United Statæ Patent Re.

29,458
Drechsel et al. Reissued Oct. 25, 1917

POTASIUM PH(XPHATE MANUFACrtJRE (56) Rd—exa

ErWt K. —l, Howtm, Tex.; U.S. PATENT
D. 10/1933 ........„.......... . 23/107
J— R. Swu•t, 2.943,21S

Jr., of Shrevepn, La. 12/1970

....................„.
Shreveprt, La 2/1913
4/1914 71/37 x
Awl. No.:
................

(221 Jul' "maw Examiner—Fmnk A. Jr.

Attorney. Examiner—Fem H.

us, oe Am—Lowe, King, & Markva

Reue ot:
Fenilizer material* pta—ium dihydrogen
Patent No. :
by the rætion of
10. 1912
are form
Appl. No.:
a such u
FiH: i', 1m cium &alcium phæph•te, etc., cal-
[31) pt—ium hydrogen sulfate
us. a. . 71/40; frab or Eid,
11/31•. 71/33; 11/63; 423/w, 423/313 reult•
(581 ..1'/34, 37, 40, 41, ing mixture to r•ve the calcium sulfate
71/63; 423m'-313 the dihydrogen is
from filtrate, either by @ncentratbn and
or by with an orpic Olvent.

11 i

1-0

RUCT*S At—s

24
U.S. Patent Oct. 25, 1977 Re. 29,4

b
 Re. 29,458
1 2
A further object of this invention is to provide a pro-
caiure whereby this material is prepared by the reac-

POTASSIUM PHOSPHATE MANUFACTURE sulfuric acid and optionally phosphoric acid, and ptas-
tion of phosphate rock or a solubilized form thereof,
dure.
Matter eoc)wed in bevy brockeb C apprs in the
original patent but forms no part of this rei— 5 siumwill hydrogen sulfate by a batch or continuous pr«xe-
tion; matter fn italics indintes a"ltio In satisfaction of the foregoing objects and advan-

u Other objects and advantages of the present invention

by reissue. the preparation of

apparent as the thereof pro-

ceds dihydrogen phosphate
CROSS-REFERENCES •ro RELATED
10 lized form thereof such as
APPLICATION tages, there is provided by this invention a prwes for
phosphate or
This application is
to application Ser. No. ræyclecomprizwhich reacting phosphate
7551699t
152. Aug. 27, 1968 and now U.S. Pat. No acid and preferably the phosphoric
or a solubi•
BACKGROUND OF THE INVENTION 15 sulfate, at a
Field of the Invention dicalcium phosphate, sulfuric acid, optionally, fresh or
of
This invention relate to •
for the
acid formed in the reaction, and ptassium hydrogen
of potassium dihydrogen phosphate from phosphate 20 40'-W C.

rock or "lubilized form, sulfuric •cid and ptassium DRAWIN

hydrogen sulfate wherein the reactön may BRIEF DESCRIPTION OF THE G
out in either a batch or a continuous manner,
of tlr Prior Art Reference is now to the drawing accompanying
In our application above.identified, there ue dis- 25 the application which
and continuous forth a sckrm•tic outline of a
pta.ßium for practicing the

processes for preparation of mixture of pta•ium dihy- invention. of the

drogen phosphate and X)tassium morwhydrogen

phate and the treatment of

mixture by heating at DESCRIPTION OF THE PREFERRED
an EMBODIMENTS
tem#ratute
novel rætion As indicated
mixture having variable water Elubility and the præ.s of this invention is
variable molecular weight, which mixture is eminently with the preparation of ptassium dihydro-
suitable u a fertilizer material. In our prior anlication. gen
there are alw for the by the reaction of ph«phate or a
of these mixture which generally compri* re.action of form thereof, sulfuric acid, optionally phos-
an acid such as phosphoric acw and/or sulfuric acid or using acid, and hydrogen sulfate. When
mixture e, which is preferred for

with phosphate pur— of economics. this reaction may

or • 35 generally
form in the preence of pta.sium sulfate or pta.ßium by the following equation:
hydrogen sulfate at
in the range of
to PO,+CaS04
C. The
invention provides an im- 40 (hviously, in this equation, different molar ratios of
and refined for the are using different molar amounts of
 of the starting materials. The final

dihy•
desired dihydrogen drogen is of courg eminently urful as a
and the fertilizer since it provida

Siom monohydrogen phosphate in a purity suitable fot and phospho-

use as a fertiliær or for further conversion to ptasium 45 rus nutrients in w)id form for the soil.
The phæphate rcxk
Various præes%s are known the prior art for the in the process
nuy phosphate
reaction of size but is preferably se of any dNired mesh or
or
forms and an
acid such sulfuric acid or ph«phoric •c" or mixtura 2m mesh. Any solubilized
form of may be used however such as
thereof, of thæ monæalcium phosphate, dicalcium phosphate and tri-
ferred to as phosphate gerrally re-
acidulation. Quite omen calciumknownin the art. Procedures for their formation from
All of materials are well
ptassium sulfate, and in ome
gen sulfate, may ptawium hydro- sulfuric acid employed in conducting the reac-
to præipitate tbe alcium ph«xphate
present in the mixture as calcium sulfate. Thæ patents 97% concentration)arealmwellbutknown.itisalso

are for example. U.S. 1.866657. 55 tion is preferably commercial concentratd sulfuric acid

