9

The Extractive Distillation Process

for Nitric Acid Concentration
Using Magnesium Nitrate

J. G. SLOAN
Imperial Chemical Industries Ltd., Organics Division, Stevenston, Ayrshire, Scotland,
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KA20, 3 LN
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

Enhancement of relative volatility in the nitric acid-water sys­

tem by the presence of magnesium nitrate as dissolved salt
component makes possible an economic and reliable process
for making high strength nitric acid. The process has a con­
tinuous extractive distillation stage producing 90% HNO 3

vapor which is further rectified to nearly 100% concentration.

Diluted magnesium nitrate solution from the still base is read­
ily reconcentrated to the preferred feed strength of 72%
Mg(NO ) by vacuum evaporation. Steam provides process
3 2

heat supply for the distillation and evaporation sections, some

2.5 parts being needed to concentrate one part HNO from 3

60% to 99.5% concentration. Extended commercial opera­

tion has confirmed that this is a robust and satisfactory pro­
cess.

T hough there are c o m m e r c i a l processes for the p r o d u c t i o n of h i g h

strength n i t r i c a c i d (98-100 w t % HNO3) directly f r o m a m m o n i a using
oxygen, the b u l k of such a c i d is m a d e f r o m the weaker aqueous solutions, ca. 60
w t % H N O 3 , w h i c h are p r o d u c e d b y conventional air oxidation plants. Since
the nitric acid-water system has an azeotrope of 68.2 w t % H N O 3 at 760 m m H g ,
concentration of weaker acids b y direct distillation is not possible. F o r m a n y
years, w h e n a m m o n i a oxidation plants operated at atmospheric pressure a n d
produced acid containing 45-55 w t % H N O 3 , the h i g h strength product required
by the explosives and dyestuffs industries was made b y extractive distillation with
sulfuric a c i d as the t h i r d component. T h e a m m o n i a oxidation plant was thus
associated w i t h a sulfuric acid concentration plant i n w h i c h essentially the water
present i n the original aqueous nitric acid was removed, using such commercial

128

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 9. SLOAN Extractive Distillation Process 129

a c i d concentrating units as the P a u l i n g Pot, G a i l l a r d tower, d r u m concentrator,

or M a n t i u s concentrator. Such processes still f i n d c o m m e r c i a l acceptance.
As a m m o n i a oxidation technology developed, it became possible to produce
aqueous weak nitric a c i d of super-azeotropic composition, t y p i c a l l y 6 9 - 7 3 w t %
HNO3. Such acid is theoretically distillable to higher concentration i n one step.
At the same time, acid of azeotropic composition is returned to the plant absorbers;
the higher the weak a c i d concentration, the lower is the recycle of azeotrope.
Extractive distillation processes are still w i d e l y used for n i t r i c a c i d con-
centration. Because the operational and maintenance problems associated w i t h
sulfuric a c i d concentration plants are considerable, and their capital cost sub-
stantial, attention has been directed p e r i o d i c a l l y to the use of extractive agents
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other than sulfuric a c i d . Phosphoric a c i d (I) acts like sulfuric a c i d but poses
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

similar problems of reconcentration. Solutions of certain m e t a l l i c salts, i n par-

ticular metallic nitrates, p e r m i t similar enhancement of relative volatility a n d
are readily reconcentrated i n straightforward evaporation e q u i p m e n t , o f f e r i n g
the possibility of a compact integrated concentration process.
Extractive D i s t i l l a t i o n of N i t r i c A c i d i n the Presence of M e t a l Salts. The
nitrates of magnesium (2,3, 4), l i t h i u m (4,5), potassium, c a l c i u m (3, 4), sodium,
a l u m i n u m , iron (3), b a r i u m (4), and zinc (6) have been studied for this purpose,
and i n general terms it has been f o u n d that:

1. Potassium, s o d i u m a n d b a r i u m nitrate produce very little alteration i n

the relative volatility of nitric a c i d - w a t e r .
2. Magnesium, zinc and l i t h i u m nitrates have a m u c h greater effect on the
equilibrium.
3. C a l c i u m nitrate has less effect, at a given concentration, than magnesium,
zinc, or l i t h i u m but, b e i n g more soluble, it can have greater overall effect.

