Information
-
Patent Grant
-
6451280
-
Patent Number
6,451,280
-
Date Filed
Tuesday, March 21, 200024 years ago
-
Date Issued
Tuesday, September 17, 200222 years ago
-
Inventors
-
Original Assignees
-
Examiners
- Silverman; Stanley S.
- Johnson; Edward M.
Agents
- Roylance, Abrams, Berdo & Goodman, L.L.P.
-
CPC
-
US Classifications
Field of Search
US
- 423 488
- 423 395
- 423 592
- 423 DIG 1
- 423 483
- 423 484
- 423 633
- 423 DIG 16
- 423 3942
- 422 182
- 095 234
- 095 224
- 096 275
- 096 323
- 096 355
-
International Classifications
-
Abstract
A process for regenerating spent acid liquor feeds an acid liquor into a reactor having a first heating zone for evaporating a substantial portion of the liquid from the spent acid to produce acid vapors and metal salts without decomposing the acid. The metal salts are transferred to a second heating zone where the salts are roasted to form metal oxides. The acid vapors from the primary roasting furnace are then transferred to an absorption column to regenerate the acid. The first heating zone is operated at a temperature below the decomposition temperature of the acid and the metal salts. The second heating zone operates at a higher temperature to completely oxidize the metal salts.
Description
FIELD OF THE INVENTION
The present invention is directed to a process and apparatus for the regeneration of acids by pyrolysis of a spent acid liquor solution. More particularly, the invention is directed to a process and apparatus for the heating of spent acids in a primary heating zone of a furnace followed by heating in a secondary roasting zone.
BACKGROUND OF THE INVENTION
Pickling acids, such as hydrochloric acid and nitric acid, are used in the treatment of iron and other metals. Typically, the spent acids are regenerated for reuse in various processes to minimize waste and problems associated with disposal.
Several acid regeneration processes spray the spent acid through a furnace to pyrolyze or roast the various components and to produce acid vapors. The vapors are passed through an absorption column counter-currently to an absorption liquid which is typically water. The regenerated acid is then withdrawn through the bottom of the column. The pyrolysis exhaust gases are withdrawn from the head space of the absorption column by an external exhaust fan before discharging through a chimney.
Pickling acids of hydrochloric acid used to treat iron or steel produce numerous metal chlorides in the spent acid liquor. Many metal chlorides can be thermally converted into metal oxides and hydrogen chloride. The metal oxides are separated from the gaseous hydrogen chloride. The hydrogen chloride is then recovered as hydrochloric acid for regenerating the pickling acids.
The spent acid solutions are aqueous solutions that are sprayed as fine droplets into a heated reactor. The droplets are heated to evaporate the water from spent acid. After the water is evaporated, the metal compounds begin to decompose to the metal oxide. The droplets descend through the reactor in a free fall to a lower section in the reactor. The residence times are generally very short so that the droplets and metal compounds must be calcined by pyrolysis into the metal oxide and the acid vapor in a few seconds. The acid must be split from the metal oxide before the acid vapors can be removed from the head space in the reactor and the oxides removed from the bottom end.
The short retention time in the reactor always produces a certain amount of residual acid bonded to the metal salt. The residual acid is difficult to remove completely and remains in the oxide as an undesirable contaminant. To minimize residual acid in the metal oxide, the reactor temperature must be set sufficiently high to ensure that the larger droplets and the droplets in the center of the spraying cone are substantially calcined. There is a time delay in the conversion process starting at the outer edges of the spraying cone and moving inwards. As a result, the oxide is overheated and quality of the oxide deteriorates with the specific surface area becoming smaller. In addition, there is always a risk of higher or lower levels of acid vapors being discharged with the oxide.
One example of this type of process is disclosed in Austrian Patent No. 395,312. A disadvantage of this type of process is that evaporation and decomposition takes place in a single step at high temperatures causing considerable acid decomposition. When nitric acid is treated, high levels of nitric oxides (NO, NO
2
) are produced. In addition, considerable cooling is needed to compensate for the high temperatures and, in some instances, the addition of oxidants is necessary. A similar process is also disclosed in U.S. Pat. No. 5,149,515. In this process, the acid being regenerated is evaporated in a counter-current flow using the exhaust from the reactor and then decomposed in the reactor. An other example of processes for regenerating acids is disclosed in U.S. Pat. No. 4,049,788.
Accordingly, a continuing need exists in the industry for an improved process for regenerating spent acid liquors.