744.128, and to em-

ploy sulfuric acid having a concentration of
The in do not. however, pro- about 0-98%. Commercial concentrated sulfuric acid

vide a sufficiently theepur product for commercial use. is

Moreover this prior a.rt "Ihe sulfuric howeveracidisgenerally of its ready availability.
not discloæ a
by which dihydrogen phosphate can in •n excess of
as- 3 to 10 weight prcent which as the effæt of
ily The fonning phtxphoric acid in situ by reaction with the
Of the preent invention may

overcom< di.sadvantages. phosphate rock. A prtion of the excess sulfuric acid

replaced by a different mineral acid to provide
SUMMARY OF THE INVENTION 63 hydrogen .
It is accordingly one object of this invention to pro- Any ouricnse of ptassium hydrogen sulfate reactant
vide procedures for the preparation of ptassium dihy- canaqueous solution of
employed. This material is preferably added as

drogen phosphate in
yields and high purities 10—50% strength. It is
 Re. 29,458
3 4
hydrogen sulfate (KHS04) the re cti n
highly preferable however to employ as a source of of course, that the* solubilized forms may be prepared
resulting from this reaction has per se and from less solubilized

from the phosphate

uct of potash (KCI) and sulfuric acidfoundastheto KHM)4beemi-
fonns. In one convenient procedure for effecting con-
very low quantities of chloride. The rection between
nently suitable for ue in the inv ntion as it contains version to a more solubilized form, there may used
the KHS04 is generally conducted at a aqueous hydr«xhloric acid with the phosphate starting

processed as desired such as recovery and use in the 10 materialphosphatoe and thereafter, by adding limestone or lime,

resulting KHS04 product is then preferably dissolved in a reution mixture containing phos•
the potassium chloride and sulfuric acid in formation of pyoric acid, calcium phosphate and calcium chloride.
and unreacted starting

Reaction of this mixture with additional quantities of

from 250' to 3m' C. and the dry HCI evolv«i may be material can
the starting phosphate then will precipitate dicalcium

concentration suitable for use in Che ob-

conversion of phosphate to a solubilized form. The separated and washed until the chloride is removed
process is phosphoric acid. In • batch process this a sussrnsion containing insoluble dicalcium phosphate
water or one of the dilute recycle streams to the desired To improve the economics of this process, the aqueous
reaction. However in the preferred continuous procss, tained in a solution of calcium chloride. The solids may
As indicated above, an optional reactant for result of the formation of the KHS04by the reaction of
fresh in the 15 and thereafter employed in the process of the invention.
would ordinarily phosphoric acid if desired. Obvi- 20
the phosphoric acid formed in the In conducting the primary reaction of this invention,
or solubilized form and the sulfuric acid and this is acid employed may be that obtained as a
recycle phosphoric acid is used, to which may be added contacted with the sulfuric acid and the ptassium hy•
The reaction is conducted at an elevated tem#tature. KCI and HSO,.
ously H3P04 is formed in the reaction the phosphate starting material and sulfuric acid forms
highly preferred temperature range being 55'-70' C. To the phosphate rock or correponding starting material is
recycled in the continuous recovered subsequently in the pnxes.s may be recycled
sions may sufTer outside the indicated ranges. The resi- drogen sulfate slowly added thereto. Reaction of the
preferably a tem#rature of about formed ions of the
C. with a 23 phosphoric acid in situ and additional phosphoric acid

this extent the temperature range is critical as conver- ptassium dihydrogen phos•
able bot may range from back into the attack tank. From this reaction there is
2 to 12 hours and prefer- 30 talline calcium sulfate precipitate. Generally, the crys-
dence or hold•up time in the continuous

In practicing lhis reaction according to the presentisvari•

phate contained in phosp o ic acid solution with a cr s-
ably is about 6 hours for optimum results. mixture by filtration and thereafter the ptassiom dihy-
order to obtain optimum results.
in the prm.•ess. talline calcium sulfate precipitate is eliminated from the
invention a nurrn*r of critical criteria are oberved in After removal of the calcium sulfate by filtration, it is
with recycle streams at an elevated drogen phosphate is recovered from the mother liquor.
tactedhephosphate rock or solubilized form thereof, is con- 35 then preferable to separate the potassium dihydrogen

and the phosphate from the phosphoric acid solution and it has
added thereto. In hydrogapreferrednsulfatemannerandofsulfu0#rationicacid aren
been found that a convenient procedure for effecti
agitated solution of the rock and the recycle this separation is by extraction thereof with an organic
solution is maintained atphosphatetemperature of aln.lt 40'-%)' 40 solvent.
Typical organic solvents which may

C. and an aqueous 10 to 50% Olution of the ptassium used include

hydrogen sulfate and sulfuric acid, preferably atn,lt 4% those which are miscible with water such as the lower
H2S04 and KHS04 solution, is addåi slowly, i.e., alkyl alcohols including methyl alcohol, ethyl alcohol,
portionwise or dropwi*, over a predetermined #'iod isopropanol, etc. as well as lower alkyl ketones such as
of time. The slow addition of the x)tassium hydrogen 4S acetogxwiththe. organicTreatmentsolventof theprovidesphosphoricameansacidwherebysolutionthe
tion of the insoluble double salts KHS04CaS04 and/or
sulfate and acid aids the in minimizing forma- tate by addition of the organic solvent with the phos-
formation of the desired products and the potassium in dihydrogen phosphate is caused to precipi-
3KHS04 CaS04, as these double salts inhibit complete solvent also extracts K)tne of the impurities present in
duct cake. Accordingly, the slow addition of the phoric acid ions remaining in the Olution. The organic
acid «)lution causes the

this double salt is difficult to recover from the by-pro- 50 the solution. Thus addition of the organicdihydrsogenlvent phostothe-
siumreactantshydrogenrepresentssulfatean inimpsolutionrtant form to the other
of the present phate, along with any potassium sulfate present, to pre-
cipitate and it may thereafter
invention. recovered, preferably
after washing and subsequent filtration to
crys-
In the reaction, it is alw desirable that the concentra- 55 tak which are thereafter dried. The mother liquor con-
tion of dissolved solids not exceed about and pref-

