THE FLUOREX PROCESS

FOR REGENERATION OF NITRIC/HYDROFLUORIC

STAINLESS STEEL PICKLE LIQUORS
Craig J. Brown, Michael Sheedy
Prosep Technologies Inc.
Subsidiary of Eco-Tec Limited
1145 Squires Beach Road
Pickering, Ontario
Canada L1W 3T9

ABSTRACT
The Fluorex process utilizes sulfuric acid distillation to volatilize nitric and hydrofluoric
acid. Unlike previous systems which use crystallization, acid sorption technology is employed to
remove ferric sulfate and other metal contaminants from the sulfuric acid. As a result, it is possible
to operate the system at sulfuric acid concentrations of less than 50% w/w and temperatures of less
than 90C. Fluoride and nitrate recoveries of greater than 93% and 99% respectively are achieved
by steam stripping the sulfuric acid prior to reclamation in the acid sorption unit. Purified nitric
acid and hydrofluoric acid are recovered from the vapours in an adiabatic absorber. The waste
from the acid sorption unit is a mildly acidic solution containing iron, chromium and nickel sulfate
which can be neutralized to reclaim the metal values as hydroxides. A novel neutralization process
has been devised which employs ammonia as the neutralizing agent. The ammonia then is
recovered by lime neutralization and steam stripping. Sulfate is recovered as a high purity gypsum
cake. It is also possible to incorporate rinsewater recovery into the system.

THE FLUOREX PROCESS FOR REGENERATION OF NITRIC/HYDROFLUORIC

STAINLESS STEEL PICKLE LIQUORS
BACKGROUND
During annealing of stainless steel, an oxide surface layer is formed. The usual method of
removing this oxide layer is by immersion in a mixed nitric acid/hydrofluoric acid solution in a
process called pickling. These pickling solutions become contaminated with dissolved metals,
through use. As the metal concentration increases, the free acid concentration decreases and
pickling efficiency drops. In addition, the solubility of iron fluoride may be exceeded, resulting in
the formation of a precipitate that must be periodically manually removed from tank bottoms and
walls. Additions of fresh, concentrated acid are made from time to time to rejuvenate the bath, but
eventually it becomes spent and must be discarded and replaced.
PRIOR TREATMENT PROCESSES
Neutralization
Spent pickle liquors are neutralized with an alkali such as sodium hydroxide (caustic soda)
or calcium hydroxide (lime). In the case of stainless steel pickle liquors containing fluoride, lime is
usually utilized. Calcium fluoride is only slightly soluble, so that fluoride ions are precipitated
simultaneously with the metal ions. Unfortunately, neither lime nor caustic are effective in
removing nitrate ions which are tightly regulated in many jurisdictions. The cost of these
neutralizing chemicals and disposal of the resulting sludge is considerable and can contribute
appreciably to the overall cost of pickling the metal.
Sulphuric Acid Distillation
Various processes have been employed to purify or regenerate (i.e. recover) spent pickling
liquors. For example, a number of attempts have been made to utilize so-called 'sulphuric acid
distillation' of spent nitric/hydrofluoric acid pickle liquors (1 ,2 ,3 ,4 ). The basis of this process is the
fact that nitric and hydrofluoric acids are much more volatile than sulphuric acid. Sulphuric acid is
added to the spent pickle liquor, which is then boiled. The sulphuric acid increases the vapor
pressure of the hydrofluoric and nitric acids, causing them to evaporate together with the water.
Nitrate and fluoride displaced from metal salts by the sulphate, combine with hydrogen ion from the
sulphuric acid to form additional nitric acid and hydrofluoric acid, which are also evaporated,
leaving behind a sulphate salt solution. When the vapors are condensed, a purified solution of nitric
acid and hydrofluoric acid is recovered. A distillation or adiabatic absorber column can also be
incorporated to partially separate the condensed water vapor from the condensed acids, thereby
increasing the concentration of recovered acid.
Operation of the distillation process results in a buildup of metal sulphate salts and a
decrease in the sulphuric acid concentration in the evaporator bottoms. In order for the process to
continue functioning, it is normal to maintain the free sulphuric acid concentration in the evaporator
greater than 60% H2SO4 through additions of sulphuric acid. Eventually a point is reached where
the solubility limit of the metal sulphate salts is reached, whereupon the sulphate salts crystallize
out. The solids are filtered out and the recovered sulphuric acid, with a portion of the metal sulphate
removed, is recycled back to the evaporator.
Thus, this process potentially can achieve the basic objective of recovering a large portion of
the waste nitrate and fluoride ions- both free acids as well as metal salts. The metals are rejected as
sulphate salts which can be dissolved in water and re-precipitated by neutralization with base. The
hydroxide sludge produced can then be disposed of, or possibly reclaimed.
Despite it's obvious potential benefits, the sulphuric acid distillation process has not
achieved widespread acceptance. This is because there are a number of problems inherent to the
process: It is a difficult task to filter these crystals from such a highly corrosive solution and
corrosion resistant equipment for this purpose is very expensive. The crystals are laden with

