US007 172742B2

(12) United States Patent (10) Patent No.: US 7,172,742 B2

Feng et al. (45) Date of Patent: Feb. 6, 2007
(54) METHOD OF PREPARING WET PROCESS (58) Field of Classification Search ............. 423/1574,
PHOSPHORIC ACID 423/32O
See application file for complete search history.
(75) Inventors: Yisheng Feng, Shandong (CN); Jiutian (56) References Cited
Feng, Shandong (CN): Xigang Liu,
Shandong (CN); Yurui Wang, U.S. PATENT DOCUMENTS
Shandong (CN); Tianbao Lu, 3.416,887 A 12, 1968 Matsubara et al.
Shandong (CN) 3,552,918 A * 1/1971 Fitch et al. ................. 423,166
3,653,826 A * 4, 1972 Ishihara et al. ... 423,320
(73) Assignee: Shandong Lubei Enterprise Group 4,059,674. A ck 11/1977 Lopker ............. ... 423, 1574
Company (CN) 4,777,027 A ck 10, 1988 Davister et al. ............ 423,320
FOREIGN PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this CN 1043521 7, 1990
patent is extended or adjusted under 35 JP 57129811 8, 1982
U.S.C. 154(b) by 259 days. RU 2094.365 10, 1997
* cited by examiner
(21) Appl. No.: 10/362,845
Primary Examiner Wayne A. Langel
(74) Attorney, Agent, or Firm—Lackenbach Siegel LLP
(22) PCT Filed: May 15, 2001
(57) ABSTRACT
The present invention relates to a method of preparing wet
(86). PCT No.: PCT/CNO1/OO796 process phosphoric acid, which comprises: dividing raw
materials which contain phosphate rock slurry and Sulfuric
S 371 (c)(1), acid into two parts, and then feeding these two parts into two
(2), (4) Date: Jul. 18, 2003 reactors separately. In the first reactor, feeding 70–90 wt.%
(87) PCT Pub. No.: WO02/20400 of the total amount of the slurry and sulfuric acid, in which
the ratio of phosphate rock slurry to sulfuric acid to recycled
PCT Pub. Date: Mar. 14, 2002 phosphoric acid is set to be 1:0.6-0.8:1.0-2.5. 10-30% of
the reaction solution directly flows into conversion cell,
(65) Prior Publication Data participating in the conversion reaction of dihydrate gyp
sum. Thus resulted phosphoric acid concentration is 33-39
US 2004/OO47790 A1 Mar. 11, 2004 wt.%. The recovery efficiency of POs is 99% or more.
When putting coke powders in the conversion solution as
(30) Foreign Application Priority Data filter aid, the filtration efficiency can be improved by
Sep. 1, 2000 (CN) ................................ OO 1 11330 10-30%, and in so produced hemihydrate gypsum, P.O.s is
0.05-0.2%, water of hydration is 4-8%. The product can be
(51) Int. Cl. used for producing Sulfuric acid and cement without baking
COIB 25/222 (2006.01) dry.
COIB 25/23 (2006.01)
(52) U.S. Cl. .................................... 423/320:423/157.4 8 Claims, 1 Drawing Sheet

SEPARATOR PHOSPHORIC ACID PRODUCT

10
SULFUREC ACD

PHOSPHATE ROCK
SLURRY

-
FIRST SECOND COVERSION HEMEHYDRAE
REACTOR REACTOR CEL GYPSUM
 US 7,172,742 B2
1. 2
METHOD OF PREPARING WET PROCESS and sulfuric acid; making all of them to react com
PHOSPHORIC ACID pletely; in the second reactor, the reaction temperature
is controlled between 70–80° C.; the ratio of liquid to
TECHNICAL FIELD solid is 2.3–2.7; the concentration of SOs in the second
reaction solution is 0.03–0.05g/L, the concentration of
The present invention relates to the field of preparing POs in the second reaction solution is 30-35%.
process phosphoric acid. More particularly, the invention 3. Dividing the second reaction solution into two parts.
relates to an improved method of preparing wet process Part 8, which contains 10-30% of the reaction solution,
phosphoric acid. flows into conversion cell 4; the other part 7 flows into
10 separator 5, where the product phosphoric acid is
BACKGROUND ART extracted; the resulted concentration of phosphoric acid
is 33-39 wt.%.