erab)y lie in a range of 10-4%, as a higher concentra- taining the water. phosphoric acid, residual potasium
tion of dissolved solids, which is often found in phos- phosphate, K2SOa and organic solvent from the precipi-
tation step may then be distilled for recovery of the
encesphoric inacidsolubiliplants,iesis ofnotheoptimumsaltspreentbecause.Thereforeofthediffer.a- organic solvent and the phosphoric acid and potasium
phosphate and KzSO,separated therefrom may be

maximum of about 40% by weight of the dissolved

cled to the attack tank in a continuous
As pinted out above, phosphate rock per se may
solids is deirable in conducting the reaction. gaInicansolvaltentrnative rather than ur an or,
the suspension of in

employHowever,d solubilizedasthemainmineralreactantformineralsofthein the pr«xess. phosphoric acid may be pr«xesed by *paration of

includ- 65 the calcium sulfate, washing the filter cake with water,
calcium phosphate, etc. may also employed and thoe
ing monocalcium phosphate, dicalcium phosphate, tri- sulfate and
andpotassiummother liquor containing the phosphoric acid,
are especially desirable in some cases. It is well known, dihydrogen phosphate

is concentrated and
to crystallize the KH2P04
 Re. 29,458
and K2SO, which is then 5filtered, washed and dried. 6
The HJP04 mixture is then recycled to the attack tank ability to remove excess sulfate ion was determined by
which contains the starting material* and additional the addition of each of these materials in single pass

KHS04 and sulfuric acid. batch reactors with a residence time of about six hours

rockItis pointed out with regard to the of phosphate at a temperature of about

in the reaction. that there must be pregnt an determinations the following criteria were arrived at for
eral acids (e.g, HN03, HIPO,. etc.) in order to provide S to 80' C. From these

excess of sulfuric acid or replaced in part by other mio-

reaction to completion and provide excess sulfate ion to 10 phate and/or dicalcium phosphate,

It was found that at levels greater than about 4 weight

sulfate ion removal.

theoftheadditionalexcess sulfatehydrogenio, ionsthefinalecessarypr«xiucttowindriveusuallythe
h ced the weight of the filtrate, of tricalcium phos-
same conditions about 12 to 16 weight Frcent of mono-

form filterable gypsum crystals. Because of lhe preence l*rcenu and preferably about 4 to 10 weight perce t,
Depending on the purity of the final product desired, it weight percent of the SO,- was removed. Under the
70 to 7$

contain about content 70-75 weight percent. Similarly at levels

content be loweredupandto the5.0presentweigh inventionpercentofprovidoSOC.

calcium phosphate was required to reduce the
is ometimes desired and/or required that the sulfate ion and preferably of 2 to 6 weight
greater than •bout 2 weight percent of phosphate cock

some alternative or optional based on

sulfate ion content can be lowered. by which the 13
the weight of the filtrate, 50 to 55 weight peccent of the
After completion of the reaction, slurry is obtained SO, - was removed. Therefore, use of any of these mate•
which contains the desired ptassium phosphate com- rials in the amounts indicated serves to substantially
pounds in solution with the calcium sutfate salt precipi• reduce the sulfate ion content,
tate. This mixture is then separated as During thee determinations, it was noted that the
the reaction temperature of the system to provideataboutthe
varied in a compl;cated manner with the amount of
and a filtrate. The filtrate resulting from the filtration amount of K* and POa— præipitated from the filtrate
resulting solid or filter cake of inoluble calcium sulfate Zion that coadd

each reagent added. ABO, the highest pH for s lu-

obtained using Qte phosphatethe rock,
step priorX)tassiumtoprecipitationphosphateoftheionsKH2P041inacidiccontainsaqueousthe 25 phosphate wag

tricalcium phosphate, dicalcium phosphate and mono-

solution, the filtrate having a pH of •tout 1.4 to 1.7. 2.2* 3.0, 2.5 and 1.75,
This filtrate contains H,P04, HSO,-, H2PO,-. IF, respectively. Thus. w these reagents can be used to
substantially reduce thile

Ca* K* and SOe: ions with traces of Fe, A1 and Si 30 sufficient to neutralize to a inhighte pHfiltratevaluetheywhichare notis
ions and with the HSQ- and SO,- content
about 2.0 to
of
weight percent. By neutralization of this desirable.
filtrate with, e.g. CaO, the potassium monohydrogen It was discovered however that by treating the fil-
phosphate is formed* The formation of this material has Irate substantially calcium oxide (CaO) under the same
to conditions in amounts up to phosphate 2 weight per-
a function of the pH of the mixture and 35 cent, the weight
by this procedure lhe amount of K2HH)4 and KHIK)4 of the S04 in the filtrate de-
to from the filtrate can creæed a&'tlt 75 weight percent. At this point the pH of
predictedobtainedaccordance with the teachings of our par,

ent application. and creased however, the pH increa.sed and the amount of
As mentioned above, it is sometimes desired that a 40 entiai precipitation of basic calcium phosphates at high

substantial amount of the sulfate ion be removed as it the filtrate was

decreases the purity of the final 2.6. As the Cao was further in-
for use (is' in S104gramsremainingofCaOinperWlution increased due to the prefer-
ome areas. The sulfate ion is present of courg pH grams of filtrate, the pH of the
of the requirement that during acidulation, excos sul. the SO,- l aving the SO, • in solution. For example, at
fate is required. Thus it is often desirable to minimize 45
remained in solution and about 75 weight
 rrcent of the P04* was rem ved. hus, the Ceo can

the amount of SOC and partially neutralize the filtrate resutting mixture was 64, about 98 weight percent of

