United States Patent (19) 11 4,378,342

Manor et al. 45) Mar. 29, 1983

54 PROCESS FOR THE MANUFACTURE OF Primary Examiner-G. Peters
POTASSUMNTRATE Attorney, Agent, or Firm-Schwartz, Jeffery, Schwaab,
75 Inventors: Shalom Manor, Haifa; Moshe Mack, Blumenthal & Koch
Bar-Guri, Kfar Hasidim; Amiad 57 ABSTRACT
Alexandron; Moshe Kreisel, both of The present invention relates to a process for the manu
Haifa, all of Israel facture of potassium nitrate from potassium chloride
73 Assignee: Haifa Chemicals Ltd., Haifa, Israel and nitric acid. According to the invention, potassium
(21) Appl. No.: 249,355 chloride and nitric acid are reacted in an aqueous me
dium at a temperature in the range of between -25 C.
22 Filed: Mar. 31, 1981 to -10 C. From the brine solution obtained after the
30 Foreign Application Priority Data separation of the resulting potassium nitrate, nitric acid
Apr. 20, 1980 (IL) Israel....................................... 59884 is extracted by an organic solvent solution containing at
least one compound selected from the group consisting
51) Int. Cl. ................................................ CO1C 9/04 of ketones having five to ten carbon atoms, straight or
52 U.S. C. ..................................... 423/399; 423/390 cyclic polyethers having molecular weight in the range
58) Field of Search ....................... 423/390, 399, 408; of 100 to 1000, polyalkylene glycols slightly miscible in
22/297 R water and having molecular weight in the range of 1000
56) References Cited to 3000, and organic esters of phosphoric acid, phos
U.S. PATENT DOCUMENTS phonic acid and phosphinic acid, or mixtures thereof, in
an organic diluent which does not substantially extract
1,86,303 7/1931 Thorssell ............................. 423/399 hydrochloric acid. The remaining aqueous solution
2,902,341 9/1959 Baniel et al. . ... 423/399 consists of a substantially nitrate-free brine containing
4,291,007 9/1981 Baniel .................................. 423/390 hydrochloric acid. The NO3-loaded solvent is
FOREIGN PATENT DOCUMENTS washed, the nitric acid as well as the organic solvent
1383684 11/1964 France ................................ 423/399 being respectively recycled in the process. The process
saves appreciable amounts of nitric acid. Optionally,
OTHER PUBLICATIONS pure hydrochloric acid could be obtained from the
"Chem. Abst.", vol. 54, 25,626g. nitrate-free brine, by distillation or by solvent extraction
"Chem. Abst.”, vol. 74, 68,375.j. using butanols or pentanols as extractants.
Solovkin, A. S., "Zh. Neorg. Khim.'; vol. 16; 1971; pp.
272-273. 11 Claims, 2 Drawing Figures
U.S. Patent Mar. 29, 1983 Sheet 1 of 2 4,378,342

I G U R E 1.
ammumumamoan
o
U.S. Patent Mar. 29, 1983 Sheet 2 of 2 4,378,342

F G U R E 2.
 4,378,342 :
2
and energy requirement, which are of course a disad
PROCESS FOR THE MANUEFACTURE OF vantage of the process.
POTASSIUM NITRATE The organic solvents used in the above process are
specific for acids, i.e. salts are not extracted, but they
The present invention relates to the manufacture of 5 suffer from the fact that they are not selective for hy
potassium nitrate by the reaction of potassium chloride drochloric acid, so that nitric acid is coextracted. This is
with nitric acid. More specifically, the invention relates another disadvantage of the process, which requires an
to the manufacture of potassium nitrate, wherein a sub additional treatment of the solution, for example, treat
stantially complete recovery of the nitric acid is ment with formaldehyde to eliminate its nitrates con
achieved and, optionally, potassium-free aqueous solu 10 tent. In addition to the fact that this additional treatment
tions of hydrochloric acid, of relatively high concentra consists a nuisance for the entire process, it also requires
tion, are obtained as by-product. reagents and thus effects to a certain extent the costs of
Potassium nitrate is now fully recognized as one of production. The organic solvents claimed in the above
the most important potassium fertilizers which contains mentioned ofU.S. Patents are selected from the group
46.58% potash (expressed as K2O) and 13.6% nitrogen 15 consisting aliphatic monohydric alcohols having four
(N). As a chemical compound it is neutral and its nitro to The five carbon atoms.