Table I summarizes the effect of such nitrates on the azeotropic composition

i n the nitric a c i d - w a t e r system. A d d i t i o n of potassium nitrate increases the
azeotropic composition, but other nitrates decrease it, the a m o u n t b y w h i c h the
azeotrope is displaced b e i n g proportional to the amount of nitrate added. The
azeotrope is e l i m i n a t e d completely at salt concentrations of 45, 48, 54, or 64%
b y weight for a d d i t i o n of magnesium, zinc, l i t h i u m , or c a l c i u m nitrates respec-
tively.
F o r a continuous extractive distillation process to be possible there must be
adequate enhancement of the nitric a c i d - w a t e r relative volatility, and a system
e q u i l i b r i u m w h i c h permits v i r t u a l l y complete separation of n i t r i c a c i d f r o m
m a g n e s i u m nitrate, the latter t a k i n g u p the water content of the weak a c i d
feedstock. This requires a d d i t i o n to the weak n i t r i c a c i d of solutions of m a g -
nesium nitrate usually containing 60 w t % or m o r e of M g ( N O s ) 2 . U n d e r these
conditions a nitric a c i d - w a t e r relative volatility of greater than 2.0 is obtained
at the l o w end of the l i q u i d phase concentration at a n i t r i c a c i d mole fraction
below 0.05 {4, 7).

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 THERMODYNAMIC BEHAVIOR O F ELECTROLYTES

Table I. E f f e c t o f Nitrates o n A z e o t r o p i c
Weight of Wt % ofHN0 3 in the azeotrope
metal nitrate
in liquid phase KN0 3 NaN0 3 Fe(N0 ) 3 3 Al(N0 )
3 3

0 68 68 68 68
10 75 67 60 61
20 78 63 52
30 81 57 Other
azeo-
40 85 45 tropes
appear
50
60
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70 48
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

I80H

frlHVPRATE
I40r-

—I l _
60 70 dO dO IOO

Figure 1 Magnesium nitrate-water solubility diagram

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 9. SLOAN Extractive Distillation Process 131

Composition in H N 0 — H 0 3 2

in the presence of:

LiN0 3 Ca(N0 ) 3 2 ZnN0 3 Mg(N0 ) 3 2

68 68 68 68
58 60 52 58
47 52 45 44
37 42 30 32

25 32 10 14

8 20 0 0
0 8
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0
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

M a g n e s i u m Nitrate Solutions. A n u m b e r of hydrates exist i n the m a g -

nesium n i t r a t e - w a t e r system. F i g u r e 1 is a solubility d i a g r a m showing, for i n -
stance, a hexahydrate melting at 8 9 . 9 ° C and a dihydrate melting at 130.9°C w i t h
intervening eutectic mixtures (8). Progressive thermal dehydration b y m e l t i n g
a n d evaporation of water forms lower hydrates but at temperatures f a r above
1 2 0 ° C , a n d if the t i m e of heating is prolonged, hydrolysis takes place w i t h loss
of nitrogen oxides a n d the f o r m a t i o n of basic compounds.
Aqueous solutions of m a g n e s i u m nitrate are a p p r e c i a b l y denser a n d more
viscous than water. T a b l e II illustrates data (9) o n the densities (in g/ml) of
concentrated solutions at h i g h temperatures. F i g u r e 2 illustrates the viscosity
variations i n concentrated solutions (9).
F r e e z i n g points of aqueous solutions m a y be obtained f r o m the solubility
d i a g r a m , F i g u r e 1. T h e b o i l i n g point at 760 m m H g is shown i n F i g u r e 3. It
w i l l be seen f r o m these graphs that at solution concentrations above 70 w t %
Mg(NC>3)2, the freezing point rises rapidly (more rapidly than the b o i l i n g point)
a n d the viscosity rises r a p i d l y also. F o r ease of h a n d l i n g therefore, solution

Table II. V i s c o s i t y V a r i a t i o n s i n C o n c e n t r a t e d S o l u t i o n s (9)

% by weight MgfNO,)^
Temp
(°C) 60 62 64 66 68 70 72
100 1.564 1.588 1.612 1.636 1.660 1.684 1.708
120 1.553 1.575 1.601 1.624 1.648 1.672 1.696
140 1.564 1.588 1.612 1.637 1.662 1.686
150 1.631 1.657 1.680

Zhurnal Priktal K h i m i e

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 132 THERMODYNAMIC BEHAVIOR O F E L E C T R O L Y T E S
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Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

SO 55 GO 65 7o "75

Figure 2. Viscosity of magnesium nitrate solutions

concentrations used i n the extractive distillation process do not n o r m a l l y exceed

72-74 w t % M g ( N 0 ) .
3 2

T h e specific heat of solid anhydrous M g ( N O s ) 2 m a y be calculated f r o m the

equation:

Cp (cal/g mole) = 10.68 + 71.2 X 1 0 " T + 1.79 X 3

MftT~ 2

( T i n ° K ) (JO)

T h e equivalent values i n cal/g are f o u n d i n T a b l e III.