concentrated sulphuric acid and it is not feasible to efficiently wash these crystals with water to
recover this acid, since the salts tend to re-dissolve. As a result, the salts are of no commercial value
and must be considered hazardous waste. As pointed out by Blomquist5 , crystallization of the
nickel and chromium does not occur as readily as iron. These metals are somehow sequestered in
solution. In order to deal with this problem, Blomquist utilized a second evaporator operating under
a greatly increased temperature (150-220C), high sulphuric acid concentration (80% H2SO4) and a
long residence time, to aid in crystallizing these metals. This second evaporator adds greatly to the
cost and complexity of the process.
Acid Sorption
A large number of ion exchange/sorption systems have been installed over the past few
years for recovery of waste stainless steel pickle liquors (6 ). These systems use an ion exchange
resin which has the ability to sorb acids from solution, while excluding metallic salts of those acids.
This sorption is reversible, in that the acid can be readily de-sorbed from the resin with water. It is
thus possible, by alternately passing contaminated acid and water through a bed of this resin, to
separate the free acid from the metal salt. The most commonly used system of this type is called
an APU. The APU was first commercialized in the late 1970's for purification of sulphuric acid
anodizing solutions (7 ). Since that time, hundreds of units have been installed around the world on
a wide variety of different acid recovery applicatons.
There are basically two steps in the APU operating cycle: In the upstroke, acid containing
dissolved metallic salt impurities is pumped into the bottom of a fixed bed of sorption resin. The
free acid is sorbed by the resin as the solution passes through the bed, so that a de-acidified metal
salt 'byproduct' solution is collected from the top of the bed. Next, during the downstroke, water is
pumped down through the resin bed. Water strips the acid from the resin as it passes through the
bed, so that a purified acid 'product' is collected from the bottom of the bed. The total cycle time is
typically only about 2-5 minutes. No chemicals or significant energy inputs are required to operate
the APU process. By utilizing a novel ion exchange technique called Recoflo which incorporates
short (30-90 cm) beds of fine mesh resins, dilution of the acid has been minimized and purity
maximized.
In the usual configuration, contaminated pickling acid flows from the pickle bath through a
pre-filter to the APU. The acid is removed by the APU and the metal salt bearing byproduct
solution exits from the unit to be neutralized in the mill waste treatment system. The purified acid
product recovered by water elution is recycled directly back to the pickle bath.
The acid sorption process has the advantages of being compact, simple and low cost. In
addition, with this process it is possible to operate the pickle tank at any desired concentration of
dissolved metal and free acid, so that pickling performance can be optimized.
The major disadvantage of acid sorption systems is that they generate a byproduct or waste
stream consisting of a mildly acidic salt solution of the metals being dissolved in the pickling
process. This byproduct stream must be further treated, usually by neutralization with base, in order
to render it harmless to the environment. In the case of stainless steel pickling, where hydrofluoric
acid is employed, this byproduct stream contains an appreciable quantity of fluoride, since some of
the metals are strongly complexed by fluoride, as well as a certain concentration of nitrate. The
byproduct is usually neutralized with lime to remove the fluoride ions as well as the metals. This
still leaves a residual of nitrate which may be objectionable. The presence of fluoride in the sludge
may obviate the possibility of pyro-metallurgically reclaiming the metal values from the sludge.
Regular additions of concentrated makeup acid are required to replace acid neutralized through
metal dissolution. Even when a recovery system of this type is employed, it is normally not
possible to reclaim more than about 50% of the fluoride values in a spent stainless steel pickling
solution.