gen-potassium oxide (N:K2O) ratio of approximately lized atprocess of potassium nitrate manufacture as uti
Haifa Chemicals plant is based on the conver
1:3.4 is fixed. Pure potassium nitrate is only slightly sion of potassium
hygroscopic and less subject to caking than pure potas 20 ing amyl alcohol aschloridethe
into potassium nitrate utiliz
organic solvent.
sium chloride. Potassium nitrate is also less hygroscopic Although the process operates smoothly, being quite
than other nitrate salts used as fertilizer.
attractive from an
Most of the potassium nitrate made until 1967 was from two main disadvantages: economic point of view, it suffers
obtained from reacting sodium nitrate with potassium
chloride. The potassium nitrate thus manufactured was 25 (1)reaction The excess of reaction brine accumulating in the
system contains about 6% nitric acid
aimed principally at industrial applications because of which has to be eliminated by an additional treat
its high cost. In 1968 a plant was erected at Haifa Chem ment, and
icals Ltd. (Haifa, Israel) to produce potassium nitrate (2) the low concentration of the hydrochloric acid
from potassium chloride and nitric acid, using solvent by-product obtained.
extraction technique in accordance with Israeli Pat. 30 In the last twenty years several theoretical papers
Nos. 9539 and 9660 and their corresponding U.S. Pat. appeared in the literature on the preferential extraction
Nos. 2,902,341 and 2,894,813. According to these pa of low ionization acids such as nitric acid, over highly
tents the process involves the reaction: ionized acids such as hydrochloric acid. Thus, for in
KC1--HNO3)KNO3--HC stance, in determination of extractions carried out for
The essence of the process lies in the removal of HCl 35 nitric acid and hydrochloric acid separately (Baldwin et
from the reaction mixture, thus driving the equilibrium al., J. Phys. Chem. 63, 118, 1959) in a system of tributyl
to the right. This is accomplished by contacting the phosphate and water containing one of said mineral
reaction mixture with an organic solvent, partially mis acids, it was found that the largest distribution coeffici
cible with water, into which the HCl formed is ex ent measured between an organic and aqueous phase is
tracted. The reactants, nitric acid and potassium chlo for HNO3 followed by HCl, Two different mechanisms
ride are fed to the reaction, substantially in stoichiomet were proposed:
ric proportions. In the presence of a solvent, the trans (a) HNO3 displaces water from tributyl phosphate
formation of KCl to KNO3 is complete and takes place and is extracted due to the formation of a specific
virtually in the solid phase. For processing conve salt complex, and
nience, however the presence of a certain quantity of 45 (b) HCl adds water to tributyl phosphate and its ex
aqueous phase is preferable, this aqueous phase being an traction is usually difficult and strongly influenced
acid-containing brine at a level dependent on the reac by hydration phenomena.
tion temperature and the acidity of the reaction solvent, Another review (Irving et al., J. Inorg. Nucl. Chem.,
which is saturated with respect to KCl and KNO3. The 10, 306, 1959) compared the extraction of HCl versus
water balance over the entire process is so adjusted that SO HNO3 respectively, with, tributyl phosphate and kero
the quantity of aqueous phase (brine) remains constant. sene mixtures from aqueous solutions. The coefficients
The preferred reaction temperature is in the range of 0 of distribution reported for, HNO3 and HCl separately,
C. to 10 C., said patent mentioning that the reaction with various mixtures of tributyl phosphate: kerosene,
between the KCl and HNO3 and the extraction are shown that in all cases, HNO3 extracts better than HCl.
carried out at temperature not exceeding 63' C. The 55 The above references on the preferential extraction of
conversion of KCl into KNO3 is carried out in a series one acid over another which might have some impor
of stirred reactors, the reactants, recycle solvent and tance from a theoretical point of view, should be con
recycle brine being fed to the first vessel. The three sidered as part of the general background but without
phase reaction mixture consisting of (1) solid potassium any teaching on its possible use from a mixture of these
nitrate; (2) hydrochloric acid and nitric acid-charged mineral acids and, particularly, in a complex technolog
solvent; and (3) the brine, are fed to a decanting vessel. ical system such as prevails in the manufacture of potas
The solvent phase is separated and is passed to the liq sium nitrate.
uid-liquid contacting system to remove as by-product It is an object of the present invention to provide a
hydrochloric acid in the form of a very dilute aqueous simple process for the manufacture of potassium nitrate
solution having a concentration of between 5 to 8% by 65 from potassium chloride and nitric acid, the reaction
wt. In order to become a saleable product, this hydro between said reagents being carried out in an aqueous
chloric acid requires substantial concentration in a mul medium in the absence of an organic solvent. It is an
tiple effect evaporator, but this means additional costs other object of the present invention to provide a pro
 4,378,342
3 4.