The phosphoric acid is one of the important chemical 4. In conversion cell 4, feeding the dihydrate gypsum 10
materials. The processes for preparing phosphoric acid are separated by separator, the part 8 of second reaction
classified as wet-process and heat-process. Typical wet 15 slurry from the second reactor and some additional
process for preparing phosphoric acid is comprising: decom sulfuric acid, which conduct the conversion reaction by
posing phosphate rock with sulfuric acid and separating the introducing steam; the amount of added sulfuric acid is
resulted phosphate rock slurry into phosphoric acid and 0–15% of the feeding amount of the sulfuric acid in the
calcium sulfate. In accordance with condition and the num first reactor; in the conversion cell, the reaction tem
ber of crystalline water in produced calcium sulfate, the perature is controlled between 90–105° C.; the ratio of
wet-processes are classified as dihydrate, hemihydrate, liquid to solid is 2.5–3; the concentration of SO in
anhydrous, hemi-dihydrate and di-hemihadrate process. reaction solution is 0.07–0.09 g/L, the concentration of
Among them, the anhydrous process can't be industrialized POs in reaction solution is 24–30%.
by now, and hemihydrate process is used seldom because of 5. In filter 6, filtering the conversion solution; feeding the
its severe operation. Now, the dihydrate process is the main 25 filtrate 9 (the concentration of POs is 24–30%) back
one for preparing phosphoric acid. The production by Such into the first reactor. The filter cake is crude hemihy
process is up to 80% or more of total production of phos drate gypsum, which contains 4-8% of crystalline
phoric acid, and the scale of its apparatus becomes larger and water and 18–20% of adsorptive water. The crude
larger. However, dihydrate process has two shortages: one is gypsum can be converted naturally into dihydrate gyp
the co-crystallation of CaFIPO in the gypsum crystal lattice, 30 sum through hydrolyzation, which contains only
and thereby the loss of POs is high and recovery efficiency 5–10% of adsorptive water; the product can be used for
is low; the other is that the concentration of phosphoric acid producing sulfuric acid and cement, as well as making
is low and only about 30%. Now in China, the dihydrate plasterboard and other building materials.
process is dominant, and hemihydrate or hemi-dihydrate The present invention is characterized in dividing phos
process takes second place, and di-hemihadrate process has 35 phate rock slurry and sulfuric acid into two parts and then
not been reported. feeding these two parts into two reactors separately. In the
DISCLOSURE OF THE INVENTION
first reactor, feeding 70–90 wt.% of the total amount of the
slurry and sulfuric acid makes it possible to control the
concentration of POs in lower level and to maximize
The purpose of the invention is providing a method of 40 concentration of free sulfuric acid in order to obtain the
preparing wet process phosphoric acid. The process is better crystallization condition and to reduce the loss of
subjected to dihydrate-hemihydrate process. By such pro P.O. because of the co-crystallation. In the second reactor,
cess, the high concentration phosphoric acid is made from feeding additional phosphate rock slurry and sulfuric acid
lower class phosphate rock, and a good quality low-phos make it possible to control concentration of POs in higher
phorous apatite is obtained to satisfy requirement of pro 45 level (up to 30–35%) and to obtain the better condition for
ducing sulfuric acid and cement. the crystallation of gypsum. In this way, the resulted gypsum
The resolution of the present invention comprises that: crystals are big, uniform, which facilitates the filtration. As
dividing raw materials which contain phosphate rock slurry a result, the loss of POs due to co-crystallation and the loss
and sulfuric acid into two parts; then, the one of these two of water-solubility POs are reduced; the amount of unde
parts directly flows into conversion cell, and participates in 50 composed POs is decreased; the yield of POs is increased.
the conversion reaction of dihydrate gypsum. The process Thus, the high concentration phosphoric acid can be pro
comprises: duced by using middle class phosphate rock.