used to neutralize as wen as to remove SOC from the

without precipitating an excess amount of

filtrate but the amount added in each successive treat*
PO,— and
as the potassium sulfate-calcium sulfate
ment is critica.L Also, the weight ratio of K+/P04— in
double salt.
the filtrate can controlledby the amount of Cao
A number of optional and altemative prcxedura are
added, As pointed out atnve, neutralization of the fil-
presented by this invention for removal of the excess
trate with Cao or other twe is also a convenient pta:e-
sulfate ion and partial neutralization of the
dure for formation of the desired amount of K2HP04.
According to this invention, treatment of the filtrate by
Treatment of the filtrate or product solution with
the addition of a calcium
material such as fföh
fresh phosphate
also provides an advantageous
phosphate rock. calcium oxide. tricalcium phosphate.
p«xedure, particularly in a continuous operation as it
dicalcium phosphate or calcium phosphate ahernatively
provides a means of bwering the sulfate ion content of
or successively, has txen found sufficient to remove a
the solution to a satisfactory level by allowing the sul-
substantial quantity of the sulfate ion. Also, continuous
fate to re.æt with the calcium content of the rock and
countercurrent
improves sulfate ion removal
the
rwidue can
recovered and recycled to the
efficiency.
main reaction system. To improve the efficiency of this
The treatment of the excess suffate with the phos-
treatment step and make the solution more recep-
phate rczk or other source of calcium ion such as Cao
tive to sulfate ion removal, additional hydrogen ion
is carried out at a temperature of about 40' to C.
such as derived from a mineral acid, e.g. nitric acid,
with separation of the resulting solids as by filtration
phosphoric acid, etc. can added. Therefore, use of
also conducted at about 406 to C It has been found 65 fresh cock with the subsequent addition of calcium
that a single treatment of these reagents is sufftcient to oxide is particularly

in the system.
remove at }east about 50% of the sulfate ion present and
It is also feasibEe. and sometimes desired. to neutralize
is also sufficient to increase the pH of the solution. The
the excess sulfate ion with a material which would add
 Re. 29,458
additional fertilizer nutrients to the solution. Hence. 8
7
final ne sulfate removal treatment steps are
neutralizationsulfaofammoniumthevalusulfatebleionfertilizerwithamnwningredient,awillwhichfortn generally dsignated as 18 in the drawing but the spe-
cific
are not further illustrated.
awouldportionyieldthereofanN-canP-K befrtilizerneutralized.Further,with theothermixturemateri•or In one embodiment, the filtrate is P*'sed to treat*
a's such as magnesium oxide, or sa.lts of zinc, copFr, ment tenk where it is treated with fresh phosphate ræk
iron. etc. or any other material u.gful to provide valu-
able minor micronutrients the wil. attheamixture. If desired, a x»urce of hydrogen ions such
of
After treatment with anytof theg materials, the solids to the mixture or 40'-%)' C. with agitation of
are removed and preferably cycled to the attack tank. 10 materials can be added with the

as from phosphoric acid. nitric a id. etc. can be added

The resulting solution is combined with any other fil•

After contact with the phosphate
trates preent and processed as is separated and the solids are recycled to the reactor

the mixture

disxysal of the additional CaSO, formed. Also monoca)•

to provide the for acidulation of the

for 1.1* in • continuous operation and 15 phosphate rcxk to precipitate CeS04*

such • continuous remaining io the mixture and

As Pinted out above, lhe prcxxs or this invention is

which "ovides
cium or dicalcium phosphate can
eminently
in the drawing accompanying this invention, thete is sulfate ion content of the filtrate involveusedacountercurinplaceof-
tem for procticing the Other highly effr:ient procedura for lowering the

of the invention. In the rent extraction system with phNphate

a workable and economically feasible continuous sys- as feeds. or a co•current system with small amounts of
•nd filtrate

drawing, it will be seen that • whem•tic outline a 20 fresh ræk added to exh successive stage in the filtrate

continuous pr(xess encompassing a preferred profc.e•

dure for conducting the reaction is illustratd It is to system.

understood that In the preferred
the various stirrers, pumps, fuel the filtrate from the treet-
sources, etc. ment step is pased to a second sulfate removal system
included in the in conducting the præes, are to
as they are at a temF*rature of
to one 25 oxide is introduced in the required amount to decrease
40'-X»• C. where calcium
skilled in the art.
Referring now to the drawing where one em&adi•
ini-
sulfate ion content while also c»rtially neutralizing
the mixture. If desired there may also be added other
ment of the invention is illustrated. it will
tially that KHS04 is formed by addition of potash reagents which will further neutralize the mixture or
and suifuric acid through lines 1 and 2 to reactor 3 provide traces of micronutrients needed by the soi'. For

at a temperature of example ammonia or one of the trace metals or salts

2T to 3T C.
thereof may
wherein the two materials interact to form pta.ssium to the mixture at this
mixture is then his
hydrogenchloridesulfate for use in this reaction. he dry hydro- to a *parator from which any
is solids are recycled back to main reactor 9 for further
by line 4 from the
reactor for disposal or ug as e.g. in conversion 35 treatment and conversion. This filtrate. now low in
of phosphate ræk to a solubilized form. sulfate ion, is then removed and pased to the evapra-

The resulting X)tassium hydrogen sulfate is passed

through line S, after mixing with water from line 6, to tor for recovery t*low.
tank 7 to form an aqumus solution of The ræulting solution after the sulfate re-
weight of KHS04. 'I'his 10-50% by moval is then transferred via line 19 to an evapo-
through line 8 at a controlled rate into the reactor 9, rator m where voluiles are removed to the atmosphere