Table III. Specific Heat of A n h y d r o u s M g ( N 0 ) 3 2

Temperature (°C) C p (Cal/g)

25 0.229
100 0.260
120 0.269
140 0.278
160 0.287
180 0.296
200 0.304

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 SLOAN Extractive Distillation Process
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Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

Figure 4. Integral heat of solution of magnesium nitrate

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 134 THERMODYNAMIC BEHAVIOR OF ELECTROLYTES

T h e h y d r a t i o n of anhydrous m a g n e s i u m nitrate evolves heat, 25,730 cal/g

mole M g ( N 0 ) 3 2 Mg(N0 ) • 6H 03 2 2 (II). L i k e w i s e , the dissolution of
M g ( N 0 ) or the hydrates i n water or the a d d i t i o n of further water to these so-
3 2

lutions also evolves heat ( 1 2 , 1 3 , 1 4 , 1 5 ) . F i g u r e 4 illustrates the molar integral

heat of solution of M g ( N 0 ) , the value for i n f i n i t e d i l u t i o n b e i n g 21,575 cal/g
3 2

mole. F r o m these figures, the enthalpies of magnesium nitrate solutions m a y

be computed.

The Ternary System Nitric Acid-Water-Magnesium Nitrate

T h e displacement of the azeotropic composition b y progressive a d d i t i o n

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of magnesium nitrate has been shown i n Table I above. V a p o r - l i q u i d equilibria

Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

have been determined (3, 4). F i g u r e 5 depicts e q u i l i b r i u m vapor compositions

i n the ternary system at the b o i l i n g point, w h i l e F i g u r e 6 shows b o i l i n g points
i n the system at 760 m m H g .

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 9. SLOAN Extractive Distillation Process 135

HNOj

m
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Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

20 A * 0 5 1

/ \ / \ \ /\ V/\ J /
/\ >
<
ae -ro

Figure 6. Magnesium nitrate-nitric acid-water boiling points (760 mm)

Since i n an extractive distillation process based on this ternary system the

extractive agent is nonvolatile and remains i n the l i q u i d phase, a n d since because
of the s i m i l a r i t y of the molar latent heats of n i t r i c a c i d a n d water there is sub-
stantially constant molar l i q u i d overflow, the mole fraction of magnesium nitrate
remains almost constant throughout the process. It is appropriate to represent
the e q u i l i b r i u m situation as a pseudo-binary system for each magnesium nitrate
concentration, and F i g u r e 7 shows v a p o r - l i q u i d e q u i l i b r i a on a nitric a c i d - w a t e r
basis at a series of m a g n e s i u m nitrate concentrations f r o m zero to 0.25 mole
fraction i n the l i q u i d phase.
F i g u r e 5 shows that w h e n nitric acid solutions containing 5 0 - 6 0 w t % H N O 3
are m i x e d w i t h m a g n e s i u m nitrate solutions c o n t a i n i n g 6 0 - 7 0 w t % Mg(NOa)2,
the e q u i l i b r i u m vapor composition at the b o i l i n g point does not exceed 8 5 - 9 0
wt% H N O 3 . Thus, to achieve concentrations higher than this the process must
p r o v i d e for rectification of the top vapor.
T h e r m a l data for the ternary system have not been widely reported, but may
be evaluated as required for process calculations f r o m available data for the nitric
a c i d - w a t e r a n d m a g n e s i u m n i t r a t e - w a t e r b i n a r y systems.