1. In the first reactor 1, feeding phosphate rock slurry, The present invention is also characterized in that one part
sulfuric acid, and recycled low-concentration phospho of the reaction solution obtained in the second reactor
ric acid 9 from filter 6; the weight ratio of phosphate 55 directly flows into conversion cell, and participates in the
rock slurry to sulfuric acid to recycled low-concentra conversion reaction of dihydrate gypsum separated by sepa
tion phosphoric acid is 1:(0.6-0.8):(1.0-2.5); the molar rator. In this step, according to the situation, feeding addi
ratio of phosphate rock slurry to sulfuric acid is 1:5; in tional sulfuric acid maintains the higher concentration of
the first reactor, feeding amount of the slurry and sulfuric acid and phosphoric acid in the solution of the
sulfuric acid is 70–90 wt.% of the total amount; the 60 conversion cell. This can promote the conversion process
reaction temperature is controlled between 75-85°C.: and the growth of hemihydrate gypsum crystal, as well as
the ratio of liquid to solid is 2.3–2.6; the concentration prevent hemihydrate gypsum from “excess dehydration'.
of SO, in the first reaction solution is 0.04–0.07 g/L.; In present invention for preparing phosphoric acid, a
the concentration of POs in the first reaction solution filtration-supporting cell 5 can be added between the con
is 28-30%. 65 version cell 4 and filter 6. In other words, a filtration
2. In the second reactor 2, feeding the first reaction supporting step is added to the process. In the filtration
solution and the other part of the phosphate rock slurry supporting cell 5, the coke powder and the conversion
 US 7,172,742 B2
3 4
solution from conversion cell are fed. The ratio of added tion flows into conversion cell, and the rest flows into
coke powder to gypsum is 1:16–30. The mixture is fed into separator, where the product phosphoric acid is
the filter 6 to carry out following filtrate step. The porous extracted to obtain phosphoric acid in which the con
coke powder can absorb the fluorosilicic acid in the solution, centration of POs is 37.14 wt.%.
so that the filtration speed of hemihydrate gypsum can be . In conversion cell, feeding the dihydrate gypsum
increased and the filtration efficiency can be improved by separated from separator, the second reaction slurry
10 30%.
from the second reactor and some additional Sulfuric
BRIEF DESCRIPTION OF THE DRAWINGS acid, which conduct the conversion reaction by intro
10 ducing steam; the amount of added Sulfuric acid is 11%
The FIGURE is a schematic diagram of the process for of the feeding amount of the sulfuric acid in the first
preparing phosphoric acid. reactor; in the conversion cell, the reaction temperature
Please refer to the FIGURE. In the first reactor 1, phos is controlled at 96° C.; the ratio of liquid to solid is
phate rock slurry, Sulfuric acid, and recycled low-concen 2.77: the concentration of SO in reaction solution is
tration phosphoric acid 9 from filter 6 are fed to be decom 15 0.079 g/L: the reaction time is 54 minutes; the concen
posed for 1.5–2 hours; feeding amount of the phosphate rock tration of POs in reaction solution is 27.4%.
slurry and sulfuric acid is about 80 wt.% of their total . In the filtration-supporting cell, feeding the conversion
feeding amount in the present process. In the second reactor, Solution from conversion cell and the coke powder, and
feeding the first reaction solution and the rest of the phos making the ratio of the coke powder to the conversion
phate rock slurry and Sulfuric acid makes the reaction solution be 1:21; feeding the mixture into the filter to be
complete; the reaction is carried out for 1.5–2 hours; feeding filtrated. In filter, after filtration, the filtrate (POs
amount of the phosphate rock slurry and Sulfuric acid in the 27.1%) is fed into the first reactor, and the filter cake is
second reactor is about 20 wt.% of their total amount. crude hemihydrate gypsum, which contains 6.78% of
Dividing the reaction solution obtained in the second reactor crystalline water and 19.16% of adsorptive water. The
into two parts, among which part 8 flows into conversion 25 amount of POs in the hemihydrate gypsum is 0.13%
cell 4, and the other part 7 flows into separator 3 to produce and the recovery efficiency of POs is 99.1%. The crude
phosphoric acid in which the concentration of POs is 33-39 gypsum can be converted into dihydrate gypsum natu
wit. '%. In conversion cell 4, the dihydrate gypsum 10 rally through hydrolyzation, which contains only
separated from separator 3 is mixed with part 8 of second 6.81% of adsorptive water; the product can be used for
reaction slurry from the second reactor. Some additional 30 producing Sulfuric acid and cement, as well as making
Sulfuric acid is added according to the situation. In the plasterboard and other building materials.