BASIC DESCRIPTION OF THE FLUOREX PROCESS

The Fluorex process combines the sulphuric acid distillation process with the acid sorption
process in an attempt to overcome the disadvantages of each, while retaining their inherent
advantages.
There are five basic elements or unit operations in the Fluorex system: reactor, absorber,
condenser, stripper and APU. While each element by itsef is not novel, having been field proven
for years in many other applications, the combination is unique and has been recently patented (8 ).
The basic system is shown in Figure 1.
Reactor
Spent pickle liquor is drawn into a reactor containing sulphuric acid. The reactor is heated
using a steam fired heat exchanger causing the solution in the reactor to boil. The free hydrofluoric
acid (HF) and nitric acid (HNO3) are readily vaporized along with water.
The sulphuric acid reacts with the iron and chromium fluoride complexes as well as any
nitrate salts according to equations (1)-(3) to liberate free hydrofluoric acid and nitric acid.
3H2SO4 6HF

2FeF 3

2CrF3

+3H2SO4 6HF

Ni(NO3)2

Fe2(SO4 )3

Cr2(SO4)3

3H2SO4 2HNO3 +

NiSO4

(1)

(2)

(3)

Once the hydrofluoric and nitric acids are thus formed they are then vaporized, however
small residuals of hydrofluoric acid and nitric acid are left in the reactor solution. The level of
residual hydrofluoric acid and nitric acid is dependent on the sulphuric acid concentration. Higher
sulphuric acid concentrations increase the vapour pressures of the HF and HNO3 and cause them
to volatilize, thereby driving the above reactions to the right, resulting in lower concentrations in the
reactor solution.
As noted in the above equations, reaction with sulphuric acid results in the formation of
metal sulphate salts which will accumulate and so must ultimately be removed from the system.
Previous regeneration processes based upon sulphuric acid distillation typically operate at a
sulphuric acid concentration in excess of 60% H2SO4 (ie. 18 N) which promotes volatilization of
the acid and crystallization of metal sulphate salts. Fluorex, on the other hand, depends on keeping
the metals in solution and avoiding crystallization. As shown in Figure 2, the solubility of iron, the
least soluble species is inversely related to the sulphuric acid concentraion. Fluorex typically
operates at about 50% H2SO4 (ie. 14.2 N), which corresponds to an iron solubility at room
temperature of about 20 g/L. The total metal solubility (ie. including chromium and nickel) at the
reactor operating temperature of approximatley 90 C is significantly higher.
The solutions processed by the reactor are very corrosive and the materials of construction
must be carefully chosen, however because Fluorex operates at lower sulphuric acid concentrations
with lower boiling points than previous systems, corrosion problems are somewhat alleviated.
Fluorex vessels are FRP/thermoplastic dual laminates while the reactor heat exchanger is silicon
carbide.