cess for the manufacture of potassium nitrate from po e.g. the production of vinyl chloride monomer, wherein
tassium chloride and nitric acid, wherein substantially the presence of small amounts of foreign impurities does
no losses of nitric acid are encountered. It is yet another not interfere the reactions. When pure hydrochloric
object of the present invention to provide a simple pro acid is required, this can be easily accomplished by
cess for the manufacture of potassium nitrate from po distillation from said nitrate-free brine, as known in the
tassium chloride and nitric acid wherein the nitrate-free art. Since the brine entering into the distillation system
brine may be further processed to obtain a substantially is nitric acid-free, no particularly corrosion problems
potassium-free, relatively concentrated solution of would be expected in the equipment utilized for said
aqueous hydrochloric acid by-product. distillation.
Thus the invention consists in a process for the manu O According to another embodiment, the hydrochloric
facture of potassium nitrate from potassium chloride acid present in the NO3"-free brine obtained in step (c),
and nitric acid, which comprises the steps of: can be recovered by solvent extraction, using an or
(a) carrying out the reaction between potassium chlo ganic solvent possessing a selective extraction power
ride and nitric acid in an aqueous medium at a temper towards hydrogen chloride. The literature is quite
ature in the range of between -25 C. to +10 C., 15 abundant with such solvents, preferred solvents accord
said reactants being in the range of 0.9 mole of HNO3 ing to the present invention being selected from the
per mole of KCl and up to 3 moles of HNO3 per mole group consisting of primary, secondary and tertiary
of KCl; alcohols which are sparingly soluble in water. Option
(b) separating the crystals of potassium nitrate from the ally, these organic solvents are used in conjunction with
resulting brine containing K+, Cl-, Hit and NO3. 20 an inert organic diluent. The hydrochloric acid-loaded
ions; solvent can easily be washed with water, thus obtaining
(c) extracting the nitric acid from the brine obtained in relatively concentrated aqueous solutions of hydrochlo
step (b) by an organic solvent solution containing at ric acid. This embodiment has a particular advantage,
least one compound selected from the group consist by saving considerable amounts of fuel, which are re
ing of ketones having five to ten carbon atoms, 25
quired for concentration of aqueous solutions of hydro
straight or cyclic polyethers having molecular
weights in the range of 100 to 1000, polyalkylene chloric acid. A person skilled in the art, will select the
glycols slightly miscible in water and having molecu particular method according to the commodities and
lar weights in the range of 1000 to 3000 and phospho facilitates available at the plant producing the potassium
rus containing organic compounds such as deriva 30 nitrate.
tives of phosphoric acid, phosphonic and phosphinic One of the main features which characterizes the
acid, and phosphine oxide derivatives, in an organic improved process for the manufacturing of potassium
diluent which does not extract hydrochloric acid, nitrate according to the present invention, is the extrac
obtaining a NO3-loaded solvent extract and produc tion of the nitric acid from the brine resulting after the
ing a NO3-free brine containing hydrochloric acid, 35 separation of the potassium nitrate,
and Suitable classes of solvents are: ketones having be
(d) washing the NO3-loaded solvent extract, the re tween five and ten carbon atoms, straight or cyclic
covered aqueous nitric acid being recycled into step polyethers having molecular weight in the range of 100
(a). to 1000, polyalkylene glycols slightly miscible in water
The potassium nitrate product is obtained as crystals 40 and having molecular weight in the range of 1000 to
in a pure form without any occluded impurities. 3000 and phosphorus-containing organic compounds
One of the main advantages of the process is the fact such as derivatives of phosphoric acid, phosphonic
that substantially no losses of nitric acid are encoun acid, phosphinic acid and phosphinic oxide derivatives.
tered, any unreacted nitric acid going out from the Typical examples of such solvents are methyl isobuty
reaction system, being quantitatively recovered and 45 ketone, methyl cyclohexanone, methyl ethyl ketone,
recycled to the process after washing the solvent ex methyl propyl ketone, dibutyl ether, diethylene glycol
tract in step (d). The above advantage is contrary to the di-butyl ether, polypropylene glycol (M.W. 2000 ),
process described in said U.S. Patents, wherein any tributyl phosphate, trioctyl phosphine oxide, tributyl
unreacted nitric acid should be eliminated, e.g. by its phosphine oxide, triphenyl phosphine oxide, hydrogen
being destroyed with the aid of chemical reagents. An 50 dibutyl phosphate etc. It could be also preferable to
other advantage of the process according to the present utilize these solvents in conjunction with an inert or
invention is the fact that the subsequent handling of the ganic diluent such as toluene, benzene, kerosene and,
NO3-free brine is more convenient than the original particularly, dearomatized kerosene.