SUMMARY OF THE INVENTION
The present invention is directed to a process and apparatus for regenerating spent acids, and particularly pickling acids. More particularly, the invention relates to a process and apparatus for the spray roasting of spent acid liquor where the reactor has a first heating zone serving as an evaporation zone and a second heating zone serving as a roasting zone.
Accordingly, a primary object of the invention is to provide a process and apparatus for the complete and uniform roasting of a spent acid liquor and recovering the acid vapors.
Another object of the invention is to provide a process and apparatus for heating a spent acid liquor in a first heating zone of a reactor to separate a substantial portion of the acid vapors and water from the metal salts and transferring the metal salts to a second heating zone or roasting chamber for converting the metal salts to metal oxides.
A further object of the invention is to provide a process for the spray roasting of spent pickling acids and regenerating acid without the formation of waste water.
Another object of the invention is to provide a process for regenerating acid by heating a spent acid in a first heating zone to vaporize the acid substantially without decomposing the acid.
A further object of the invention is to provide a process of regenerating acid by heating spent acid in a first heating zone of a reactor to separate acid vapors from metal salts substantially without decomposing the metal salts or forming metal oxides in the first heating zone.
Still another object of the invention is to provide a process and apparatus for heating a spent acid liquor at first temperature to evaporate the water from the liquor at a sufficiently low temperature to prevent decomposition of the acid and to prevent the formation of metal oxides followed by heating the metal salts to a second temperature to oxidize the metal salts.
The objects of the invention are basically attained by providing a process for regenerating spent acid liquor, comprising the steps of feeding a spent acid solution into a first heating zone of a reactor and heating the spent acid solution at a first temperature sufficient to evaporate a substantial portion of the water from the acid solution and to form particles of metal compounds and acid vapors, feeding the particles of metal compounds to a second heating zone of the reactor and heating at a second temperature to decompose the metal compounds, wherein the second temperature is higher than the first temperature, and recovering and regenerating an acid solution from the acid vapors.
The objects of the invention are further attained by providing a process of regenerating an acid solution from a spent acid solution containing a metal compound. The process comprises the steps of feeding the spent acid solution into an evaporating chamber of a reactor and heating the spent acid solution at a first temperature sufficient to evaporate a substantial portion of water from the spent acid solution and forming acid vapors and metal salts substantially without decomposing the acid and substantially without forming metal oxides, feeding the metal salt to a pyrolysis chamber of the reactor and heating the metal salts to decompose the metal salts and produce a metal oxide, and recovering the acid vapors from the reactor and regenerating the acid solution.
These and other advantages and salient features of the invention will become apparent from the annexed drawings and the detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring to the drawings which form a part of the original disclosure in which:
The FIGURE is a schematic diagram of the acid regenerating plant in an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a process and apparatus for roasting spent acid liquor in the regeneration of an acid. More particularly, the invention is directed to a process for heating a spent acid liquor at a first temperature to separate acid vapors and metal salts and then heating the metal salts at a second temperature to roast and oxidize the metal salts to form metal oxides.
The process and apparatus is suitable for large scale acid regeneration plants. The present invention primarily relates to a process for separating and recovering acid vapors from spent acids that contain metal compounds. The acid vapors are recovered from the furnace and carried to further processing devices such as scrubbers and absorbers to regenerate the acids as shown in FIG.
1
and discussed hereinafter in greater detail. An example of suitable processing components for regenerating acid solutions from acid vapors is disclosed in commonly owned U.S. Pat. No. 5,149,515 to Karner which is hereby incorporated by reference in its entirety.
The process of the invention is particularly suitable for spent acids used in the treatment of various metals. Examples of acids that are particularly suitable for recovery include hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, and mixtures thereof. The spent acids can include pickling acids used in the treatment of iron, chromium, nickel, titanium, zirconium, aluminum, and the like. The spent pickling acids typically contain large amounts of metal salts that must be separated or decomposed during the roasting process to regenerate the spent acid efficiently. The process of the invention is particularly directed to regenerating hydrofluoric acid, nitric acid and mixtures thereof from spent acid solutions containing compounds of iron, chromium and nickel.