80.00
70.00

[Fe] (g/L)

60.00
50.00
40.00
30.00
20.00
10.00
0.00
0

10

15

20

[H2SO4] (N)

Figure 2 - Solubility of ferric iron in sulphuric acid at 25C

Absorber
The vapors leaving the reactor enter the absorber which is a packed tower. The hydrofluoric
acid and nitric acid are absorbed into water which is sprayed into the top of the absorber and a high
purity mixture of hydrofluoric and nitric acid is collected from the bottom of the absorber at pickle
bath strength and recycled back to the pickle bath. The water vapors leaving the top of the absorber
are passed to the condenser
Condenser
The water vapors emanating from the top of the absorber are condensed in a water cooled
shell and tube heat exchanger and the condensate is collected. A portion of this condensed water is
recycled or 'refluxed' back to the absorber for use in absorbing the acid. The remainder of the
condensate can be used by the APU for elution or discharged.
Stripper
The action of the sulphuric acid in the reactor results in the formation of metal sulphate salts
which will tend to build up. Reactor liquor must be removed from the system and replaced with
purified acid to avoid exceeding the solubility limit and prevent the precipitation of salts in the
reactor.
As stated above, the solution in the reactor maintains a low residual concentration of
hydrofluoric acid and nitric acid.
The disadvantage of operating at lower sulphuric acid
concentrations is higher residual fluoride and nitrate levels. In order to reduce these levels, the
solution removed from the reactor is contacted with steam in a packed stripper tower. Most of the
residual hydrofluoric acid and nitric acid is vaporized by the steam and so removed from the
solution. The vapor leaving the stripper contains water vapor bearing some hydrofluoric acid and
nitric acid. This is then processed in the absorber along with the reactor vapours, for recovery of
the fluoride and nitrate values. The solution collected at the bottom of the stripper is a sulphuric
acid/metal sulphate solution containing significantly reduced levels of fluoride and nitrate.
The steam used in the stripper can be fresh steam or a compressor can be employed to
recompress a portion of the vapour leaving the top of the absorber for use in the stripper. By this
means, the amount of steam consumed in the stripper can be reduced by typically up to 75%. The
amount of steam used for the stripper only (ie. not including that used for the reactor heat
exchanger) is shown in Table II.

APU
In order to recover the sulphuric acid values in the solution leaving the stripper, the solution
is passed to an APU. This is the same type of unit that has been used to directly purify pickle
baths. In fact, if for some reason another component of the Fluorex system is out of service, the
APU can be utilized for direct pickle bath purification in the usual manner, as an interim measure
until the Fluorex system is back up again.
The free sulphuric acid values in the solution fed to the APU are sorbed by the resin while
the metal sulphates pass through the resin bed and a de-acidified metal salt byproduct or waste
solution is collected. This can then be economically neutralized or various techniques for recovery
of the metal can be employed as discussed below. The sulphuric acid is recovered from the APU
by elution of the resin with water. The reclaimed sulphuric acid is then recycled back to the reactor.
Thus the APU provides an alternative to crystallization for removing metal sulphates from
the evaporator. Unlike the crystallization process, the APU is equally effective for removal of all the
metals including iron, chromium and nickel. Moreover, unlike the crystallization process, the metal
concentration chosen has no lower limit with an APU. It works equally well on dilute or
concentrated solution.
Table I shows typical APU performance. Based upon these results it can be seen that the
APU removes 50% of metallic contamination while recovering 97% of the sulphuric acid values. It
should be noted that the APU is capable of higher metal removal efficiencies, however for this
particular application, it was found that the sulphuric acid recovery efficiency is maximized at this
level of metal separation.
Because of the difficulty in removing nitrate from effluents, there is great interest in
maximizing nitrate recovery efficiency. It was found unexpectedly that the APU showed preference
for recovery of nitric acid over sulphuric acid. As a result, the loss of nitrate in the APU byproduct
is lower than may have been predicted. The amount of nitrate lost to the APU byproduct is only
1% of that fed to the APU, the balance being recycled back to the reactor in the product stream
This indicates that the APU is very selective in recovering nitrate and significantly augments the
stripper in maximizing nitrate recovery efficieny.
The amount of fluoride lost to the APU byproduct is 37.5% of that fed to the APU. This
indicates that the APU is not particularly selective in recovering fluoride, so that we have to depend
primarily on the stripper to achieve good fluoride recovery.
Sulphuric acid is required to replace the sulphate lost in the byproduct. Concentrated
sulphuric acid is added directly to the reactor to maintain a constant concentration. The quantity of
sulphuric acid consumed is included in Table II.
Table I - Typical APU Mass Balance
Stream