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 136 THERMODYNAMIC BEHAVIOR O F ELECTROLYTES

lo -
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Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

O .| -a -3 -4- -5 -C -7

MOLE FRACTION H N O ^ tN l-lQPtfc> ( ~ Ha.O BINARY)

Figure 7. System magnesium nitrate-nitric acid-water, liquid-vapor

equilibrium, pseudo binary basis

Process Conditions for Extractive Distillation

Consider the concentration of 60 w t % n i t r i c a c i d b y extractive distillation

w i t h 7 0 - 7 5 w t % solutions of magnesium nitrate. It m a y be seen f r o m F i g u r e
5 that the vapor composition above b o i l i n g solutions is at the level 8 5 - 9 0 w t %
H N O 3 over a wide range of mixtures, f r o m 3.5 parts of magnesium nitrate solution

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 9. SLOAN Extractive Distillation Process 137

per part of weak nitric a c i d u p to about 8 parts. In the particular case of 5 parts
of 72 w t % Mg(NC>3)2 solution a n d 1 part of 60 w t % n i t r i c a c i d , the m i x t u r e has
the composition 60 w t % M g ( N 0 ) , 10 w t % H N 0 , a n d 30 w t % H 0 w i t h an
3 2 3 2

e q u i l i b r i u m vapor composition of 88 w t % H N 0 3 at the b o i l i n g point. A rec-

t i f y i n g section of the c o l u m n gives a top product of nearly 100 w t % H N 0 , w h i l e 3

the nitric a c i d content at the base of the distillation c o l u m n m a y be taken as zero.

A suitable reflux ratio m a y be d e t e r m i n e d b y trial a n d error. F o r the case of a
3:1 ratio w i t h the heat requirement supplied b y an external reboiler, the reboiler
outlet l i q u o r composition is 66.6 w t % M g ( N 0 ) . 3 2 A s s u m i n g constant m o l a r
overflow, the vapor rate is 1.15 parts per part of H N 0 3 distilled, m a k i n g the
column base composition 59 w t % M g ( N 0 ) . This molar composition (0.15 mole
3 2
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fraction) applies throughout the s t r i p p i n g section of the c o l u m n , a n d the ap-

propriate e q u i l i b r i u m curve is selected f r o m F i g u r e 7. G r a p h i c a l methods (16,
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

17) m a y be used to calculate the n u m b e r of theoretical plates r e q u i r e d for the

separation.
A variety of feed compositions a n d reflux ratios m a y be thus e x a m i n e d ,
preferably b y c a r r y i n g out detailed plate-to-plate e q u i l i b r i u m calculations w i t h
check heat balances, as the t h e r m a l effects are substantial, a i m e d at o p t i m i z i n g
the reflux ratio (representing operating cost) against the n u m b e r of theoretical
plates (representing capital cost). In particular terms, I C I has f o u n d that feed
ratios between 4:1 a n d 7:1 (parts of magnesium nitrate solution per part of weak
nitric a c i d feed) are possible, w i t h reflux ratios i n the range 2:1 to 4:1. The
theoretical plate requirement for the complete c o l u m n is between 15 a n d 20.
W i t h i n this range the process w i l l concentrate 60 w t % H N 0 3 to 99.5 w t % using
72 w t % M g ( N 0 ) as extractive agent a n d d e n i t r a t i n g it to less than 0.1 w t %
3 2

HNO . s

H e a t R e q u i r e m e n t of the Process. H e a t is r e q u i r e d for v a p o r i z a t i o n i n

the extractive distillation c o l u m n , a n d for the reconcentration of m a g n e s i u m
nitrate solution. Overall thermal effects caused b y the magnesium nitrate cancel
out, a n d the heat d e m a n d for the complete process depends on the amount of
water b e i n g removed, the reflux ratio e m p l o y e d , a n d the t e r m i n a l (condenser)
conditions i n distillation a n d evaporation. T h e composition a n d temperature
of the m i x e d feed to the still influence the relative heat demands of the evapo-
ration a n d distillation sections. F o r the concentration of 60 w t % H N 0 3 to 99.5
wt% H N 0 3 using a still reflux ratio of 3:1, a still pressure of 760 m m H g , a n d an
evaporator pressure of 100 m m H g , the theoretical overall heat re q u i re me nt is
1,034 k c a l / k g H N 0 . 3

I d ' s C o m m e r c i a l Process. In 1960 I C I constructed a concentration plant

using this extractive distillation process (18) w i t h a capacity of 16,000 tonnes/
a n n u m of product acid (99.5 w t % H N 0 ) w h i c h has subsequently been extended.
3

A flowsheet is g i v e n i n F i g u r e 8, a n d the process description is as follows.