brine with the nitric acid which is very corrosive. The One of the most preferred solvents for the extraction
process can be carried out either continuously or in a 55 of the nitrate values from the brine resulting after the
batch manner. If the process is performed batchwise, separation of the potassium nitrate is selected from the
either complete or partial conversion of the potassium trialkyl phosphates, in particular suitable being tributyl
chloride to potassium nitrate may be obtained, depend phosphate. This solvent fulfills practically all require
ing upon the specific case and the reaction conditions ments of an organic solvent for an industrial purpose
employed. In the case of a partial conversion, the mix such as: almost complete water insolubility, low vapor
ture of potassium nitrate and potassium chloride may be pressure and availability at relatively low costs. How
commercially used as a fertilizer. ever, tributyl phosphate being an organic ester could be
The resulting brine after extraction obtained in step conceived to undergo an easy hydrolysis in the very
(c), contains appreciable amounts of hydrochloric acid concentrated acidic brine which prevails in the system
and being free of nitric acid should be considered a 65 according to the present invention. It has been unex
valuable starting material for various processes. Typical pectedly found, that tributyl phosphate is almost com
examples of such processes are the production of cop pletely stable when utilized with an inert organic dilu
per oxychloride or various oxychlorination reactions ent, such as dearomatized kerosene, at a temperature
 4,378,342
5 6
range of between 0° C. and 25 C. which might be en TABLE 4.-continued
countered in the process. Stability tests for TBP at 23° C. by Infrared Spectroscopy (IR).
The stability of solutions of tributyl phosphate (TBP) (The composition of the aqueous brine was as in Table 2).
in dearomatized kerosene under the working conditions Diluent 1030 cm-l 1260 cm
of the process according to the present invention, has dearomatized days of contact
been demonstrated by direct methods such as Gas-Liq kerosene O 4. 10 O 4. O
uid Chromatography (GLC) and Infrared Spectros 30% TBP 52 52 S4 20 20 22
copy (IR) as well as by indirect methods such as ab
sence of butanol and phosphate ion decomposition
products in the aqueous brine resulting from the pro 10 The conclusion which can be drawn from the above
CeSS. Tables is that TBP is completely stable in contact with
The stability results are illustrated in the following the concentrated acidic aqueous brine solution even
Tables 1, 2, 3 and 4 which summarize GLC and IR data after prolonged periods of contact.
with TBP with or without diluents, after having been From the practical point of view the range of 10% to
contacted under constant mechanical stirring with 15 30% TBP in dearomatized kerosene is preferable;
aqueous acidic brine at 0° C. and at 28 C., the volume higher concentrations will cause difficulties in phase
ratio of organic to aqueous phases being kept at 1:10. separations and handling.
The above tests were followed by testing for butanol Various modifications or alterations to the scheme
and phosphate ion in the conjugated aqueous phase, the 20 presented can be envisaged without being outside the
results for both being negative for all periods of contact. scope of the present invention. Thus in the reaction
system, the concentration of the nitric acid can be in a
TABLE 1.
very broad range of between 20% to 75% (wt. percent).
Of course, a higher concentration will be preferred in
Stability tests for TBP at 0° C. by Gas Liquid Chromatography. order to deal with lower volumes of reaction products
Composition of aqueous phase (in g/l) 25 and also to obtain a higher concentration of hydrochlo
% Tributyl phosphate after contact days
ric acid. On the other hand, lower concentrations of
Diluent O 3 5 10 17 27
nitric acid which might be available in a plant, could be
successfully utilized in the process according to the
None 98 97 98 98 98 95 present invention.
30% (by vol.) in 30 It has been found according to the present invention,
dearomatized kerosene 32 32 31 29 29 29
that a small number of stages will be sufficient to com
pletely extract the nitric acid from the brine as obtained
TABLE 2. after the removal of potassium nitrate, containing nitric
Stability tests for TBP at 23' C. by Gas Liquid Chromatography. acid and hydrochloric acid together with the unreacted
Composition of aqueous phase (in g/) 35 potassium chloride. This is a result of the relatively high
H: 7.6: K: 26.2: Cl: 205:NO: 153. distribution coefficients which exist in the system. In the
Diluent: dearomatized % Tributyl phosphate after contact days following Table 5 are summarized some equilibrium
kerosene O 7 10 concentrations obtained in the extraction of the nitric
10% TBP 10 11.5 9.5 + (+not determined) acid content from actual brines obtained in the process
20% TBP 20 20 20 20 according to the present invention, by tributyl phos
30% TBP 30 30 - 27 phate in dearomatized kerosene (25% by volume) as
diluent.