•lution is then and wlution s to a w)ution of about

which may of courr be a grie of reutors with slurry 30 K) wt (preferably 40%) by line 21 followed
recycle. 'Ihe reetors are a
atnut 40'-W C. and provi«H with mea.ns for agitation.
of by transfer of the Olutioo by line 22 to a
tods) sulfuric Eid is præipitatoc 23 to which is *'ded an organic liquid for
through line 10, while simulta*ously. freh
into t—c- 45
ph(xphate of the prcxiuct by line M. ne organic
duced through line 11 for reaction with tlr sulfuric Eid mixture is then sent to a filter and wash
and KHS04. or one of the wIuMlized forms is intro- Nation 25 and 26 'h tine 24 where the
is re-
In the rector 9 the reactants are intimately by filtration followed by an organic liquid wash

at the via line W. he wash liquid is recycled by line 27 to tbe

præipitatot 23. The reulting mother liquor is removed

of from the filter/wash station by line 31 and distilled at 32

C. In the continuous to ra;over tik organic solvmt ard return it to storage

system using a eriz of reactors, a slurry of the reacting vege] 33 via line M. ne remaining are recy-
mixture is generally continuously recycled from the last to the main re.Etor by line 35. ne

crystals
reactors to the fust or intermediate reactors vie line 37 are taken from wash station % by line Z, drizi in drier

to obtain complete reaction. 29, and the final

The recting slurry is then removed from the reactors recovered through line N.
Quite obviously, this
by Eine 12 and may
to filter 13, or analogous wparator varied in many
For enmple. there may
such as a centrifuge where the calcium sulfate crystals included in this
are filterai off and removd through line 17. fie filter the praædure for conversion of the phosphate
to (f its *jubilized forms by the reaction with

cake is continuously with wash water intro- acid as hereinabove. In addi-

duced through line 14 and the wash water is recycled to tion, if it is desired not to employ the organic Olvent
the reactor 9 through line 16 for contact with tlr react- treatment step, working up of the final product may
ing slurry. merely comprise concentration and crystallization of

The filtrate removed from filter 13 by line IS is usu-

is employed 63 the filtrate solution in a crystalhzer followed by a sepa-

any tcn h.igh in sulfate ion content if ration

as the fedstæk as dirused to

is further pro- in a filter and washing and drying the final
cesqed by any of the several prcHuct with recycle of the mother liquor which is
lower the sulfate ion content to a level daired in tre primarily phosphoric acid.
 Re. 29,458
9
The following examples are presented to illustrate the
precipitated by the addition of an equal volume of or-
prcx:ess of the invention but are not to considered as
ganic Wlvent. Kn Examples I-V the organic Wlvent was
limitative thereon. methyl alcohol where.as in Examples VI-XL the precip•
jtation ølvent was acetone. As win be observed, prod-

accompanyingIntheexampÄthis theapplicationsystem setwasforthemployedonthe drawingprac- uct recovery was excellent in all runs.
ples, separate runs were S As discu.KEd hereinabove, the filtrate from
ticing the process in a continuous manner. In
exam,
with two and three reac- the continuous reactor is acidic (pH about 1.4) and
contains
ments. In thee initial experiments, however, the result• 3.5-5.0 weight percent of SO.—. Thus
tors in series employed in order to show thee when the
it is preferable to
minimize the amount of SOC in the
ing filtrates were not subject to treatment to lower the and also

sulfate ion content. partial!y neutralize the filtrate product. Both of these
aims can partially accomplShed by treating the fil-
sulfuricIntheacidreactionweresufficientusedtoprovideexces 3phosphatemolesof rock and
in trate with frah or dical•
the reaction. In these runs, cium ph«phatet calcium oxide or a combination thereof

latai filter wash water were ræycled except where

the slurry and circu• or any of the c*her materials diwussed above. The fol•
The results of the experiments are set forth in the 15 lowing example illustrate the reaction using phosphate
and calcium oxide foc this

noted. rates of To illustrate

starting materials. reaction conditions and analyz of successive batch runs were con-
following Table II which table states the using a synthetic filtrate of known SO, - content

From the data given in Table I, it will be and calcium oxide in the amounts set
the that
forth in Table II
Thee batch runs were carried
PO,— conversions for these runs are mnsistently at 20 out at a
of
and.tion It will also be C. with a residence
thus demonstrating the efficiency of the reac- time of six tours wilh agitation of the reactor. After the
however that SO,- content in cun was
the slurry was
and the fil-
ofthethefiltraterun. Thisratherwouldhigh,nota factor attributable to the size
trate
for the next succasive treatment. nus, thwe
to 25 filtrate are
u Filtrate At, A't and A'",
in • larger wale run.
significant It WII from the reults of Table II
that
In thee runs the wu a final (filtrate) sdution is obtained which has
tntion of the resulting filtrate to a weight Frcent of
by c«ucen• pH of 3.5 to 3.8, a weight ratio of S04-/total
TABLE 1

race. wt. KHjSOd W'. KHW4/ Reuto•r tetiFtture ( •

1
Eumple qm/min„ wtrmk wt. mole Ca
33
out a 703 0.0143 77 80

0.442 "9

0.442 33 38
 0.4% 1.073 33

0.426 D.6t8 1.018 80

0.428 o. ns 0.0139 80

0.0131 1.u.6 62 63 64

0.146 64
00163 77 83

x c 0373 0.0 00128 1.071 63

0.410 0374 l. L02

can,
With Witha•t Wt.
filtrate filtrate on ceal of cent K Overall W'.
mtet in ræovered cent H
•ing 3 2 Oke fttræ in in
Ena.m*e rætors (rrcent} filtrate
4.94 93.6 0.08%
94.4 94 4 00888
02.21 91.8 115 93.6 3,13

1249 91.9 921 OFO%8

ons

0.221 88.7 481 91.9 0.0784

911 6.04

0.198 92.9 6.46 00128

o. 176 a 142 9_6.2 o, 169
x 0.197 0.162 92.3 4.35 93.7 4.13 00170
5.78 0084
Sir Ca -".34 wt. 43M M. (B) S.E. 34.79 wt. 0.24
wt. (C) Ca 33.21 43.48

