1
S-i <C
CU
fr^ ;
C CJ>
o
CO
o CN
co
a. H
O
o
e <:
m CUCN
cd
a,
cu
5-i
4J
i
PI
PI 0)
3 T3
a)
5-i
PH
CU o Pu
4J 4=i
iI
co co
P-i
4J
5-1
O 4=i
00
o CN
<U cd
P-I
O N
CO
<
4J
4J
cd
cu
5-1
ZD
r^.
II
< !
< !
< !
120
P 0
APPENDIX C
EXPERIMENTAL FILTRATE P 0 YIELDS, IMPURITY REJECTIONS AND FILTRATION
RATES FOR DISSOCIATION OF MONOCALCIUM PHOSPHATE PREPARED FROM VARIOUS
GRADE OF PHOSPHATIC MATERIALS IN METHANOL AND ACETONE
The experimental procedures outlined in Chapter II were used to
investigate the dissociation of crude monocalcium phosphate, prepared
from various grades of phosphatic materials, in the presence of methanol
and acetone after different reaction time periods.
Solvent/monocalcium
to filter the slurry sample until the top portion of the cake appeared
dry and after analyzing the resulting filtrate for P 0,., the filtration
rate in units of pounds of filtrate P90,- per hour per square foot of
filtration area was then calculated.
122
m
5-1
O
M-l Td
d
o
r-i
ti
CO
4J
ti
r-i
ti
o3
si
rH
rH
4-1
5-1
d
rH
m
ex
d) 03 CO cu
5-1
+J x : o
oj a, x : d)
P i CO a.
&
o
a x: m r-l
O CM o
o
rH
ti
5-1 - r H
4J
O
i1 i1
r-l
pM
T3)
03
O
O
d
a03 og
03
d)
T3)
03
5-1
M
puri
Cont
x:
4J
d)
T3)
^
4J
5-1
03 C_>
S-l
4J
M-l
03
03
T3>
r-l
d)
d)
O
r-i
4_)
c_>
>N
M
H
5-1
dP*
CU
rH
cvtd
PH - H
M-l
O
d
O
H
4->
oj
rH
5-i
o3
>
m
m
cu
.o
o3
O
S-l
d
o
I N
r-l
>X) 0 0
r-l r-l
CNJ 0 0
d> I N
o o o
o o o o
t1
o o
o o
o o
o o
r-l
r-l
r-l
o o o
r-l
IN
en < t
o r - l r1
o o o o
r-l
o
o
00
<t
<r
m <r ON
m <r <r
o o o
4J
ti
0)
O
5-i
CU
PH
m
CNJ
cu
PM
V>
0 0 I N CNJ ON
00 r - l
o O O r-l
o o o o
en en en CNJ
O O
o o
o
o
r-l
ON
o
03
c_>
4J
T3)
TH
C3N I N
00
VO
r-l
<r m m vo
o o o o
<d
ti
ON
d)
O
5-1
CU
PH
i n
ON
r-l r-l
<J" | N
O
r-l
rN
O
IN
00
r1
V>
ON
r1
r-l
r-l
en
ON
00 r - l
00 r - l
<r
ON
0 0
ON
r1 r - l
0 0 ON
CNJ
m
o m o
CNJ
m r- o
O m
m
CNJ
O
O
CNJ
o o
r1
o o
o o
cNi en en
CU
o CNJ I N I N
<r <r <r <r
o o o o
v>
O
as CO m
o o o
en en en en
CNI
en m
ON
IN
r-l
I N 00 00 00
CNJ CNJ CNJ CNJ
en
ON
ON
CO
en
ON ON
00
CNJ CNJ CNJ CNJ
a\
so
a
e
o
CO
T3
d
3
o
PH
o3
S-l
4J
r-l
rH
.