TABLE 3. TABLE 5
Stability tests for TBP at O' C. by Infrared Spectroscopy (IR). 45 Distribution coefficients (D) of NO3 and Clt at equilibrium
(at room temperature).
(The composition of the aqueous brine was as in Table 1).
IR absorbance. The composition of the organic phase: TBP in dearomatized
1030 cm 1260 cm-l kerosene, at various concentrations.
Frequency days of contact:
The composition of the aqueous phase: 7.7 g/1 Hit; 209 g/1 Cl;
138 g/1NO3 and 20 g/1 K.
Diluent O 3 5 10 17 27 0 3 S 10 17 27 50
None 76 75 77 76 74 57 54 54 54 55 D = concentration in organic phase
30% concentration in aqueous phase
(by vol.) in Concentration of
dearomatized
kerosene 58 57 58 61 53 57 29 28 28 30 22 28 TBP (by vol.) DC- PNO
30% 55 10% 0.033 0.10
(by vol.) in 20% 0.030 0.15
chloroform 76 76 78 76 74 77 50 60 58 56 47 57 30% 0.026 0.22
(The stretching frequency of 1030 cm is characteristic of the P-O bond and that
of 1260 cm is characteristic of the P-0-C bond (which exist in TBP) The above figures show clearly the preferential ex
60 traction of the nitrate ion by the TBP over the chloride
TABLE 4. ion. Therefore this method could be successfully ap
Stability tests for TBP at 23° C. by infrared Spectroscopy (IR). plied for the removal of appreciable amounts of NO3
(The composition of the aqueous brine was as in Table 2). ions codissolved with Cl" ions in aqueous acidic brine.
Diluent 1030 cm 1260 cm One of the advantages of the present invention is the
dearomatized days of contact 65 fact that inexpensive plastic material such as ordinary
kerosene 0 4. 10 O 4. 10 polyvinyl chloride (P.V.C.) can be used as material of
10% TBP 24, 24 25 6 7 7 construction for the equipment. However, tributyl
20% TBP 40 41 43 14 4. 5 phosphate or ketones are known as plasticizers so that
 4,378,342
7 8
PVC would appear to be unsuitable and a more expen removed from stream (6). The aqueous phase contain
sive construction material would be required. It was ing mainly hydrochloric acid, nitric acid and potassium
discovered by the present inventors, that the incorpora salts is conveyed through stream (7) into a multi-stage
tion of a pentanol or a butanol e.g. amyl alcohol, in the liquid-liquid contactor 8, wherein a washed selective
range of 1 part of TBP (or ketone) to 7 parts butanol or organic solvent solution is also introduced through
pentanol to 12 parts of TBP (or ketone) to 1 part buta stream (14). The resulting aqueous brine containing
nol or pentanol, has a stabilizing effect on the PVC. mainly hydrochloric acid and potassium salts, is con
The temperature range for carrying out the reaction veyed through stream (9) and enters into another multi
is between -25 C. and -10° C. and preferably be stage liquid-liquid contactor 10, wherein it comes in
tween -20° C. and 0° C. The optimal conditions will be 10 contact with another washed organic solvent solution
selected by varying the ratio between the reactants and (16) which extracts only the hydrochloric acid leaving
the temperature, in accordance with the required purity the potassium salts in the aqueous solution. The aqueous
of the solid product. Thus, for instance, a lower temper phase leaving the liquid-liquid contactor 10 through
ature of about -20°C. will lower the rate of potassium stream (11) contains mainly potassium salts and is con
nitrate which will precipitate, while the upper tempera 5 veyed to another multi-stage liquid-liquid contactor 12
ture limit, will be determined by the solubility data. The wherein it contacts the nitric acid-loaded solvent
reaction time is quite short and can vary in accordance (stream 5) resulting from the liquid-liquid contactor 8.
to the other parameters of the system, generally being in The resulting aqueous phase (stream 13) consists of a
a range of about 5 to 60 minutes. solution containing potassium salts and nitric acid
If a higher purity of the potassium nitrate product is 20
which are recycled into the cooled reaction vessel 3.