Fed
of a.L.tfmd'i'.
27 M.
'WI. ions F'i&.nte tx

of nereafter the was

TABLE u
 Re. 29,458
11 12
•continued

Synoptic fit Filt. A"

Filt •te Filt. F l ra e A'
1.4 1.98 1.98

6.16 5.18 5.26

s. 10 2.31 1.96

12.22 14.39 14.36

0089

Filt.
3.2. c.o

iou of 0.055 to 0.07 and a weight ratio of K•/PO,- of Analysis of the synthetic filtrate was:
0.413 to 0.499. They rum therefore illustrate how suc-
c—ive treatmztts with weigh' (punt) 6.16
and calcium 5.10
oxide will substantially reduce the SO,- content while 23 1.4
s'htantially raising the pH of the mixture. 0.94
To further illustrate this •spctt two successive con- Wt. r•tio SO, - "00]
tinuous filtrate treatment runs were made using a syn.
thetic filtrate (analysis This filtrate was subjectd to continuous
resulting Filtrate as with each successively recovered

A'" from theand phosphate rock. ne mtrate Filtrat

run was conunu. 30 e A', Filtrate A" and Fil-
ously •
trate
with CaO. For each run three vessels
were
Table Ill contains the conditions and results
for these runs.
TABLE 111
Run t Run 2 Run 3
Fint Cao
treatarnt tratment
Gnu. gms. filtrate 2.0 2.0 2.4
Fill. rate (ccJmim) n. 24
Wid race (z./min.) 1.22
væls 1/2/3 ( • C.)
Radence time of 1/2/3 (hrs.) 1.3/2.1/3.3

Filtrtre A"'
RAu.Ie Filtrate X Filtrate A"
, SO, (wt. 17.4 53.9

2. Of (wt. 8S.6
3. Wt. K/wt. 6ttrae 0.312
4. WI. SOdwt. åltrate
S. Wt. of K in filtrate 9.3 MO

6. Wt. F•rcent of in (Llin•e 69.1 46.0

7. Wt. ot in filtrate 9.0 83.9
8. pH of filtrate 1.75 2m 3.ss
 TABLE tv

Filtrate Fittmte
+KHSO Fit. FUt. A' Filt. A"'
1.3 23 3.83

6.53 6.26 6.23 6.29

1.28 3.69 249

10.61 13.29 1130 12.55
SOdToca] 0.298 (1158
 Re. 29,458
13
-continued

Alt.

Filtrate A'"
302
6.27 6.26
2.12 1.71
P04*
SO,tTma1 cao 0M2
(5) cecoveriag the gold potassium dihydrogen phos•
A"', the latter of courg the filtrate from which 15 phate from the filtrates and provide a phosphoric
the final is recovered.
From the Table III, it will be obærved that Filtrate acid mother liquor.]
A*" of Run 3 has the most desirable characteristics, i.e. t2. A pr«xas according to claim 1 wherein the potas-

pH of 3,$5, of S04- (on a dry K)lid basis) of

6%, and a weight ratio of K 4./K)4— of 0.414. Actually 20 siatumre hydrogenof sulfate solution is prepared by the reac-

in Run 3, the K* /PO,— ratio could have increaed tion of ptasium chloride and sulfuric acid at e temper•
by increasing the amount of calcium oxide added. Of is dissolved in water to form an aqueous solution of
coutse, the more Cao that is added, the more 2SO'-3Ü C.. the hydrogen chloride is

that will which would bave to ranoved and the resulting potassium hydrogen sulfate
recy• [3. A prc• according to claim 2 wherein the sulfu-
cled to the acidulation reactor. Obviously therefore. the 23 tic acid has a concentration of about

K+/PO,— ratio can also about 10-50%.] to 98% and is

adjusted by the a.mount of
employed to provide an excess of about S to 10 weight
Cao added.
*rcent exces sulfate ion in the reacting mixture.]
Below, in Table IV are blæk diagrams of rwults from
C4. A prgx:ess according to claim 2 wherein the potas•
various batch runs, using phosphate
and CaO. Fot
sium hydrogen sulfate solution contains
4%
thee runs the temperature and residence time were
and about
KHS04.]
C. and 6 hours, respectively. in opration, the synthetic
CS. A prcxes according to claim 1 wherein the fil•
filtrate and the solid additive were put into the vesels 30 trate. from step (4), after renoval of the calcium sulfate*
initially. nea a 30% aqueous KHO, solution was fed
is treated with a
material selected from
into the vesel over a
of 3 hours to minimize
the group consisting of phosphate tricalcium
double salt fornution. As previously explained, the 35 phosphate, dicalcium phosphate, calcium phosphate.

addition of more Cao in either scheme would h•ve

calcium oxide and mixtures thereof, alternatively or

resulted in a higher
weight ratio.
swcesively, at a
From Table NV, it of 40'-W C, to precipi-
will be observed that the
tate additional sulfate ion and partially neutralize the
(Filtrate A"') provid— desirable characteristics
pH 3.0, the content is mixture. and removing the solids to provide a lower•sul•
if 2.0, andthe 40 fate filtrate containing the ptassiurn dihydrogen phos•
K*/PO,— ratio is above 0.40. •nerefore. th«e runs