The process of the invention in a preferred embodiment feeds a spent acid solution into a reactor having at least two heating zones that can operate at two different temperatures. A first heating zone is preferably operated at a temperature that is sufficient to evaporate a substantial portion of water from the acid and produce acid vapors. Preferably, the temperature in the first heating zone is maintained at a sufficiently low temperature to prevent or inhibit decomposition of the acid and to prevent the formation of metal oxides in the first heating zone. However, the temperature in the first heating zone is sufficiently high to evaporate all or most of the water and produce the metal salts in particulate form.
The metal salts and other metal compounds in the spent acids are separated as solids in the first heating zone by the evaporation of water and vaporization of the acids. The metal compounds free fall downward through the first heating zone and are then immediately directed into a second heating zone. The second heating zone is operated at a second temperature that is higher than the first temperature and defines a decomposition zone. The metal salts are heated to a roasting temperature to decompose the metal compounds and form metal oxides. The metal oxides produced by the process of the invention are clean and substantially pure metal oxides being substantially free of acid residues and other impurities. The clean and substantially pure metal oxides produced by the process of the invention are suitable for sale and use in various processes. For example, the metal oxides are suitable for use as ferrites for the manufacture of magnetic strips.
Referring to the figure, the acid regenerating apparatus in a preferred embodiment of the invention includes a reactor
10
having a first heating zone
12
and a second heating zone
14
. The reactor
10
includes a substantially circular side wall
16
and a frustoconical bottom wall
18
converging toward the center axis. A discharge opening
20
is provided in the bottom wall
18
and positioned substantially concentric to a vertical axis of the apparatus
10
. An annular collar (not shown) extends downwardly from the bottom wall
18
and surrounds opening
20
. The reactor
10
further includes a top wall
22
having an outlet opening
24
. In the embodiment illustrated, a supply pipe
26
for supplying acid to reactor
10
extends through opening
24
into the top end of the first heating zone
12
. A nozzle
28
is attached to the end of pipe
26
for spraying the spent acid solution into the first heating zone
12
. A burner
30
is connected to a fuel supply pipe
32
and air supply pipe
33
for feeding hot combustion gases into the first heating zone
12
.
A housing
34
is coupled to the lower end of the spray roasting apparatus
10
. Housing
34
includes a substantially cylindrical side wall
36
and a bottom wall
38
. Generally, bottom wall
38
is a flat wall substantially perpendicular to side wall
36
. In the embodiment illustrated, side wall
36
is coupled to the conical bottom wall
18
of the apparatus
10
. Housing
34
encloses and defines the second heating zone
14
and is positioned directly below the first heating zone
12
. In one preferred embodiment, second heating zone
14
is coupled directly to first heating zone
12
so that metal compounds that are separated from the spent acid in first heating zone
12
are fed directly into the second heating zone
14
. The second heating zone
14
is positioned directly below the first heating zone
12
so that the particulates are gravity fed to the second heating zone. In a preferred embodiment, the second heating zone
14
is integrally formed with the first heating zone
12
. In alternative embodiments, the second heating zone is a separate unit coupled to the first heating zone
12
.
As shown in the FIGURE, discharge opening
20
of the conical shaped bottom wall
18
has a substantially annular shape at the apex of the conical bottom wall
18
. A cone
40
is positioned in the opening
20
to restrict the size of the opening and restrict the size of particles flowing from the first heating zone
12
into the second heating zone
14
as discussed hereinafter in greater detail. Cone
40
defines the size of the opening and restricts the flow of gases into the second heating zone
14
. Cone
40
includes a solid tip and is coupled to a shaft
46
.
Cone
40
is positioned in the discharge opening
20
and is dimensioned to provide a small gap between cone
40
and discharge opening
20
. In embodiments of the invention, cone
40
can include a plurality of ridges or ribs to assist in breaking the particles into smaller pieces as they pass from the first heating zone
12
through the discharge opening
20
into the second heating zone
14
. Shaft
46
is coupled to a motor
52
for rotating the cone
40
to feed the particulate materials from the first heating zone
12
into the second heating zone
14
at a substantially uniform and constant rate. The size of the gap between opening
20
in the bottom wall
18
and the cone
40
is selected to define the particle size of the metal compounds passing into the second heating zone
14
. Generally, the particles entering the secondary heating zone
14
are about 1 to about 300 microns. In preferred embodiments, the gap is sufficiently small to effectively separate the first heating zone
12
from the second heating zone
14
.
As shown in the FIGURE, a burner
54
is included in the second heating zone
14
. Burner
54
is connected to the fuel supply
32
and air supply
33
to operate the second heating zone
14
at a temperature independent of the temperature of the first heating zone
12
.