conversion cell 4, dihydrate gypsum is transformed into
hemihydrate gypsum, the conversion reaction carries out for EXAMPLE 2
40–60 minutes. In filter 6, after filtering the conversion
solution, the filtrate which contains 24–30% of POs is fed 35
. In the first reactor, feeding phosphate rock slurry,
into the first reactor. The filter cake is hemihydrate, which
contains 48% of crystalline water, 18–20% of adsorptive Sulfuric acid, and recycled low-concentration phospho
water and 0.05–0.2% of P-Os; the product can be used for ric acid with 27.9% POs from filter; their weight ratio
producing Sulfuric acid and cement, as well as making is 1:0.68:1.4; the molar ratio of phosphate rock slurry
plasterboard and other building material. 40
to sulfuric acid is 1:5; in the first reactor, feeding
Preferred Embodiments of the Invention
amount of the slurry and that of Sulfuric acid is respec
tively 78 and 80 wt.% of their total amount; the
EXAMPLE 1. reaction temperature is controlled at 83°C.; the ratio of
liquid to solid is 2.41; the concentration of SO in
1. In the first reactor, feeding phosphate rock slurry, 45
reaction solution is 0.053 g/L: the reaction time is 2
Sulfuric acid, and recycled low-concentration phospho hour, the concentration of POs in reaction solution is
29.1%.
ric acid with 27.1% of POs from filter to conduct . In the second reactor, feeding the first reaction Solution
decomposition reaction; their weight ratio is 1:0.75:1.6:
the molar ratio of phosphate rock slurry to sulfuric acid and the other 22% of phosphate rock slurry and 20% of
is 1:5; in the first reactor, feeding amount of the slurry 50 Sulfuric acid; making reaction complete; in the second
and that of the sulfuric acid is respectively 71 and 72 reactor, the reaction temperature is controlled at 78° C.;
wt.% of their total feeding amount in the process; the the ratio of liquid to solid is 2.57; the concentration of
reaction temperature is controlled at 79°C.; the ratio of SO in reaction solution is 0.031 g/L: the reaction time
liquid to solid is 2.55; the concentration of SO, in is 1.6 hour; the concentration of POs in reaction
solution is 34.3%.
reaction solution is 0.064 g/L, the reaction time is 1.8 55
hour; the concentration of POs in reaction solution is . Dividing the reaction solution obtained in the second
28.9%. reactor into two parts, 23% of obtained reaction solu
2. In the second reactor, feeding the first reaction Solution tion flows into conversion cell, and the rest flows into
and the other 29% of phosphate rock slurry and 28% of separator, where the product phosphoric acid is
Sulfuric acid; making reaction complete; in the second 60 extracted to obtain phosphoric acid, in which the con
reactor, the reaction temperature is controlled at 74°C.; centration of POs is 38.03 wt.%.
the ratio of liquid to solid is 2.59; the concentration of . In conversion cell, feeding the dihydrate gypsum
SO, in reaction solution is 0.038 g/L: the reaction time separated from separator and the second reaction slurry
is 1.6 hour; the concentration of POs in reaction from the second reactor, which conduct the conversion
solution is 33.1%. 65 reaction by introducing steam; in the conversion cell,
3. Dividing the reaction solution obtained in the second the reaction temperature is controlled at 94° C.; the
reactor into two parts, 28% of obtained reaction solu ratio of liquid to solid is 2.91; the concentration of SO
 US 7,172,742 B2
5 6
in reaction solution is 0.067 g/L; the reaction time is 1 (1-3) dividing the reaction solution obtained from the
hour; the concentration of POs in reaction solution is second reactor into two parts: one part (8) comprising
28.3%. 10–30% of the reaction solution flows into conversion
5. In filter, after filtering the conversion solution, the cell (4), and the other (7) flows into a separator (3),
filtrate (POs 27.9%) is fed into the first reactor, and the 5 wherein the product phosphoric acid is extracted;
filter cake is crude hemihydrate gypsum, which con (1-4) in a conversion cell (4), feeding the dihydrate
tains 7.13% of crystalline water and 18.94% of adsorp gypsum (10) separated out from the separator, some
tive water. The amount of POs in the hemihydrate additional sulfuric acid and the one part (8) of the
gypsum is 0.08%, and the recovery efficiency of POs second reaction slurry from the second reactor to
is 99.4%; The crude gypsum can be converted into 10 conduct the conversion reaction; and obtaining a con
dihydrate gypsum naturally through hydrolyzation, version solution; and
which contains 6.58% of adsorptive water; the product (1-5) in a filter (6), after filtering the conversion solution,
can be used for producing Sulfuric acid and cement, as feeding the filtrate (9) into the first reactor; wherein the
well as making plasterboard and other building mate filter cake is the crude low-concentration phosphoric
rials. 15
acid hemihydrate gypsum useful for producing Sulfuric
acid and cement.