desired, it would be preferable to wash the crystals The organic solvent solution possessing a selective ex
coming out from step (b) with an aqueous solution satu tractability towards the hydrochloric acid enters
rated with potassium nitrate. This additional treatment through stream (16) into the liquid-liquid contactor 10
will remove the adhering brine, the crystals of potas wherein it extracts the hydrochloric acid. The organic
sium nitrate being subsequently separated by a centri 25
solvent extract loaded with the hydrochloric acid enters
fuge. through stream (17) in another liquid-liquid contactor
While the invention will now be described in connec
tion with two preferred embodiments as illustrated in 18, wherein by washing with water (stream 19) it results
FIGS. 1 and 2, wherein two block diagrams describing in a substantially potassium-free, relatively concen
the process are presented, it will be understood that it is 30 trated aqueous solution of hydrochloric acid (stream 20)
not intended to limit the invention to these particular as by-product.
embodiments. FIG. 1 represents in a schematic manner Taking in account that various streams at relative low
a block diagram of one embodiment according to the temperatures are involved in the system, it is suggested
present invention, wherein a NO3-free brine contain for energy considerations and assistance in phase sepa
ing hydrogen chloride is obtained as by-product to 35 ration, to incorporate also heat exchange such as for
potassium nitrate. Streams of nitric acid () and potas example between stream (7) and stream (13).
sium chloride (2) are introduced into a cooled reaction The invention will be hereafter described by the fol
vessel 3, wherein the reaction between the two reagents lowing Examples, it being understood that it is pres
takes place. The reaction products in the aqueous phase ented only for a better understanding of the invention.
are conveyed through stream (4) into a decanter vessel In the Examples the various streams mentioned in the
5, wherein wet crystals of potassium nitrate, with or block diagram are referred to, the concentrations being
without potassium chloride depending on reaction pa given in wt. percent unless otherwise stated.
rameters, are separated and wet crystals of potassium EXAMPLE 1 (see FIG. 1)
nitrate product are removed from stream (6). The aque
ous phase containing mainly hydrochloric acid, nitric 45 In the following Example, the step of nitrate ion
acid and small amounts of potassium salts, is conveyed removal will be illustrated in a more detailed manner
through stream (7) into a multi-stage liquid-liquid con presenting the various concentrations obtained at equi
tactor 8, wherein a washed selective organic solvent librium, starting with an actual brine solution after re
solution for NO3 is also introduced through stream moval of the potassium nitrate crystals, in a continuous
(12). The resulting brine obtained as stream (9) is sub 50 run on a laboratory scale.
stantially free from any nitrate ion and contains hydro An amount of 90 ml/h of an aqueous acidic brine
gen chloride as main constituent. The organic phase (stream 7) leaving the decanter vessel 5 and a suitable
stream (11) loaded with essentially nitric acid, enters heat exchanger, entered a solvent extraction battery 8
into a multi-stage liquid-liquid contactor 10, wherein a consisting of 3 mixer-settlers arranged in series. This
water stream (14) is also introduced. The aqueous phase 55 stream was contacted with about 470 ml/h of a 25%
stream (13), consisting of substantially nitric acid, is solution of tributyl phosphate in dearomatized kerosene
returned to reaction vessel 3. (stream 12). The nitric acid-loaded solvent (stream 11)
FIG. 2 represents in a schematic manner, a block was washed in another solvent extraction battery (10)
diagram of another preferred embodiment wherein the consisting of 4 mixer-settlers (arranged in series) by
hydrochloric acid is recovered by solvent extraction. stream (14) of about 130 ml/h of tap water. The aqueous
Stream of nitric acid (1) and potassium chloride (2) are phase (stream 13) consisted essentially of nitric acid (to
introduced into a cooled reaction vessel 3, wherein the be recycled in the process) whereas the aqueous stream
reaction between the two reagents takes place. The (9) leaving the battery was substantially nitrate-free and
reaction products in the aqueous phase are conveyed contained 230 g/l of HCl and 18 g/l of potassium ions.
through stream (4) into a decanter vessel 5 wherein wet 65 In the following Table 6 are presented the analyses of
crystals of potassium nitrate, with or without potassium the individual ions, in order to illustrate the variation of
chloride, depending on reaction parameters, are sepa concentrations within the extracting and washing bat
rated and wet crystals of potassium nitrate product are teries.
 4,378,342
9
TABLE 6.
Concentrations in g/l of individual ions in the extraction and
washing batteries.