d) M-l
^~s
J5
<J H
T3> > N
N_^
d
r^
03 CU
TH
5-1
ti TH
O d) O
4J
H
O
,G
4J a)
a
CO 4-1
O CU o3 co
si
d) CU
PH
Pi
5-1
d
o
o
<J
CO
S-l
PC
r-l
m rN
m o
m r- o
O
r-l
m o m O
m rN o
CNJ
Pi
M-l
c_> d
g o
H
cu 4-1
T3>
"
<L)
3
oo3 TB
H O
ex
LTVH
rrj
H
4J
>- o
5-1
en
r-l
4J
O
CM d
PH H
d
o
mpH
a>
4J
i1
>
CO I N
O
o <r
IN
M-l
13
0)
o
d
rH
> CU
B oo3
0
5-1
O
T3) M-l
d)
S-l CO
- H 03 d)
5-1
-u
03 d) 3
- H 5-1 4-1
O
o3
O
S-i
CO
d) d)
co M
- H cu
d)
Q
4-1
PM
JH
T3)
rH
CM
CN
r-l
PH
T3)
d
d cu o3 o
4J
O
r-\
d)
O 4J
S-l O
d)
3
P-l T3
rH
d
ti
d <j
03
ON CN] en
O
CNJ CNJ CN]
ON
T3>
CD
r-l
4J
03
4J rH
O
O
03 PH
H
i r I d ) CJ
S-l
O
a) M-i
o
PH
O PH
T3)
PI
3
O
d) PH
4J
ti
>
r-l
>-" g
iti
P
ti
r-l - H
03
o u
5-1
d)
PH
ti
T3)
1
ti
mp
0)
4J PH
O CJ
03
g
d)
S-i
>
o a,
u- 1
o J
PH
r~-
ON
r-l
CNJ
CN)
r1
CO
CN]
r-l
v>
v>
v>
v>
O
O
O
O
< !
46
B
3
ent S
4J
o3
bO
T H
P*,T4
4J 03
IN
VO
Acetone
<t
m
bO
C_>
P 4J 0
03 O
d) J2
en
IN
vO I N
en 0 0 m <r
en en en en
46
4J
rH
03
Florida
Methanol
Concentrate (II)
(34.2)
si w
B ti
o
rH
ON en
CO 0 0 ON
47
^ rHa
O
SH
PH
Acetone
bfl
ON
fc
47
o CNJ
^ <JCNJ
CNl
5-1 r - l
t t i rH
- N
m
m
d)
4J
03 T)
CO
r-l
<I
Florida
Methanol
Concentrate (I)
(34.3)
03
a)
o3
cu
S-i
Solvent
o3 c_>
ti
o
To
??0
4-> CU
M-i
CNJO
PH
4-1
CU h rH
4J
4J
03 CT 03
SH CO 5-1
4J
- N
4J
Raw
Materials
r-l
CO
4-1 X>
03 r-l
5-1
4J
d)
r-l
4-1 r - l
rH
03 r4
pM P i P M
cu o3
B
r-i
M-l
O
r1
123
IT)
o *u
<4-\
CNO
PL,
G
o
O
4-J H
H
CO CU P H 4-J CtJ
4-J JD 4-1
ClJ I - J
CtJ C T CtJ cu
^4
SM
J-i c o
SM
4-J
CD 4-J
4J
<
iI 4-1 iI
^4
H
CtJ - H |X| - H
h
Pi
h \
PM
I
O <t"
^4 LO
PM
OC
60
a a
H
>^ a
O
^
4-)
CO
S-J
PM
PM
H3)
o
u
cu
cu
o
cu
4-1
O
tt
4-)
i-l
O
CU Pi
H t t
>H
O H3)
^4 - H
g
H
4-1
LOPM
O
O
<
CMC
PL) H
CO
CO
4-J
a
cu
H3)
iC/J
-l
P^4
M
CN v D CO
CN CN CN
LO
CN
vO
O
CO
O
o o o
ON LO
00
o o o o
o o o o
co ii o r^-
00
O
o o o
vO
O
n <t H <t
o o o o
CN CN CN CN
a>
O
o o o
o o o o
o o o o
r-*
<f
CO
LO LO ON VO