phate.'
illustrate preferred procedure for conducting the rec•
[6. A præes according to claim 1 wherein the fil•
tion.
trate from step (4), after ranoval of calcium sulfate, is
The invaution has
illustrated herein by reference
concentrated and then cu)led to precipitate the potas-
to certain preferr«l However, it is to be 45 sium dihydrogen phcxphate.'
that the invention is not to
A
according to claim 1 wherein the prod-
thereto as obvious variations thereon will
ap-
uct is
by adding a water•miscible organic
parent to th0E
in the art.
solvent to the filtrate from step (4). allowing the solid
What is claimed is:
ptasium dihydrogen phosphate to precipitate and
(1. A process for the preparation of
dihy- 50 separating the solid product.]
drogen phosphate which compris«;
O, A proces according to claim 7 wherein the or•
(I) contacting phosphate rock or a solubilized form
genic solvent is a lower alkyl alcohol, a lower alkyl
thereof with a sufficient excas of sulfuric Eid to
ketone or mixture thereof,]
drive the reaction to completion at a
of
9. A
for the precipitation of potassium dihy.
40' to
C;
$5 drogen phoshate which comprises:
(2) adding thereto a aqueous solution of po-
(l) contacting phosphate rc:wk or a solubilized form
tassium hydrogen sulfate in sufficient amount to
thereof with a sufficient exc«s of sulfuric acid to
form a rention mixture containing ions of rntas-
drive the reaction to completion at a temperature of
sium dihydrogen phosphate
at a rate
as to
to
C. in a main reactor,
minimize the fomulation of insoluble salts of K)
(2) reEting M)tasium chloride and sulfuric acid in a
KHS04 and CaSOa and under such conditions that
*parate rætor at a temF•ature of 250' to 3m• C
the concentration of dissolved solids in the rection
with removal of the dry hydrogen chloride evolved
mixturc dcx•s not exceed about
and disolving the resulting potasium hydrogen
(3) maintaining the reaction mixture under these aqueous solu-
ditions for fonnation of an easily fdterab)e calcium 65 sulfate with water to form a
tion;
sulfate precipitate;
(3) adding said 10-30% aqueous solution of
(4) removing the solid calcium sutfate from the reac•
hydrogen sulfate to said main reactor in sufficient
lion mixture to provide a filtrate; and
amount to form a rection mixture containing ions
 Re. 29,458
of potassium dihydrogen15 phosphate and at a rate so 16
(1) contacting phæphate ræk or a solubilized form
as to minimize the formation of insolubk salts of thereof with a sufficient excess of sulfuric acid to
KHS04 and CaSO, and under such conditions that
drive the reaction to completion at a temperature of
the concentration of dissolved solids in the reaction 40' to M)' C. in main reactor:

mixture does not exceed

(2) adding t ereto a 10-50% aqueous solulion of po•
(4) maintaining the reaction mixture under theg con- 3 Cassium hydrogen sulfate in sufficient amount to

ditions for fornmation of an easily filterable solid,

calcium sulfate precipitate; formsiu hydrogenreactiona phosphatemixturecontainingandata ionsrate ofso potasto-
(5) removing the solid calcium sulfate from the reac-
tion mixture to provide a filtrate; and CaS04 and under such conditions that the con-
minimize the formation of insoluble salts of KHSO.
(6) said filtrate with a
matericontactiaglselected from the group consisting of phos-10 ture does not exceed about
centration of dissolved solids in the reaction mix-
ph•teate.rock,calciumtricalciumoxideandphosphate,mixtures thereofdicalcium.alternaphos- ditions fot formation of an easily filterable, solid.
C. to precipitate additional sulfate ion and partially (3) maintaining the reaction mixture under these con-
tively ot successively, at a tent*rature of 40'-W 15 (4) removing the solid calcium sulfate from the reac•

calcium sulfate precipitate;

tated solids to provide a filtrate lower in sulfate ion
neutralize the mixture and removing the precipi- (5) contacting said fdtr•te with a calcium•bearing
(7) recovering the solid rx»tassium dihydrogen phos- 20 tion mixture to provide a filtrate;
and containing potassium dihydrogen phosphate; ph•te
mother liquor: and mateül tricalcium phosphate, dicalcium phos-
10. A process wcording to claim 9 wherein the fil• from the group consisting of phos-
phate from the filtrate to provide a phosphoric acid ture thereof, altematively or successively, and
centrated and then cooled to ph*'e, calcium phosphate, calcium oxide ond mix,
(8) rwycling the mother l@unr to the main reactor. ont solution lowered in sulfate ion;
the potassium removing the precipitate solids to provide a resub
trate from step (6), after removal of the nlidst is con- 25 Gal equal volume of a water•miscible organic gob
II. A (6) contacting said resultant solution with a substan-
dihydrogen phosphate. ph*te to
according to claim 9 wherein the fil- vent. allowing the Bk'tassium dihydrogen phoso-
and form solid ptassium dihy-
with a water-micible organic solvent. the *'lid
(7) removing the solid
drogen phosphate;
andtratethenfromthestepsolid(6). after removal of the w)ids is mixed
dihydrogen phos,
is cæovered by filtration. phate to provide a phosphoric acid mother liquor;
sium dihydrogen phosphate is

to precipitate (8) removing the organic solvent; and

drogen phosphate which (9) r"'cling the phosphoric acid mother liquor to the
12. A præess for the preparation of m)tassium dihy• main reactor.
thereof with • sufficient excess of sulfuric acid to 35 [14. A continuous paxes for the preparation and
(1) contacting phosphate

40' to or a Olubihzed form recovery of dihydrogen phosphate from the

rection of ph«xphate or more solubilized form
drive the reEtion to completion at a thereof, sulfuric acid and ptassium hydrogen sulfate,

C. in a main reactor; of
the
(i) contEting
phosphate
tassium hyd ogen sulfate in steps which comprise:

(2) adding thereto a 10-50% Olution of p- 40

amount to form thec«jf with a sufficient excess of sulfuric acid
formsiu dihydrogen phsphate and at a rate or more solubilized

reaction mixture ccmtaining ions of pta.s-

as to ing slurry at • of
 to drive t.he reaction to completion to form a react-

and Caw, and under such 40$ to C. in

minimize the of innluble salts of KHS04

that the con• 45 a main reactor comprising series of reactors with
continuous recycle of a prtion of the reacting
centration of disolved solWs in the reution mix, slurry
ture dcps not exceed
fr«n the last reactors to the first or interme-
diate reactors:
(3)ditionsrnaintainingforformationthereactionofanmixtureeasily filterable. solid, (2) adding thereto a 10-50% aqueous solution of
con- t. hydt0ßD sulfate sufficient amount to
(4) removiag the solid calciurn sulfate from the teac- formasiumruction mixture containing ion of ptassium

calcium sulfate precipitate;