W e a k nitric a c i d (normally 60 w t % H N 0 ) a n d concentrated m a g n e s i u m
3

nitrate solution (72 w t % M g ( N 0 ) ) enter at the feed point of a n extractive dis-

3 2

tillation c o l u m n . T h e rectifying section above the feed point has a water-cooled

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 Downloaded by PURDUE UNIVERSITY on June 9, 2013 | http://pubs.acs.org
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

WATER 0>f

CONCENTRATED \
N I T R I C ACID

NITRATE si - • u
EVAPORATOR
1
| r -] REFLUX
STRIPPING

COLUMN

HITRIC ACID
C O O L E R
S T 3 3 5 % NITRIC ACID
CONCENTRATED
MAQNCS1UM
NITRATE RECTIFYING
TANK COLUMN

z
COOLER
. <9
p REBOILER
6Q% NITRIC ACID FEEb

GO°/a MACNBtttUM

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
NITRIC ACID
STORAQC

Figure 8. Flowsheet of the concentration of nitric acid by the magnesium nitrate process
 9. SLOAN Extractive Distillation Process 139

condenser and reflux supply and gives concentrated top product, normally 99.5
w t % HNO3. T h e s t r i p p i n g section below the feed point has an external steam-
heated reboiler, and its bottom product is d i l u t e d magnesium nitrate solution,
n o r m a l l y 65-67 w t % M g ( N 0 ) , containing less than 0.1 w t % HNO3.
3 2 This
weaker magnesium nitrate solution is reconcentrated to the feed strength i n a
steam-heated v a c u u m evaporator.
T h e original plant h a d the f a c i l i t y to fractionate the vapors f r o m this
evaporator to recover nitric a c i d present i n the magnesium nitrate stream, but
the h i g h degree of denitration obtainable i n the extractive distillation c o l u m n
made this recovery operation unnecessary and it is no longer used.
W a t e r vapor f r o m the evaporator passes to a water-cooled condenser, a n d
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the w e a k l y acidic condensate is discharged as l i q u i d effluent. T h e extractive

distillation section of the plant is maintained under slight negative pressure, and
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

the condenser off-gases are scrubbed w i t h water a n d discharged as gaseous ef-

fluent.
In the distillation system used i n the I C I plants, the s t r i p p i n g section is de-
signed as a packed c o l u m n , constructed as a t i l e - l i n e d shell w i t h silicon iron i n -
ternal fittings, end cover, and ring packing. T h e feed point temperature is 120° C
a n d the bottom, 1 6 0 ° C ; operating pressure is atmospheric or just below. T h e
separate rectifying section is a silicon iron bubblecap column. The columns were
sized by conventional fractionator design methods, and both types of construction
have given good service i n practice.
Concentrated nitric acid vapor f r o m the top of the rectifying section passes
to vertical silicon iron condensers with water-cooled U-tube bundles i n high purity
aluminum. Condensed a c i d is refluxed through a d i v i d e r system, the product
fraction being cooled i n t i t a n i u m coolers. Off-gases are scrubbed w i t h water
in a tail gas absorber w i t h final discharge to atmosphere through a steam ejector.
T h e magnesium nitrate concentrator is a vertical long-tube natural c i r c u l a t i o n
v a c u u m evaporator of standard design h a v i n g a water-cooled shell a n d tube
condenser, v a c u u m b e i n g m a i n t a i n e d b y a water r i n g p u m p .

Materials of Construction

The handling of boiling saturated salt solutions and concentrated nitric acid
l i q u i d a n d vapor, i n the presence of nitrous gases, restricts the choice of con-
structional materials a n d places constraints on the c h e m i c a l engineering of the
process. H i g h - s i l i c o n iron is an exceptionally corrosion-resistant material used
successfully for column stills, packing, lines, and ducting, but it is relatively brittle
and has a high coefficient of t h e r m a l expansion so that adequate thought must
be given to the supporting and jointing of equipment, w i t h expansion bellows
where appropriate.
W h e n the process is used to make nitric acid of over 98.5 w t % concentration,
particular care is necessary i n the selection of materials for h a n d l i n g the l i q u i d
product. Unstabilized stainless steels w i t h extra low carbon content (<0.03%

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 140 THERMODYNAMIC BEHAVIOR O F E L E C T R O L Y T E S

C ) gave reasonable service at n o r m a l temperature, but for severe jobs it m a y be

appropriate to use the more exotic metals such as tantalum. Z i r c o n i u m or tita-
n i u m may also be used, though i n high strength acids w i t h an appreciable content
of dissolved nitrogen oxides these metals can develop unstable, potentially haz-
ardous oxide films. T h e newer varieties of h i g h silicon austenitic stainless steels
m a y be of service.