i-l i-l O
O
o o o o
o o o o
o o o o
LO O
ON iI
<f LO <t- LO
<f
VD LO
o o o o
v O v O iI CO
O
O
i-l i-l
^ I O H
o
co r-* VD co
ii
iI iI
LO
r ii
iI iI
o o
r^~O
LO
00
ON
vO
iI
ii
vO
00
LO
r-*
O
ON
O
il il
o o ii c>
ON o <t- ON
CO <t" <t" <t"
VD
o o o
o o o o
o o o o
o o o
o o o o
vo CTI oo I s -
1^
ii CN
ON
iI
ON
r-*
r-*
00
CO
CM
si"
!-* VO ON <f
ON CO <t" O
00
CN
ON ON
CN CN
ON
CN
1^ 00 00 00
CN CN CN CN
LO
00
LO
ON CN CO
G \ vO
<}- c o
00
r-
CN CN CN CN
0 0 CTi 0 > ON
CN CN CN CM
ON
VO
ON
CO
iI
CM
r^ oo oo oo
CN
CN CN
LO O
LO
LO O
LO
LO
CN LO
r-*
CN LO
r^
m N
i-l
rH
+j
O
CtJ
PM
00
cu
II
LO
PM
C >
P3M
vO
CN O iI ON
CN CN CN iI
CN
vD
CT\
r^
LO
i-l
LO
CN LO
r-*
i-l
LO O
LO
CN LO
r-* o
>
i-l
CU
a o
CU
0 0 iI CO CN
CN CO CO CO
LO
tt
r-* VD
CU
PM
tt
CO
CO
LO LO
r-* r-* oo oo
O
S-J
O
" CO
H
CU }-i
M
g
3
O -H
O
ctJ H
pel
CU
p<-
ctJ
H
ON vO
CO O
tt
cu
T-I
CN
CU
CN O
<t"
CN CN CN
o o o o
4-)
CN
H H
M
S-J CtJ P4-J
04
r-* oo LO CM
LO LO r-* LO
LO
ON CN iI
O
CN CO CO CO
n g
CNJH
P M pD
CO
CN
ON
CN
vO
II
CN
vO
vD
o o cu
4-1
tt
CU
4-J
O
CtJ
CU
U
c
cu crj
LOC
^4
O O P
O
4-1
CU H
CN
PM
PM
PM
U
g
o
CO
CO
vO
vO
LO
LO
o
0
cu
LO
4-1
a
CU
>
4-1
0
o
CU
4-J
CtJ
rC
iI
O
C/J
cu
o
M
M
M
CtJ
cd H
p<-
J-i
LO
O
CN
CU P M
4-> &-S
CtJ
H3)
H
U
O
ii
PM
I
a
CU
O
C
O
O
o
ti
CU
J3
4-)
4-1
CU
O
C
o
eti
cu
g
<
CU
4-1
CtJ
J-i
4-1
^
LO
.
CO
CO
w
CtJ
rC
4-1
cu
>
<
w
CtJ 1 vM
/s
H3)
H CU cu o
.
5-J o 4-J
O C CtJ CO
i1
PM
o
o
'
U
4-)
CO
'
CtJ
*U 0
H CU
J-i O
o
fn
JH
O
o
CU CO
4-J
CtJ CN
JM CO
4-J ^ - ^
ion
124
M-)
O
Cfi
4-1 X I
ci3
KJ
CU
d
O
-H
4-1 Cl3
4-1
CU Pn
4-1
Oj cr
5-1 CO
4-1 ^
5-i
Fil
Rat
Fil
5-1
4-1
M-)
CNO
P-I
Is-
nj cu
5-1 5-1
4-1 <
.-I
5-i
P-i
bO
bO
0 d
H
!-)
LT)
d oCM
uri
4-1
CT3
P-I
4-1
d
4-1
ent
5-i
CU
P-i
T3
CU
3
0
H
4-1
O
U
v
w
co
H
O
co
O
CM
.-H
<
o d
cu o cu
o
Me T 3
5-i
CO
CU
P-i
CM
CU
<
p4
4-1
O
ci3
T3
4-1
- d
CU
O
5-1
CU
P-I
ina<
o
(U
r-l
^D
Oj
4-1
Oj
CU
<t
I1 .i
.1 .i
o
CO
>-l 0 0 IT"!