A mixing and conveying device
56
is provided in the bottom end of the secondary heating zone
14
adjacent bottom wall
38
. In one embodiment of the invention, the mixing device
56
is a rake for mixing the solid materials in the second heating zone
14
and directing the materials to an outlet. A radial lock
58
is connected to the outlet of the second heating zone
14
to isolate the second heating zone
14
.
In the process of the invention, waste acid, such as spent pickling acid, is fed through the pipe
26
and nozzle
28
and sprayed into the first heating zone
12
. Hot combustion gases from burner
30
are fed through pipe
32
into the first heating zone
12
for heating and evaporating the spent acid. The droplets of the spent acid fall downwardly through the first heating zone
12
where a substantial portion of the water and acid components vaporize. The water vapor and acid vapors are withdrawn through opening
24
and directed to a suitable absorption column where an absorption liquid is contacted with the vapors to produce a regenerated acid. The metal salts in the spent acid fall through the hot combustion gases in the first heating zone
12
. The selected temperature in the first heating zone
12
is dependent on the composition of the spent acid and the desired extent of oxidation of the metal salts. In one embodiment of the invention, the first heating zone is heated to a temperature of about 110° to about 350° C. In a preferred embodiment, the spent acid is heated to a temperature of about 150° C. to about 200° C. Decomposition of nitric acid is largely avoided at these temperatures.
In preferred embodiments of the invention, the first heating zone
12
is sufficient to vaporize the water in the spent acid and vaporize the acid so that the first heating zone forms an evaporating chamber for the spent acid. The temperature of the first heating zone is maintained sufficiently low to prevent decomposition of the acid and to prevent the substantial formation of metal oxides from the metal salts contained in the spent acids. In one embodiment of the invention, the spent acid comprises nitric acid and the temperature in the first heating zone is maintained at a temperature to vaporize the acid substantially without the formation of nitrogen oxides in the vapor stream. Heating the spent acids above the decomposition temperature results in low recovery of nitric acid, typically in the range of 30% to 50% of the acids originally present. Accordingly, the first heating zone is at a temperature to prevent decomposition of the acid and maximize recovery of the acid.
The particulates formed in the first heating zone
12
, that are primarily composed of the metal salts and substantially free of acid, fall downward along the conical bottom wall
18
toward the outlet
20
and the cone
40
. The motor
52
and shaft
46
rotate the cone about its axis to break up the oversized particulates into sufficiently small size particles, such that they can pass through the gap between the cylindrical side wall
50
of cone
40
and the edge of the opening
20
of the conical bottom wall
18
. The metal salts fall downwardly through the gap into the second heating zone
14
and rest on the bottom wall
38
of housing
34
.
A fuel and air mixture is fed to the burner
54
to heat the second heating zone to a desired temperature. Mixing device
56
being connected to the shaft
46
rotates simultaneously with the rotation of cone
40
to continuously mix the particles in the second heating zone
14
. Continuous mixing of the particles by the mixing device
64
continuously exposes fresh surfaces of the particulates to ensure proper and uniform roasting and a uniform composition of the resulting metal oxides.
The temperature of the second heating zone is selected depending on the nature of the metal salts and the desired extent of roasting. In preferred embodiments, the temperature in the second heating zone is higher than the temperature in the first chamber. In one embodiment of the invention, the second heating zone is heated to a temperature of approximately 450°-900° C., and preferably 550° to 700° C. Preferably, the temperature in the second heating zone is sufficiently high to produce highly pure metal oxides. In addition, the second heating zone is at a roasting or oxidizing temperature sufficient to decompose the metal compounds and drive off any acid residues.
The secondary heating at the higher temperatures is particularly suitable for roasting metal chlorides to produce metal oxides that are substantially free of acid residues. Typically, the second heating zone is operated at a sufficiently high temperature to drive off the remaining acid residues from the particles and completely oxidize the metal salts without decomposing the oxides. The particles of the metal compounds that enter the second heating zone
14
are substantially free of acid so that little or no decomposition of the acid takes place in the second heating zone.
The exhaust gases from the reactor
10
are comprised of acid vapors, water vapor and dust. An outlet pipe
70
is coupled to reactor
10
and includes an open end defining outlet opening
24
of reactor
10
. The exhaust gas is passed through a pipe
70
from reactor
10
to a jet or Venturi washer or scrubber
72
and through a pipe
74
to an absorption column
76
. Venturi scrubber
72
can be a conventional venturi scrubber capable of treating the exhaust gases as known in the art. A scrubbing liquid is injected into the Venturi scrubber
72
to cool the exhaust gas, to remove dust particles and to remove some vapors. In one embodiment of the invention, the scrubbing fluid is a regenerated acid from an absorption column
76
.