Organic phase Aqueous phase
Stage ion NO3 Cl K H+ NO3- Cl- K Hit
W 0.43 traces 0.02 4.14 traces 0.07
W2 2.25 traces 0.05 21.7 traces 0.38
W3 7.43 0.5 o 0.3 50.9 2.5 m 0.9
W 16.3 0.36 0.28 90.8 5.3 o .6S
Stream 7 1330 208.4 5.6 7.48
El 25.5 1.8 0.47 11.5 236. 15.6 6.3
E2 9 10,3 0.45 0.28 239.6 15.6 6.2
E3 0.19 24.0 0.66 OOS 239.6 18.3 6.2

The Table above, presents each aqueous phase in

equilibrium with its conjugated organic brine. The ex 15
traction stages are denoted by E1 to E3 and the washing circulating brine (stream 11) was contacted with the
stages by W1 to W4 respectively. Thus the organic NO3-loaded tributyl phosphate solution (stream 15)
phase of stage W1 represents the washed organic phase and the resulting solution which contained about 19%
(stream 12); the aqueous phase of stage W.4 represents HNO3 was recycled to the process (stream 13). The
stream (13); the organic phase of stage E1 represents 20 HCl-loaded iso-amyl alcohol from the liquid-liquid con
stream (11) and the aqueous phase of stage E3 represents tactor 10, was washed by 2.9 m3/h of water (stream 19),
the hydrochloric acid solution (stream 9) leaving the the resulting stream (20) consisted of 3.2 m/h of an
system. From the above concentrations at equilibrium, aqueous solution which contained 480 kg/h of hydro
it appears clearly the high efficiency of nitrate ion ex gen chloride and was substantially free of nitrate and
traction over the chloride ion, so that a small number of 25 potassium ions.
stages will be sufficient to free the aqueous acidic brine EXAMPLE 4 (see FIG. 1)
of practically all of the dissolved nitrate ions.
An amount of 1000 kg/h of commercial (98%) potas
EXAMPLE 2 (see FIG. 1) sium chloride (stream 2) was fed into a reactor 3 kept at
An amount of 1000 kg/h of commercial (98%) potas 30 0' C., together with 1330 kg/h (stream 1) of 60% nitric
sium chloride (stream 2) was fed into a cooled reaction acid. The reaction mixture was continuously conveyed
vessel at about -20° C., together with 1310 kg/h of from the reactor 3 as stream (4) to a solid liquid separa
60% nitric acid (stream 1) and stream (13) consisting of tor 5. A stream of solid potassium nitrate was separated,
a recycled aqueous solution of nitric acid and minor which upon washing and drying, yielded 1290 kg/h of
amounts of hydrochloric acid. The resulting reaction 35 KNO3 of 99% purity. In addition to that a liquid phase
mixture was decanted in vessel 5 and 1270 kg/h of crys (stream 7) resulted from the separator 5 and was con
tals of potassium nitrate (on dry basis) were obtained in tacted with a stream (12) of washed commercial methyl
stream (6). The aqueous brine (stream 7) was contacted iso-butyl ketone (MIBK) in a series of six mixers-set
with a 20% (by vol) of a solution of tributyl phosphate tlers, at a phase volume ratio of 1:1.3 (aqueous:organic).
in dearomatized kerosene, the phase volume ratio being The extracted aqueous stream (9) leaving the extrac
4:1 (organic:aqueous), the nitrate ion being extracted tion step had an hourly throughput of 2100 liters and
into the organic phase. The depleted brine (stream 9) contained 20% HCl, 1.3% KCl and 2% MIBK (dis
amounting 2280 kg/h contained 20% (by wt.) hydro solved therein). This stream was then freed of its MIBK
chloric acid, 1.8% of potassium chloride and minor content by conventional azeotropic distillation, yielding
amounts of sodium chloride. The loaded organic phase 45 an azeotrope containing 76% of MIBK which was re
(stream 11) was washed by means of 1240 kg/h of water turned to the extraction stage. The loaded-MIBK phase
(stream 14). The aqueous solution obtained (stream 13) (stream 11) leaving the extraction battery 8, was washed
which contained 18.5% nitric acid and 5.5% hydro by means of 1300 l/h of water (stream 14) in a washing
chloric acid, was recycled to the reaction vessel via an step 10, the volume ratio between the phases being 2.1:1
intermediate heat exchange with stream (7). 50 (organic:aqueous). The aqueous stream (16) leaving the
EXAMPLE 3 (see FIG. 2)
washing step, contained 20% HNO3 and 0.4% of HCl,
and was recycled to the reaction stage.