CO CN CO
vO
CM
CT> < t i - O
r-l I - I
t-\
m m
o o
o o o o
CM vO r - l
m CO < t
0 0 C3N
CO CO
CT>
CO
o o
o
Is-
<t <t
o o o
<T\
vO
00
.i
.i
.i
O
IT)
CM
o>
5-1
tn
<t <t
V
IT)
.i
V v
VO
oo oo vO
o o o
vO
Is-
O
vO
IT)
IT)
IsIT)
<t
r-l IsCM .i
CN
.1
r-l
T-\
<t CO
m
vO
CO
CM
< t <t
00
ON
00
Is--
CM m
r - l ii
v>
o
o
<1- < t
<j-
CO
vO
T~\
0 0 vO vO
.1 CM T~\
00
CM
v)
CO
CM
CO
00
CM
O O
o>
m
CM
v>
CO
IT)
<t
m
vO
O
vO
r- o>
O
o
vO
0 ! r-l
T~\
o o o o
v> CN 0 0
0 0 T~\ CN
r-l
CO
VO r - l CNJ
0 0 CM CNJ
vO
00
<T\
^-1
co
<t
r-l
r-l
r-l
<T\
00
Is-
co
CM
r-l
CN
CM
CO
vO r - l
CM < t
o>
0s.
CM
o>
vO
CM
vO
CM
vO
CM
r-
CM
CM
O
O
CM
<t
<T\
O
CN CO CO CO
r-
r- oo a)
CN CM CM CNJ
IT)
CN IT)
CNJ i n
o Im
o
s
- o
r
o o -l
m o
o
m o
o
Is-
I1
00
CNJ CN
CN
m o LO
o
m I -- o
o o o
CM
T\
o>
m o IT)
m r-
o o O
CM
r-l
o> CM
o> CM
o>
rt w
Florida
Pebble
(28.9)
CO
I " 1 ,N
Oj
IT)
r-)
O
5-1
CM
CU P-i
4-1 5-S
6.18
6.14
42.10
Acetone
O
CO
42.10
>
r-l
Florida
Matrix I
(20.2)
CU
6.21
Acetone
Total
Methanol
44.80
CM
P-<
Acetone
C
4.
md c
O D c
44.80
T
1
Methanol
d
H
<T\
CM
T\
CNf
P-i H
45.40
<4-(
O
me
*
6.23
6.19
C
C
MCP
T-t
MCP
4-1
O
m IT)
o m o
r- o
o o o
T
C
i1
vO
vO
vO
- w
CU
T-\
vO
O
4-1
Raw
vO
Pounds of
Percent Solvent
Per Pound R
<T\
m <t m
0 0 0 0 o>
o o o o
I -
O
H
CO
iri
t-\
TJ 4-1
r-l
CU 3
H TJ
O T3
5-i H
O
<
CN(d
P-I H
CO
<t <t
IT)
vO
W -H
IT) LO I s - 0 s .
i1 I - I >-i i1
125
O 4^
H-J CNJO
d o PL,
O
4J
r l 01 0 h
TI
-P ,T) -P
-P Hi
rt ( J nl 0 * ni 0)
5-t en s-i s-4
p a) -P
P < :
TI
4 - J 1I
d
i-i
CO vO ON CO
< t co co co
O M 3 0 CO C^
o < t m 00
C O CNJ CNJ CNJ
N N N
vD <|- r-l
m m vo
T-I
vO VD v o VD
O O O O
i1 i1 I N
vO fN v o
I N VD h - 00
O O O O
O CNJ ON CO
vo m m
m
CNJ
00
!-)
P-i
st
toO
bO
d
CNJ
nd
o T-I co
co co co
0
3 o c
a. 0
vo
IN
fN
0
-H
d
O
>,-H
CNJ
i ) Hi CM
i-l -P
J-I a
-p
ON
ON
S-l 1I
O
J-I
cu
ON
ON
vo
t-i
0
i1 f N CNJ CNJ
< t < t m co
o> ON I N r o
r-N
m vo m
IN
CNJ f N CNJ UO
c o c o < t CNJ
O
a;
J-I
P O PL,
d <H
cu
o -P
n
o
cu d
PL, Td
P-i
CJ
I N vo 00 co
CNJ CNJ CNJ CNJ
co co c o
m < t CNJ
O i ^O (T> O
m m vo vo
00 o
O
T-I
vo
m
ON
ON
CNJ
ON ON
O
O
O
CO I N I N CM
CNJ CNJ CNJ < J -
f N ,1 VO < t
co < t m co
VO CO CNJ TI
CO CNJ CO < t
vO O CO i-l
< t < t vo i n
00 ON ON o
O O O <-!