The gases exit the scrubber
72
and are fed through pipe
74
to a bottom end of absorption column
76
. In the embodiment illustrated, absorption column
76
is a unitary structure having vertically positioned chambers. A bottom chamber
78
receives the exhaust gases from pipe
74
and regenerated acid and wash water from the column
76
. A screen
80
extends across the column for supporting a bed
82
of absorption material such as gravel. A screen
84
is also provided at an upper end of the column to contain the absorption bed
82
and define a gas chamber
86
at the top end of the column
76
. The exhaust gas is fed into the bottom chamber
78
and flows upward through the absorption bed
82
to the gas chamber
86
. An absorption liquid, such as water or regenerated acid, is supplied through a pipe
88
to a spray nozzle
90
in the gas chamber
86
. The absorption liquid is sprayed outwardly across the top of the absorption bed
82
and flows downward through the bed
82
to the bottom chamber
78
. In one embodiment, the absorption liquid is rinse water from a pickling process.
The regenerated acid collected in the bottom chamber
78
is withdrawn through a pipe
92
by a pump
94
. A portion of the regenerated acid stream is directed to the venturi scrubber
72
through a pipe
96
. A second portion of the acid stream is withdrawn through a pipe
98
for subsequent use.
A wash column
100
is positioned in the absorption column
76
and extends from the gas chamber
86
downwardly through the bed
82
of absorbent material and through the collection chamber
78
. A wash water collection chamber
102
is positioned directly below the chamber
78
such that a bottom wall
104
of chamber
78
defines the top wall of chamber
102
. Collection chamber
102
serves as a reservoir for the absorption column
76
and the washing circuit.
The wash column
100
is a hollow tube having a first open end
106
positioned in the gas chamber
86
above the bed
82
of the absorbent material and an open bottom end
108
positioned in the wash water collection chamber
102
. A washing liquid is sprayed through a pipe
110
by a nozzle positioned directly above the open end
106
of the wash column
100
. The exhaust gas which passes upwardly through the bed
82
of absorbent material into the gas chamber
86
is directed downwardly through the wash column
100
where it mixes with the wash liquid being sprayed through the nozzle so that the droplets remove any further entrained particles or vapors.
The collected wash liquid is withdrawn from the collection chamber
102
through a pipe
112
by a pump
114
and carried to the nozzles in the gas chamber
86
as the absorption liquid.
In one embodiment of the invention, the absorption column is maintained at a temperature of about 70° C. to about 90° C. during the absorption of the acid vapors. In a preferred embodiment, the absorption column is maintained at a temperature of about 78° C. to about 85° C. In a further embodiment, the absorption process can be under adiabatic conditions to eliminate the need for heat exchangers and other temperature control devices.
The exhaust gas and any remaining vapor contained in the collection chamber are withdrawn through a pipe
116
by a fan or blower
118
to a separator
120
for removing any water droplets or particulate matter. A source of fresh water or wash water from a pickling line is introduced through a pipe
122
positioned upstream of the blower
118
to assist in removing particulates and vapors from the exhaust gas stream. The amount of fresh water added to the system is determined by the desired concentration of the regenerated acid. The exhaust gas is discharged from the separator
120
through a pipe
124
to a heat exchanger
126
and then to a catalytic treatment column
28
. Liquids separated from the exhaust gas stream in the separator
120
are returned to the collection chamber
102
through a pipe
130
. The gases from the catalytic treatment column
128
are directed through the heat exchanger
126
to a discharge stack
132
.
The regenerating plant discussed above is an example of a suitable assembly. In further embodiments, a sodium hydroxide (NaOH) or calcium hydroxide (Ca(OH)
2
) scrubber can be used. However, in this embodiment, the water from the scrubber cannot be used as the absorption liquid in the column. In a further embodiment, a heat recovery stage can be included between the reactor and the absorption column to boost the concentration of the waste pickling liquor. In still further embodiments, a cyclone separator can be provided downstream of the reactor to improve dust separation from the exhaust gas stream.