Relative
Flow

[NO3 -]
(g/L)

[F-]
(g/L)

[H2SO4 ]
(g/L)

[metal]
(g/L)

feed (from stripper)

20

4.8

600

20

product (recycle to reactor)

19.8

3.7

582

10.2

byproduct (waste)

0.63

0.3

1.8

28.8

15.5

eluant (water)

0.63

TYPICAL SYSTEM PERFORMANCE

Table 2 shows a typical mass balance for a Fluorex system designed for a 360,000 tonne/A
pickling line, which represents an average metal dissolution rate of 100 kg/h. These results are
based upon several months operation of a laboratory pilot plant. The total fluoride recovery
efficiency is 94%, while the total nitrate recovery efficiency is greater than 99%. The recovered
pickle liquor is normally collected at approximately the same strength of the original acid, although
it is possible to recover a more concentrated acid by adjusting the reflux ratio in the absorber.
Negligable quantities of metals are contained in the recovered acid.
Table II - Typical Fluorex Mass Balance
Stream

Flow
(L/h)

F
(g/L)

NO 3
(g/L)

-2

SO 4
(g/L)

Metal
(g/L)

Spent Pickle Liquor

2,857

65.8

173

35

Recovered Acid

2,857

61.7

172.3

APU Byproduct

6,457

1.8

0.3

68

H2SO4 (96% w/w)

254

1,728

Water

4,112

Steam

2,046 kg

15.5

Basis: 360,000 tonne/A pickling line (100 kg/h metal dissolution)

FINAL WASTE TREATMENT
Several options are available to treat the APU byproduct (ie.waste) stream produced by the
system:
Conventional Lime Neutralization
The APU byproduct can be neutralized with lime to precipitate out the metals as hydroxides.
Most of the sulphate will also precipitate out as calcium sulphate (gypsum) so that a mixed filter
cake is produced. In most cases, this is the technique employed to treat spent stainless steel pickle
liquors. The existing waste treatment system currently employed for treatment of spent pickle
liquor can normally be used to treat the Fluorex waste.
Conventional Caustic Neutralization
Since the APU waste contains only very low levels of fluoride, lime neutralization may not
be necessary. It may be preferable to use caustic soda in lieu of lime, since the amount of solid
waste generated is significantly less than with lime neutralization because no gypsum is produced.
This method should be considered where the cost of solid waste disposal is high In addition, since
the metal hydroxide sludge is not contaminated with gypsum, hydrometallurgical or
pyrometallurgical recovery of the metals can be considered.
Lime/Ammonia Cycle Neutralization
In order to minimize the cost of neutralizaton chemicals while producing a metal hydroxide
sludge suitable for metal recovery, a novel neutralization process has been developed called LAND
(Lime Ammonia Neutralization and Disposal). The basic flowsheet for the LAND process is
shown in Figure 3.

The waste from the Fluorex system, which is the APU byproduct stream, is neutralized with
ammonia gas in tank T1 according to reaction (4). This precipitates the metals as hydroxides. The
slurry is withdrawn from T1 and filtered with a filter press, producing an ammonium sulphate
liquor and metal hydroxide filter cake. The cake, typically containing about 70% moisture, may be
suitable for reclamation of the metals.
Fe2(SO4)3 + 6NH3 + H2O 3(NH4)2SO4 + 2Fe(OH)3

(4)

The ammonium sulphate filtrate is then directed to tank T2 where it is reacted with lime
according to (5). Reaction with lime produces gypsum precipitate and ammonium hydroxide. The
slurry leaving T2 passes to tank T3. Steam is admitted to T3 which strips the ammonia from the
solution. The gas leaving T3 containing ammonia and steam is admitted to T2 and then back to T1.
The ammonia reclaimed from the reaction with lime in T2 and T3 is used for the initial neutralizaton
reaction in T1.
(NH4)2SO4 + Ca(OH)2 CaSO4 + 2NH3 + 2H2O