vo vo vo
fN
T-I
< ( TI
nd
T3
T-I
-P
o
CU d
ri-d
>-) O nd
J-I T-I
LnpM o
<U
CNJd
PL, T-)
-P
d
cu
CJ
J-I
CU
PL,
O
H
" W
CU J-i
O -H
Hi H
CU
pi
O
ffi
co
00 00
ON CO < t 00
<J- <JT-I
CNJ
CNJ <j-
tI vO vO f N
00
vo vo vo vo
CNJ CNJ CNJ CNJ
f N CO 00 00
CNJ CNJ CNJ CNJ
fN
fN
fN
f N f N f N 00
CNJ CNJ CNJ CNJ
vD \ D vO vO
CNJ CNJ CNJ CNJ
m o
cNj m
m
r^-
o
m
CNJ
IN
CNj r^00 r 00
o
o
t-i
nd
cu
03 C -P
-P !-) O PL
Hi CJ
CM
o
H
mcu
g
>
T-I J-I
O
J-I
o cu m
CNC
w
ft
o p-i t b
0
o
T-I
fN
CNJ
o
m
IN
o
o
T-I
< < C O T - I
CNJ
o
m
IN
o
o
f-H
co < t
CNJ
o
m
IN
nd
w
nd
CJ
JD
o
PM
P
C
cu
2
O
P
d
nd
d
-H
cu
cu r-i
1 - P p.,
o n> m d
o cj
J-I 4J o
!z> ni
g
3) O
M
CU
PL, H
ft
J-I
t-i
Hi
-H
CNJ
vo
<*
Hi J-I
ftf CU
P &*5
Hi
^
cd
d
i-(
-i-i
00
J-I
J-I
o -P m
il
to
<*
M
M
M
M
W
m
O
CNJ
PL,
<*
03 il
g
w
ttf
13
X ^
H T H 00
J-I J-I
O -P T-i
r-l Hi T-I
to
^
>
1-1
Hi
nd
-r-l
^"N
J-I J-i m
o -P
T-I Hi f N
to g
w
00
CNJ
o
o
T-I
126
o
M-l
M-I
(NO
O PM
O
H
CO CU
4-1 JD 4-1
cd
H-J
C
4-1
O
-H
4-1
PM
Cd
cd c r cd cu
4-1
5-1 C O
CU 4-1
H
PM
ctf - H jri
P4 PM
M
4-1
5-J
<
m ^o t^
<i o o
ti
o
O
V O N
<(- co oo m
m m m m
o o o o
Os
CM CO
o o CM o o CM
vO O
O
00
O0 O0 CO CM
r^O
T-I
o o o
O O O
<) m m rN.
<h m en I N
CO CTi <t"
CO CM CO
00
<t
r^-
Ti
CM CM CM CM
T-I
i n m i n <vD
T-I
PM
o <t5-1
bO
PM
bO
s c
iH
m
o
o
-r-l
>-> -^
H
4-1 pL,
4-1
a o d
6
cu
M
x)
J-J
CM
3
-d
4-1
>- o ' d
5-J - H
(U
LOPH
<U
5-1
CU
PL,
CNJPJ
PM
r-l
CU
4-i
Pi
d
O
nj d
4-1 -rH
Ti cu PM o
Pi >
O
PM
PM
vo m oo oo
<t- <t- m >*
co as as c^
o o o o
m r~- as oo
C ^ C ^ CM CM
oo CM as
CO CM CM CO
co co m >ct-
CM
CM C M
o o o
o o o o
TI
t r r^- r~~
o o o
o
o o o
o
v D v O CM CM
T-I
00 00 00 00
CM CM CM CM
v o r^- r- r-
m o m
CM i n r-
CM
Ti
<f
o o o o
in
1^ N CO
o o o
OS CM CM
T-I
<f m m
o o o o
CU M-l
T-I
pi
CM
r- oo oo
Ch H
h-
oo Ti m
CO
0 0 0 0 0 0 CO
CM CM CM CM
CM CM CM CM
CM
00
vO N
N
CO
CM CM CM CM
o in
m r-.