In the embodiment illustrated in
FIG. 1
, the waste wash water from the separator
120
is returned to the absorption column for mixing with the regenerated acid. Regenerated acid from the absorption column is recycled as the absorption liquid in the column and as the wash liquid in the venturi scrubber
72
. In this manner, the system is a substantially closed system and does not discharge waste water that requires processing.
While several embodiments have been shown to illustrate the invention, it will be understood by those skilled in the art that various modifications and changes can be made therein without departing from the scope of the invention as defined in the following claims.
Claims
- 1. A process for recovering acids from a spent acid solution containing metal salts comprising the steps offeeding a spent acid solution into a first heating zone of a reactor and heating said spent acid solution at a first temperature sufficient to evaporate a substantial portion of the water from said acid solution to form substantially dry particles of metal compounds, water vapor and acid vapors, wherein said substantially dry particles are formed substantially without decomposing said metal compounds, feeding said particles of metal compounds from said first heating zone to a second heating zone of said reactor and heating at a second temperature sufficient to decompose said metal compounds, wherein said second temperature is higher than said first temperature, and recovering said acid vapors from said first heating zone and regenerating an acid solution from said acid vapors.
- 2. The process of claim 1, wherein said spent acid solution is selected from the group consisting of hydrofluoric acid, nitric acid, and mixtures thereof.
- 3. The process of claim 1, wherein said spent acid solution comprises a metal compound selected from the group consisting of iron, chromium, nickel, and mixtures thereof.
- 4. The process of claim 1, comprising heating said spent acid solution at said first temperature to vaporize said acid substantially without decomposing said acid and substantially without decomposing said metal compounds to metal oxides.
- 5. The process of claim 4, comprising heating said metal compounds in said second heating zone to a temperature sufficient to produce metal oxides.
- 6. The process of claim 1, wherein said first temperature is about 110° C. to about 350° C.
- 7. The process of claim 1, wherein said first temperature is about 150° C. to about 200° C.
- 8. The process of claim 1, wherein said second temperature is about 450° C. to about 900° C.
- 9. The process of claim 1, wherein said second temperature is about 550° C. to about 700° C.
- 10. The process of claim 1, further comprising feeding said acid vapors from said first heating zone of said reactor to an acid absorption column and absorbing said acid vapors to produce a regenerated acid.
- 11. The process of claim 10, comprising feeding said acid vapors through said absorption column at a temperature of about 70° C. to about 90° C.
- 12. The process of claim 10, comprising feeding said acid vapors from said reactor through said acid absorption column at a temperature of about 78° C. to about 85° C.
- 13. The process of claim 10, wherein said absorbing step is under adiabatic conditions.
- 14. The process of claim 10, further comprising feeding exhaust gases from said absorption column through a scrubber, feeding water into said scrubber, and scrubbing said exhaust gas.
- 15. The process of claim 14, comprising recovering waste water from said scrubber and feeding said waste water into said absorption column.
- 16. The process of claim 1, wherein said first heating zone is integral with said second heating zone and said process comprises feeding said metal compounds from said first heating zone directly into said second heating zone.
- 17. The process of claim 1, wherein said reactor is a spray reactor including said first heating zone and said second heating zone, and said process comprises spraying said spent acid solution into said first heating zone to form droplets of said spent acid solution in said first heating zone.
- 18. The process of claim 17, further comprising feeding hot combustion gases into said first heating zone to heat said spent acid solution at said first temperature to produce substantially dry particles of said metal compounds.
- 19. The process of claim 18, wherein said spray reactor includes a burner for feeding said hot combustion gases into said first heating zone.
- 20. The process of claim 17, wherein said second heating zone is positioned directly below said first heating zone, said process comprising spraying said spent acid solution into said first heating zone to produce said particles of metal compounds so that said particles of metal compounds fall downwardly from said first heating zone into said second heating zone.
- 21. The process of claim 1, wherein said process is a continuous process, further comprising spraying said spent acid solution in said first heating zone and heating to produce substantially dry particles of said metal salts and feeding said particles from said first heating zone directly to said second heating zone.
- 22. A process of regenerating an acid solution from a spent acid solution containing a metal compound, said process comprising the steps offeeding said spent acid solution into an evaporating chamber of a reactor and heating said spent acid solution at a first temperature sufficient to evaporate a substantial portion of water from said spent acid solution and forming acid vapors and substantially dry particles of metal salts substantially without decomposing said acid and substantially without forming metal oxides, feeding said metal salts from said evaporating chamber to a pyrolysis chamber of said reactor and heating said metal salts to decompose said metal salts and produce a metal oxide, and recovering said acid vapors from said reactor and regenerating said acid solution.