(5)

The slurry leaving T3 is filtered to yield a gypsum filter cake typically containing a moisture
content of 30% and dilute ammonium sulphate filtrate. The filtrate is utilized as a source of water
for the APU and does not leave the system. The gypsum can be disposed of as land-fill. Potential
markets for the gypsum filter cake, such as wall board manufacture, are being investigated.
This process combines the best features of both the lime and caustic neutralization
processes ie. low operating costs, while producing recyclable metal hydroxide filter cake and
gypsum which can be readily and economically disposed of.
RINSEWATER RECOVERY
It is also possible to incorporate recovery of rinsewaters into the Fluorex system . In the
preferred configuration (see Figure 1), the majority of the pickle liquor is rinsed off with a small
amount of water in the first of a two or three stage rinse system. This dilute pickle liquor which
may typically be about 10% of bath strength flows to the Fluorex reactor for direct recovery. The
additional water entering the system is evaporated and separated from the recovered acids in the
absorber.
The balance of the rinsing is accomplished in subsequent rinse stages. In order to achieve
adequate rinsing, large flows of pure water are required. The dilute, contaminated rinsewater waters
leaving the final rinse stations are purified by ion exchange demineralization and recycled for use in
rinsing.
Upon exhaustion, the cation exchange bed is regenerated with sulphuric acid, yielding a
metal sulphate solution with a residual of sulphuric acid. The anion exchange bed is regenerated
with sodium hydroxide to yield a solution of sodium nitrate and sodium fluoride with a small
excess of sodium hydroxide. The spent regenerant solutions are also directed to the reactor of the
Fluorex system. The sulphate in the spent cation regenerant serves as a source of sulphuric acid for
the Fluorex process. The fluoride and nitrate values in the spent anion regenerant are reclaimed as
hydrofluoric and nitric acid. The metals from the cation bed are rejected in the APU byproduct,
along with the sodium from the anion bed.
In this manner, discharge of fluoride and nitrate from rinsing is totally eliminated while
effective rinsing is accomplished with high flows of deionized water.
ECONOMICS

The major operating costs of the system are energy, sulphuric acid and waste treatment.
APU resin replacement costs are not significant as they have been shown to last in excess of 5
years in similar applications. The major savings are associated with reduced consumption of nitric
and hydrofluoric acid as well as reduced waste treatment expense. Table III compares the operating
costs for a 360,000 tonne per year pickling operation with and without a Fluorex recovery system.
The following basis for comparison has been used:

300 series stainless steel being processed

Hours of operation per year:
8,400
Pickle bath composition:
Metal
35 - 50 g/L
total HNO3 175.6 g/L
total HF
68.7 g/L
Metal dissolution rate:
100 kg/h