o
o
o
T-I
o
o
m o m
CM m ho o o
T-I
o
o
T-I
in o m
m r-
CM
CU CO
co
o
cti
CU
CM
PM
5-1
CU
O
<
CU
4-J pL,
cd
cd - H
CM
mcu
Clj
T-I aD
C ^ CM CM
oCMpi
H S
o 4-> i n p i
5-1 o o PD
CU
cTi
4-i
O
Cti P M
co PM o CM
<U
Ti
<}<} m
O
CM T - I
T-I
<f
cn O < r
H
m vo vo vo
O O O O
m vo vo r-
o o o o
o
vD
sf
Q>
oo CM
T-I
o^ o
CM CO CO CO
5-1
4-> e 3
O -H O
cd H pd
CD
P4
CO
in
O
4-J
O
cu
rl
on oo vd- on
o
O 4->
5-1
O
CU
3
PM X )
T-I
t-i
tI
PM
M O D
d <J PM
cu
X)
<|- o ^ o
TI O
T-I
m
o
CM
PM
o
s
00
CO
<t-
to o
o o
si &
i
T-H
PM
CJ
CD
4-1 4-1
MM Cd
O Si
CO &
S
Ti
4-J T - I
-H
O
|5 T - I
cd
P-,
Cd
^ e
T-I
-H
<f
TI
PM
r - l
TI
CO "'
o
o
m o m o
T-I
N m N o
o o o T-I
tion
127
MH
o
CO
CNO
PM
u
o
0) P H - H
T5
4-1
D
4-)
CO cr co J-I
U co
J-I <c
Filt
Rate
Filt
/Hr/
Filt
XI
CO l-J
J-I
m
o MH
o
J-I
<tin
O
bO
PH
bO
0 d
m o
4J
o -u
U 0
'Td
cen
4-)
cu
PH
<
JH
o CN
cu
CU
PM
PH
4-1
O
CO
'Td
<^"S
00
C^
r- eg
00
o r-
co
O
00
i-H
eg
co <t-
00
00
00
r-
00
,i e g ii
,1 ,1 ,1 r-H
vD
O
vD
VD
vD
O
o o o
m
o
o
vD
O
VD
r-
O
m <t- <t"
co co CN
,1
CO
vD
r-
00
O
i1
.-H
vD
eg
r-
O
CO
C^
eg
o o o
o o
<f
i-H 0 0
1-1 < f
vD vD
r- r-
C^
CT
o o o o
<y\
CN
IT) e g
co co
o o o o
i-H
vD
o tf
VD
I - l co
vO vD
o o o
<f
O
VD vO
O
O
00
VD CO
C^ i - l
c^
O
O
i-H
CO CO CO
m
eg
o o
vD
00
vD
eg VD
o o
vD
vD
o o
m <f
o o
co
00
o J-I
<C cu
i-H i-H CN e g
CO CO co co
00
CN
eg
m
eg
m o m o
eg m
r- o
o o O .-H
r^
o o
O
eg
o o o o
,1 VD
CN r-
C^
eg
m
oo
CTi
O
CN CO
co
r-
i-H i-H ,i
CO CO co
PM
J-i
6 3
O
CO
cu H
p<
.-H
<
CO d
4
U H C
O
H
c
mc
J
CNf
d
CU
>
i-H
O
CO
JH
^s
m
O
CN
CU P M
4-) B-S
45.67
4-1
Acetone
C
J
45.67
CM
PM
O
m o
m r- o
o o o ^H
m
CN
Methanol
^
C
1 +
md c
o -p c
North
Carolina
Concentrate II
(30.6)
cu
m o
m r> o
O
o ,1
O
PM
CO
i-H
46.20
MH
O
m o
m r- o
o o O i-H
6.23
CO
6.26
~
CU
6.20
0
O
H
4-)
O
Acetone
i-H
rO
d!