Process Operation

Successful operation of this concentration process demands adequate and

consistent denitration i n the stripping section of the extractive distillation column.
If this is not achieved, instability develops, as evidenced b y fluctuating flows and
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pressure drops i n the column. T h e design value for HNO3 content i n the bottoms
Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

(magnesium nitrate stream) is 0.1 w t % a n d this is readily achievable. Higher

values, besides causing instability, promote corrosion i n the reboiler a n d the
magnesium nitrate system.
Stable operation of the process is assisted greatly b y attention to the m a g -
nesium nitrate solution. Its concentration is important a n d should not f a l l sig-
nificantly below 70 w t % Mg(NC>3)2 i n the evaporator for good denitration i n the
stripping column. Over-concentration can lead to handling difficulties associated
w i t h ' h i g h freezing points, w i t h reduced heat transfer i n the evaporator because
of increased viscosity, or w i t h f o a m i n g or l i q u i d carryover f r o m the s t r i p p i n g
column. Extraneous impurities such as i r o n salts, siliceous matter, or chlorides
can adversely affect the e q u i l i b r i u m pattern a n d give rise to h a n d l i n g and
measurement problems. These can be a v o i d e d b y selecting h i g h q u a l i t y m a g -
nesium salts.
Process performance is straightforward and predictable. W h i l e commercial
plants are comprehensively instrumented, operating features are r e a d i l y rec-
ognizable f r o m simple measurements, particularly of temperatures. Conditions,
for instance, around the base of the c o l u m n a n d the reboiler allow interpretation
of process parameters, reasoning as follows:

F o r the concentration of 6 0 - 1 0 0 w t % HNO3:

let C = wt fraction of M g ( N O s ) 2 i n feed to c o l u m n ,
let R1 = ratio of feeds (parts m a g n e s i u m nitrate solution per part of weak
acid), a n d
let R2 = c o l u m n reflux ratio,

then the weight fraction of M g ( N O s ) 2 is the magnesium nitrate solution leaving

the reboiler = CR1/R1 + 0.4
F o r constant molar vapor f l o w i n the c o l u m n system, the vapor f l o w rate
leaving the reboiler, per part of weak a c i d feed, is 0.6 (1 + R2) 18/63 a n d the
weight fraction of M g ( N O s ) 2 i n the m a g n e s i u m nitrate solution leaving the col-
u m n base
= CRi CR X

Ri + 0.4 + 0.6 (1 + R ) 18/63 ~~ R i + 0 . 1 7 R + 0.57

2 2

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 9. SLOAN Extractive Distillation Process 141

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180 / •
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s

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178
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Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

/ s
o s
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s
174- s
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a
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—17a
5
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170
7^

4 _ ^
s s

1 1
3 4- S «
REFLUX RATIO

REBOILER °C

SftSE °C

Figure 9. Column base and reboiler temperatures

F i g u r e 9 presents the equivalent b o i l i n g solution temperatures at the reboiler

and the c o l u m n base calculated for a series of feed ratios a n d reflux ratios, f r o m
w h i c h the appropriate process conditions a n d temperatures m a y be related.

Conclusions

This concentration process has been operated on a commercial scale for some
fifteen years and has proved robust a n d reliable. W e a k n i t r i c a c i d feedstocks
w i t h concentrations v a r y i n g f r o m 55 to 70 w t % H N 0 have been h a n d l e d satis- 3

factorily w i t h product strengths of 98-99.6 w t % H N 0 a c c o r d i n g to d e m a n d . 3

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
 142 T H E R M O D Y N A M I C BEHAVIOR O F E L E C T R O L Y T E S

Losses of n i t r i c a c i d a n d m a g n e s i u m salts are t r i v i a l , a n d the process c a n be r u n

in a straightforward manner w i t h m i n i m u m m a n n i n g . T h e major operational
cost is for the steam r e q u i r e d for the process heat supply; this depends on the
concentration range r e q u i r e d but w i l l be ca. 2.0—2.5 parts per part of product
acid. T h e capital cost of a c o m m e r c i a l plant compares f a v o r a b l y w i t h that for
alternative concentration processes.

Acknowledgment

T h e author thanks the Directors of the O r g a n i c s D i v i s i o n of I m p e r i a l C h e m i c a l

Industries for permission to publish this paper.
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Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0155.ch009

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RECEIVED June 13, 1975.

In Thermodynamic Behavior of Electrolytes in Mixed Solvents; Furter, W.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1976.