INDUSTRIAL APPICABILITY
2. A process for preparing phosphoric acid in accordance
The present invention relates to a process for preparing with claim 1, is characterized in that, adding a filtration
phosphoric acid, which comprises: dividing raw materials Supporting step between the step 1-4and step 1-5; that is,
which contain phosphate rock slurry and Sulfuric acid into feeding the conversion Solution obtained in step 1-4and coke
two parts, then feeding these two parts into two reactors powder into the filtration-supporting cell (5), wherein the
separately. Part of the reaction solution directly flows into ratio of added coke powder to gypsum is 1:16–30.
conversion cell and participates in the conversion reaction of 3. A process for preparing phosphoric acid in accordance
dihydrate gypsum. By Such process, the recovery efficiency 25 with claim 1, is characterized in that, in step 1-1, feeding
of POs is improved and up to 99% or more. Meanwhile, amount of Sulfuric acid and the phosphate rock slurry is
good quality hemihydrate gypsum is obtained, in which 70-90 wt.% of their total feeding amount in the process.
P.O. is 0.05-0.2%, water of hydration is 4-8%, and adsorp 4. A process for preparing phosphoric acid in accordance
tive water is about 19%. After naturally hydrating, the with claim 1, is characterized in that, in step 1-4, feeding
product can be used for producing Sulfuric acid and cement 30 amount of sulfuric acid is 0–15 wt.% of feeding amount in
without baking dry. The coke powder as filtration-supporting step 1-1.
agent is added to the reaction solution, which improves the 5. A process for preparing phosphoric acid in accordance
filtration efficiency and reduces energy consumption. The with claim 1, is characterized in that, in step 1-1, the reaction
present invention has obvious advantage in the aspect of temperature is controlled between 75-85° C.; the concen
economy and Society. 35 tration of POs in reaction solution is 28–30%; the concen
The invention claimed is: tration of SO in reaction solution is 0.04–0.07 g/L.
1. A process for preparing phosphoric acid, which com 6. A process for preparing phosphoric acid in accordance
prises: decomposing phosphate rock, separating the decom with claim 1, is characterized in that, in step 1-2, the reaction
posed solution, converting the dihydrate gypsum and filtrat temperature is controlled between 75-85° C.; the concen
ing, is characterized in that, the process comprises the steps 40
tration of POs in reaction solution is 30–35%; the concen
following: tration of SO, in reaction solution is 0.03–0.05 g/L.
(1-1) in a first reactor (1), feeding phosphate rock slurry, 7. A process for preparing phosphoric acid in accordance
Sulfuric acid, and recycled low-concentration phospho
ric acid (9) from a filter to conduct decomposition; and with claim 1, is characterized in that, in step 1-4, the reaction
obtaining a first reaction Solution; wherein the weight 45 temperature is controlled between 90–105° C.; the concen
ratio of phosphate rock slurry to sulfuric acid to tration of SO in reaction solution is 0.07–0.09 g/L.
recycled low-concentration phosphoric acid is 1: 8. A process for preparing phosphoric acid in accordance
(0.6–0.8): (1.0–2.5); with claim 1, is characterized in that, in step 1 -5, the
(1-2) in a second reactor (2), feeding the first reaction concentration of POs in filtrate which is fed back to the first
Solution obtained in step 1-1, and other phosphate rock 50 reactor is 24–30%.
slurry and Sulfuric acid thereby making the reaction
complete;