- 23. The process of claim 22, wherein said spent acid solution is selected from the group consisting of hydrofluoric acid, nitric acid, and mixtures thereof.
- 24. The process of claim 22, wherein said spent acid solution comprises a metal compound selected from the group consisting of iron, chromium, nickel, and mixtures thereof.
- 25. The process of claim 22, wherein said first temperature is about 110° C. to about 350° C.
- 26. The process of claim 22, wherein said first temperature is about 150° C. to about 200° C.
- 27. The process of claim 22, wherein said second temperature is about 450° C. to about 900° C.
- 28. The process of claim 22, wherein said second temperature is about 550° C. to about 700° C.
- 29. The process of claim 22, further comprising feeding said acid vapors from said reactor to an acid absorption column and absorbing said acid vapors.
- 30. The process of claim 29, comprising feeding said acid vapors through said absorption column at a temperature of about 70° C. to about 90° C.
- 31. The process of claim 29, comprising feeding said acid vapors from said reactor through said acid absorption column at a temperature of about 78° C. to about 85° C.
- 32. The process of claim 29, wherein said absorbing step is under adiabatic conditions.
- 33. The process of claim 29, further comprising feeding exhaust gases from said absorption column through a scrubber, feeding water into said scrubber, and scrubbing said exhaust gas.
- 34. The process of claim 33, comprising recovering waste water from said scrubber and feeding said waste water into said absorption column.
- 35. The process of claim 22, wherein said first heating zone is integral with said second heating zone and said process comprises feeding said metal compounds from said first heating zone directly into said second heating zone.
- 36. The process of claim 22, wherein said reactor is a spray reactor including said evaporating chamber and said pyrolysis chamber, and said process comprises spraying said spent acid solution into said evaporating chamber to form droplets of spent acid solution in said evaporating chamber.
- 37. The process of claim 36, wherein said spray reactor includes a burner for feeding said hot combustion gases into said evaporation chamber.
- 38. The process of claim 36, wherein said pyrolysis chamber is positioned directly below said evaporating chamber, said process comprising spraying said spent acid solution into said evaporating chamber to produce said metal salts, whereby said metal salts fall downwardly from said evaporating chamber to said pyrolysis chamber.
- 39. The process of claim 38, further comprising withdrawing said acid vapors from said evaporating chamber, directing said acid vapors to an absorption column and regenerating said acid solution.
- 40. The process of claim 22, wherein said process is a continuous process further comprising spraying said spent acid solution into said evaporating chamber and heating to produce substantially dry particles of said metal salts, and feeding said substantially dry particles directly form said evaporation chamber to said pyrolysis chamber.
- 41. A process for regenerating an acid from a spent acid solution containing metal salts comprising the steps ofspraying a spent acid solution into a first heating zone of a spray roasting reactor to form droplets of said spent acid solution and heating said droplets of spent acid solution at a first temperature sufficient to form substantially dry particles of metal compounds and acid vapors substantially without decomposing said metal compounds, feeding said substantially dry particles of metal compounds from said first heating zone to a second heating zone of said reactor and heating said particles of metal compounds at a second temperature sufficient to decompose said metal compounds, wherein said second temperature is higher than said first temperature, and recovering said acid vapors from said first heating zone and regenerating an acid solution from said acid vapors.
- 42. The process of claim 41, further comprising heating said spent acid solution in said first heating zone to vaporize said acid substantially without decomposing said acid, and to prevent oxidizing said metal compounds to metal oxides in said first heating zone.
- 43. The process of claim 41, comprising the step of feeding hot combustion gases into said first heating zone to heat said spent acid solution.
- 44. The process of claim 41, comprising feeding hot combustion gases to said second heating zone to oxidize said metal compounds.
- 45. The process of claim 41, comprising spraying said spent acid solution into an upper end of said first heating zone whereby said droplets fall downwardly through said heating zone to a bottom end.
- 46. The process of claim 41, comprising heating said droplets in said first heating zone to a temperature of 110° C. to 350° C.
- 47. The process of claim 46, comprising heating said metal compounds in said second heating zone at a temperature of about 450° to 900° C.
Priority Claims (1)
Number |
Date |
Country |
Kind |
506/99 |
May 1999 |
AT |
|
US Referenced Citations (11)