(5) contacting said filtrate with a thehydrformationgenp*Tsphateofinnlubleand atsaltscateof KHS04soastoandminimizeCa.
lion mixture to provide a mtrate;
phate tiooS04 ofanddisolvundedr suchsolidsconditionsinthereactionthatthemixtureconcentradcrs-
material Elected from the group consisting of phos-
tricalcium phosphate. dicalcil.un phos- (3)notrnaintainingexceedabout
phate, calcium phosphate. calcium oxide and mix-
turo thereof, altematively or ditions for fonnation of an easily fiher•ble, solid,
reution mixture under these con•
removing the and
solids to provide a r•ul•
calcium sulfate precipitate;
tant O)ution lower in sulfate ion content; (4) continuously removing a prtion of the reacting
(6) concentrating said reultant Olution and
(5) separating Cbe "lid calcium sulfate from the ract-
to crystallize the solid pot.assium dihydrogen phos- ing slurry to provide a solid
sulfate cake
(7) removing the solid pta.ssium dihydrogen phos- and • filtrate;
plute to provide a phosphoric •cid mother liquor; (6) washing the solid calcium sulfate cake with water
and recycling the wash water to the main reactor;

63
(7) recovering the solid
(8) recycling the mother liquor to the main ce.Etor. dihydrogen phos•
A proces fot the preparation of dihy- phatc from tir filtrate to provide a phosphoric Eid
drogen phosphate which comprises: mother liquor; and
 Re. 29,458
(8) recycling the mother liquor17 to the main ruction.] 18
(1) forming said reacting medium by initially forming a
t IS. A continuous process according to claim 14 mixtuæ of phafphate ræk or a "lubilized form and

wherein the filtrate from step (5), aner removal of the

solid calcium sulfate cake, is (2) adding fherero a 10-50% aqueous solution of pras-
an excess of sulfuric acid;

material selætd from the group consisting of 5

with a calcium-
mixture containing ions of prasium dihy-
sium hßrqen sulfate in suncient amount ro form a
formation of
phosphate in"luble .salts ofKHSO,and CaS04 and
tricalcium phosphate, dicalcium phw dmgen phosphate and at rate
phate, calcium oxide and mixture thereof, alternatively solkd "lids in the reaction mixtureas dæstominimizenotexceedthe

or successively, at a (3) maintaining the reaction mixture under these condi-

precipitate additional sulfate ion and partially neutralize 10 under such conditions ghar the concentration of dis-
of 40' to and

provide a low-sulfate filtrate containing ptasium dihy- sulfate precipitare.

C. to tbns for formation of an easily filtemble calcium

drogen phosphate from the low-sulfate filtrate to pro- sium hßr«n sulfare "lution is prepped by the raction
19. A
the mixture and removing the according ro claim 18 wherein lhe ptas•
mother liquor to the main reutor.) aht 25C-3T C. the

of ptasßum chloride and sulfuric acid at a temperatur of

low-sulfate filtrate containing the ptassium solidsdihydroto-

rhe multing ptagium chloride is remoæd and
drogen phæphate. recovering the solid ptasium dihy• sulfate is dismlped in
with a substantially qual vol-
20
ume of a water-miscible organic to form an aquwus solution of ahat 10-50%.
vide a phosphoric acid mother liquor, and recyclingsolid the IS m A

acid has a conænrragion of üug

[16. A to preipitate according eo claim 19 wherein the sulfuHc
and is from to 98% and is em,
according to claim 14 wherein the

acid motr*r liquor, excu sulfate ion in the reacting mixture.

p10*d to pmvide an
gen phosphate is ofaht S to 10 Night prene
sium phosphate is from mother liqnnr sigm
and cycleddihydrogentostorage for reug in præipitating addi• 25

21. A sullage
the organic Olvent is according to claim 19 wherein the pras-

phoric acid mother liquor is contains 4% HS04

tional ptusium dihydrogen phosphate,totheandmainthe ræ• and

22 A 42% KHSO&
according to claim 20 wherein rhe phospho-
Ell. A pr#— according to claim IS wherein cal- Hc acid flltmte containing pta.ssium dihydrogen phos-phace after
solutionciumoxidefromis stepadded(5)toin thesufficientphæphoricamountacidto rai* the
mateHal
a ofthecalcium"lecedfmmsulfaterhe.is treatedgmupconwith-
pH of the Wlution and fom ptassium monohydrogen
phosphate.' #sphate,
ph«phate, calciumphæphare,oxideanddicalciummixtures

In a the preprarh" ofpøssium alternatiæly or successi*ly. at a tempemluæ of

gen phosphate by the reac&n of phx*ate or a Elubi- 3S 4C-W C, to preipirate additional sulfate ion and
lized form thereof with a reactøn mdium containing tially neurmli* the mi.xtuæ, and removing the solids to

provide a loyr sulfate filtmte containing the prassium

sulfuric acid and prassium hßrqen sulfate at a tempm-

tum of üut 4C to dihßr%en ph*ate
C, æmoring "lid calcium sulfate 23. A
 according to claim 18 wherein after re-
fmm the æsulring reactbn mixture eopmüe a
Of
nøml of calcium sulfate fmm the Jiltmte. it
concen-
ptasium dihßrqen phßphate in
acu and
and then cmled ro precipitate solid ptassium dihy-
recoæring "lid p tassium
the
phæphate
phasphonc acid solution. the
steps compnsing:

45

55

65