H
,1 <t" CO
CO co eg
6.28
cu
00
eg
o o
e g i-H r1
,i i-H l - l ,1
46.20
co
co
cNd
PH
rin
c^ 0 0 C^
,1 ,i ti
Methanol
"^
o
VD
North
Carolina
Concentrate I
(32.9)
o
o
CU
O
MCP
TJ
H
MCP
H
4-1
o
3
CU
H T3
&H O
J-i
mpH
Total
g
0
Raw
cu
x)
i-H
eg
vD
co
4-1
Pounds of
Percent Solvent
Per Pound
X)
m
vD
00
00
co
cu
o
H
<
,i r ^ %
eg eg eg
co
O
eg
CM
PL,
,1
mpur
H
>. dCtJ
4-)
,i
eg
128
P 0
ratios are shown along with the dissociation reaction time for each
experiment.
In order to facilitate comparison of the data, the filtrate P 0
yields, the product acid impurity concentrations and filtration rates
after one hour of dissociation reaction time period are presented in
Table 10.
129
APPENDIX D
EXPERIMENTAL FILTRATE P ^
funnel.
been in contact with the acidulate, was analyzed and percent P~0
recovery
The
total P90q; yield in the product acid resulting from the stagewise
extraction of dried acidulate containing 19 percent P^O- increased rapidly
with increasing overall contact time up to 36 minutes. As the overall
130
Stages
Contact Time,
Percent Overall
Mins.
Recovery of P^O
per Stage Total
in Filtrate
Acetone
63.78
Methanol
59.72
Acetone
14
74.51
Methanol
14
69.87
Acetone
18
80.53
Methanol
18
84.74
Acetone
20
88.37
Methanol
20
87.76
Acetone
25
94.59
Methanol
25
94.08
Acetone
10
40
98.18
Methanol
10
40
96.91
Acetone
15
60
96.26
Methanol
15
60
97.22
Acetone
20
80
96.53
Methanol
20
80
98.04
Acetone
25
100
95.79
Methanol
25
100
96.94
Acetone
30
120
98.42
Methanol
30
120
98.33
131
100 i
40
80
Figure 6.
132
contact time was increased above 36 minutes the product phosphoric acid
yield became relatively constant at approximately 97 percent.
From Fig.
As the overall
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
with either methanol or acetone, an optimum yield of approximately 97
percent P^O^ in product phosphoric acid resulted when the overall contact
time was 36 minutes.
The dried
Type of
Solvent
Number of
Stages
Contact time ,
per S tage
Mins
Total
Percent Over<
Recovery of P
2-5
Acetone
27
96.43
Methanol
27
96.21
Acetone
36
97.01
Methanol
36
97.57
133
APPENDIX E
SAMPLE CALCULATION
The sample calculations listed below are the same as those given
by Drees (11):
1. Digestion of ground phosphate rock or dissociation filter
cake residue with sulfuric acid,
2. Preparation of monocalcium phosphate from phosphate rock and
phosphoric acid,
3. Dissociation filtrate P90
It was also
It
was also assumed that all the calcium oxide in the ground phosphate rock
would be converted to calcium sulfate anhydrite.
A basis of 100.00 grams of ground phosphate rock reactant is used
in the following calculation:
(100.00 gm rock) (0.3428
&
gm P 0,
gm P?0 digested
fL2
D
-T") (0.965
.
r-)
p n
x
gm rock
gm Po0r in rock
= 33.08 gm P 0
digested.
33.08 gm P 0 digested
r-,
7T7;7
r
r :
rr = 49.37 gm phosphoric acid.
r
r
0.67 gm P0,-/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.
n
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
phosphoric acid = 84.54 gm. total HS0
required.
84.54 gm H 2 S0 4
0.98 gm H7S0^
gm sulfuric acid
135
136
BIBLIOGRAPHY
1. Achorn, F.P., "Status of Fluid Fertilizers - 1970," Solutions 3,
26-31 (1970).
2.
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).
6.
7.
8.
9.
10.
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).
13.
14.
15.
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).
17.
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.
20.
21.
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).
25.
26.
27.
28.
29.
30.
138
31.
32.
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.
36.
37.
38.
39.
40.
41.
42.
Winand, L. and Martin, M., French Patent 1,435,877, April 22, (1966).
139
VITA.
Amitava Roy was born on June 12, 1948, in Calcutta, India. He
attended public schools in Calcutta and Bombay, and graduated from Bharda
New High School in Bombay in June 1964. He attended the Loyola College
in Madras and received Pre-University degree.