An amount of 1000 kg/h of commercial (98%) potas We claim:
sium chloride (stream 2) was fed into a cooled reaction 1. A process for the manufacture of potassium nitrate
vessel at about 0°C., together with 1380 kg/h (stream1) 55 from potassium chloride and nitric acid, which com
of 60% nitric acid and a stream (13) of 2050 kg/h aque prises the steps of:
ous phase containing 400 kg/h of nitric acid and 64kg/h (a) carrying out the reaction between potassium chlo
of K (potassium salts). Crystals of potassium nitrate ride and nitric acid in an aqueous medium at a
amounting to 1350 kg/h with a purity of 98.5%, were temperature in the range of between -25 C. to
obtained in stream (6). The brine stream (7) was washed -10° C. said reactants being in the range of 0.9
by a solution of 6.4 m/h of tributyl phosphate in kero mole of HNO3 per mole of KCl and up to 3 moles
sene (30% by vol.), the ratio between the phases being of HNO3 per mole of KCl,
about 2.5:1 (organic:aqueous). (b) Separating the crystals of potassium nitrate from
The brine stream (9) entered a liquid-liquid contactor the resulting brine containing K+, Cl, Hh and
10 wherein it was contacted with 7.5 m/h of washed 65 NO3 ions,
iso-amyl alcohol containing 0.5 m3/h water. The aque (c) Extracting the nitric acid from the brine obtained
ous phase containing the potassium salts (stream 11) was in step (b) by an organic solvent solution contain
distilled in vacuo, to recover the iso-amyl alcohol. The ing at least one compound selected from the group
 11
4,378,342
2
consisting of ketones having five to ten carbon 5. A process for the manufacture of potassium nitrate
atoms, straight or cyclic polyethers having molecu according to claim 1, wherein the reaction temperature
lar weight in the range of 100 to 1000, polyalkylene is in the range of -20° C. and O' C.
glycols slightly miscible in water and having mo 6. A process for the manufacture of potassium nitrate
lecular weight in the range of 1000 to 3000 and according to claim 1, wherein the organic solvent solu
organic esters of phosphoric acid, phosphonic and tion for extracting the nitric acid contains at least one
phosphinic acid or mixtures thereof in an organic compound selected from: methyl isobutyl ketone, me
diluent which does not substantially extract hydro thylcyclohexanone methyl ethyl ketone, methyl propyl
chloric acid, obtaining a NO3-loaded solvent ketone.
extract and producing a NO3-free brine contain 10 7. A process for the manufacture of potassium nitrate
ing hydrochloric acid, and according to claim 1, wherein the organic diluent is
(d) Washing the NO3-loaded solvent extract, the selected from toluene, dearomatized kerosene and ben
Zee,
recovered aqueous nitric acid being recycled into
step (a). 8. A process for the manufacture of potassium nitrate
2. A process for the manufacture of potassium nitrate 15 according to claim 1, wherein significant amount of
according to claim 1, wherein hydrochloric acid is ob energy is saved by heat exchange of the cold streams
tained from the NO3-free brine resulted in step (c), by with other streams of the process running at ambient or
higher.
contacting said brine with an organic solvent compris 9. A process for the manufacture of potassium nitrate
ing at least one of the compounds selected from the 20 according to claim 1, wherein the equipment used is
group consisting of primary, secondary and teriary made from polyvinyl chloride.
alcohols sparingly soluble in water, said organic solvent 10. A process for the manufacture of potassium ni
being optionally admixed with an organic diluent, and trate according to claim 9, wherein butanol or pentanol
contacting the hydrochloric acid-loaded solvent with is present in the range of 1 part tributyl phosphate to 7
water, recovering a concentrated hydrochloric acid 25 parts butanol or pentanol to 12 parts of tributyl phos
solution. phate to 1 part butanol or pentanol.
3. A process for the manufacture of potassium nitrate 11. A process for the manufacture of potassium ni
according to claim 2, wherein the organic solvent solu trate according to claim 1, wherein the organic solvent
tion to extract the hydrochloric acid is selected from solution for extracting the nitric acid contains at least
butanols and pentanols. 30 one compound selected from: tributyl phosphate, trioc
4. A process for the manufacture of potassium nitrate tyl phosphine oxide, triphenyl phosphine oxide, tributyl
according to claim 1, wherein hydrochloric acid is ob phospine oxide and hydrogen dibutyl phosphate.
tained from the brine resulting in step (c) by distillation. is a s

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