The economic evaluation of pickle liquor treatment without recovery assumes that waste
liquor is withdrawn from the pickle tank batch-wise once the dissolved metal level has reached 50
g/L. This waste is treated with lime to precipitate metal hydroxides and calcium fluoride. The
insoluble hydroxides and fluorides are separated, de-watered and sent to landfill. The effluent,
containing significant quantities of calcium nitrate, is discharged. A new batch of pickle solution is
then prepared and used on the line.
When recovering waste pickle solution the Fluorex system is operated continuously. Pickle
liquor, with 35 g/L dissolved metal, is withdrawn from the bath and processed. The recovered nitric
and hydrofluoric acids are returned to the bath as necessary. Small amounts of concentrated makeup acids are required to replace what is lost with the metal in the APU byproduct stream. This
stream is also treated with lime in the conventional manner to precipitate metal hydroxides and
gypsum. These solids are de-watered and sent to landfill. A steam-jet compressor (not shown) is
utilized to recover steam for use in the stripper as discussed above. Rinsewater recovery has not
been considered in this evaluation.
As the analysis in Table III shows, the net annual saving when operating a Fluorex system,
as compared to simply waste-treating the spent pickle liquor, is $1,373,805 U.S.. Clearly, the
most significant benefit associated with running a Fluorex process is the reduction in consumption
of hydrofluoric acid. The typical payback period for an installed plant is 2 - 2.5 years.
SUMMARY AND CONCLUSION
A new system for regeneration of nitric/hydrofluoric stainless steel pickle liquors has been
developed. Based upon a unique combination of existing, well-proven unit operations, the system is
typically capable of recovering 94% of total fluoride values and greater than 99% of the nitrate
values. While the main economic benefit from operating a Fluorex system will be derived from
reduced purchases of hydrofluoric acid, the dramatic reduction in nitrate discharge possible with the
system may provide important environmental advantages that are equally significant in many cases.
Use of a novel lime/ammonia cycle neutralization scheme significatnly reduces the quantity of solid
waste produced by the system and may make it feasible to recover metal values from the solids. A
rinsewater recovery system can be incorporated into the system to provide a virtually zero liquid
discharge pickle line.
While this paper has been limited to a description of nitric/hydrofluoric acid baths, other
acid formulations incorporating sulphuric and hydrochloric acid, for example, can also be treated
with the Fluorex system.

Table III - Economic Evaluation

Pickling Without Recovery

Unit Cost
$US

Quantity/yr

$US/yr

Pickle Liquor Recovery

with Fluorex
Quantity/yr
$US/yr

HNO3
(100% basis)

$220/tonne

2,950 tonnes

$649,000

17 tonnes

HF

$1,210/tonne

1,649 tonnes

$1,995,250

140 tonnes

$169,400

Solid Waste
Disposal

$55/tonne

12,417 tonnes

$683,000

13,962 tonnes

$767,910

Steam

$6/tonne

55,300 tonnes

$331,800

H2SO4

$83/tonne

3,840 tonnes

$318,720

$3,740

(70% basis)

(98% basis)

Lime

$55/tonne

4,255 tonnes

$234,000

2,967 tonnes

$163,185

$25/h

8,400 h

$210,000

(100% basis)

Labour
Maintenance

$120,000

Cooling
Water

$30/1,000M

Electricity

$85/MWH

Total
Op.Costs

$3,561,250

2,415,000 M3

$72,450

640MWH

$54,400
$2,187,445

Fluorex Net $1,373,805

Savings

REFERENCES
1.

J. O. Dasher et al, "Process for Recovering Nitric Acid Values from Mixed Acid Waste",
U.S Patent 2,993,757, 25 July 1961.

M. Sugimoto, "Process for Recovery Nitric ACid From Waste Pickle Liquor Solution",
U.S. Patent 3,840,646, 8 Oct., 1074.

J. E. Puurunen, "Method for the Regeneration of Pickling Acids", U.S. Patent 4,255,407, 10
Mar, 1981.

Hu Delu et al, "The Regeneration of Nitric and Hydrofluoric Acids From Waste Pickling
Liquid", Presented at Symposium on Iron and Steel Pollution Abatement Technology for
1980, Philadelphia, PA, 18 Nov, 1980.

S. I. Blomquist, et al, "Method For Regenerating Pickling Acids", U.S. Patent 4,526,650, 2
July, 1985.

K. Munns, "Iron Removal From Pickle Liquors Using Absorption Resin Technology", Iron
Control in Hydrometallurgy, J. E. Dutrizac, A. J. Monhemius, Eds., Ellis Horwood Limited,
Chichester, U.K., 1986

C. J. Brown, "Purification of Aluminum Sulfuric Acid Anodizing Solutions", Plating and

Surface Finishing, 66, 54 (January 1979).

C. J. Brown, M. Sheedy, "Process and Apparatus for Regeneration of Volatile Acids", U.S.
patent (pending)