Method of recovering fumed silica from spent potliner

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 09/277,804, filed Mar. 27, 1999, which is a continuation-in-part of U.S. Ser. No. 08/977,435, filed Nov. 24, 1997, now U.S. Pat. No. 5,955,042, which is a continuation-in-part of U.S. Ser. No. 08/569,271, filed Dec. 8, 1995, now U.S. Pat. No. 5,723,097, issued Mar. 3, 1998.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to processes for treating spent potliner material from aluminum reduction cells in a manner in which hazardous wastes are converted and recycled to useful, non-hazardous substances. More specifically, the present invention relates to a process of recovering, from spent aluminum potliner material, aluminum fluoride, reusable salts such as sodium sulfate and refractory material such as calcium feldspar which can be used to make brick products, for example. Further, large amounts of energy can be recovered from the carbon, e.g., 8000 to 9000 BTU/lb of carbon.

2. Description of the Prior Art

The Hall-Heroult process for the production of metallic aluminum dates from the 19

th

Century. Many refinements to the process have been made, but the basic Soderberg or pre-bake configurations using Hall-Heroult cells remain the most common processes for aluminum production throughout the world. In these processes, the bottom and internal walls of a cathode of an aluminum pot are formed with a liner of carbon blocks joined by conductive carbonaceous binder and wrapped with refractory firebricks and insulating bricks, the resulting combination being referred to as “potliner”. The insulating bricks and firebricks are composed of material such as silica and alumina (aluminum oxide).

During the production of aluminum, the aluminum reduction pot is filled with a bath of alumina and molten salts. Over the three to seven year life span of an aluminum reduction pot bath, salts migrate into the potliner, thereby resulting in the deterioration and eventual failure of the utility of the aluminum cell as a cathode. During its life span, a cathodic potliner may absorb its own weight in bath salt materials. The failed potliner material is referred to as spent potliner or SPL.

When an aluminum reduction cell is taken out of service, the SPL is cooled and fractured to facilitate subsequent handling and disposal. The fractured SPL is a non-homogenous material which contains carbon, silica and/or alumina from the insulating brick and firebricks, aluminum, significant quantities of sodium salts, aluminum salts and oxides, fluoride salts and traces of cyanides. On the average, a large aluminum smelter with a production capacity of 175,000 tons of aluminum per year will produce about 6,000-12,000 tons of SPL per year. The quantity of SPL generated annually in the United States alone has in recent years exceeded approximately 230,000 tons per year.

Because of its cyanide content, its high concentration of leachable fluoride compounds, and the high volumes of SPL produced, SPL presents a significant environmental hazard and a major burden for aluminum producers, who remain ultimately liable for the proper disposal of SPL. The SPL has long been listed as a hazardous waste by the U.S. federal and state environmental authorities. Current regulations require that SPL ultimately be treated to explicitly remove the toxic cyanide, high concentration of leachable fluoride compounds, and other characteristics which cause it to be listed as hazardous before it can be placed in a landfill disposal site.

Many different approaches have been tried over the years to convert SPL to non-hazardous materials. One major technique includes combustion or incineration of the SPL as exemplified in U.S. Pat. Nos. 4,735,784; 4,927,459; 5,024,822; 5,164,174; 5,222,448 and 5,286,274. Unfortunately, most of these processes result in an end product consisting of a glassy slag material which still contains some hazardous, allegedly non-leachable, materials.

Another process includes chemical treatment to convert SPL to non-hazardous materials. In these types of processes, as exemplified by U.S. Pat. No. 4,113,831, the initial SPL constituents are replaced with compounds which are less toxic, but which compounds are still above the hazardous listing levels established by various environmental authorities. Moreover, these residues generally have a final volume which is comparable to the volume of the input.

Another major technique of converting SPL to non-hazardous materials includes pyrohydrolysis of the SPL material. This process generally includes pyrolysis of the material in conjunction with the introduction of water to create an off-gas containing the fluoride materials as illustrated in U.S. Pat. No. 4,113,832. Such pyrohydrolysis techniques may also be used in conjunction with fluidized bed reactors as disclosed in U.S. Pat. Nos. 4,158,701 and 4,160,808. These processes also still tend to produce large volumes of waste material which must be stored in landfills and which may contain allegedly non-leachable hazardous waste. Thus, there is still a need for a process to chemically treat SPL material from aluminum reduction cells, wherein the end products of such a treatment process are all usable either within the process itself or with other commercial processes as well as secondary end products which are non-toxic to the environment and which do not include large volumes of material for the landfill or for storage.

SUMMARY OF THE INVENTION

It is, accordingly, one object of the present invention to provide a process for treating spent potliner material from aluminum reduction cells.

It is another object of the present invention to provide such a process wherein aluminum fluoride, sodium compounds such as sodium sulfate, calcium compounds and iron compounds and refractory materials which can be converted to brick or used as fuel or cement additive, are all recovered from the spent aluminum potliner material in a form which is commercially usable.

Still, it is another object of the present invention to provide a process for treating SPL to selectively recover usable compounds such as aluminum fluoride, sodium sulfate, chloride salts, refractory products and other useful materials therefrom.

Yet another object of the present invention is to provide a process for the treating of spent potliner material from aluminum reduction cells which includes a total recycle of all by-products and elimination of all hazardous wastes.

To achieve the foregoing and other objects and in accordance with the purpose of the present invention, as embodied and broadly described herein, a process of treating spent potliner material from aluminum reduction cells and recovering useful products is disclosed. In the process of the present invention, spent potliner material is introduced into an acid digester containing, for example, sulfuric acid. As a result of this step, a gas component is produced which includes hydrogen fluoride, silicon tetrafluoride and hydrogen cyanide. Also, a slurry component is produced which includes carbon, a refractory material including silica, alumina, sodium compounds such as sodium sulfate, aluminum compounds such as aluminum sulfate, iron compounds such as iron sulfate, magnesium and calcium compounds such as magnesium and calcium sulfate. The slurry component remains in the digester after the gas component is removed. The gas component is recovered and heated an effective amount to convert or decompose the silicon tetrafluoride to fumed silica, hydrogen cyanide to a remaining gas component including CO

2

, H

2

O, and nitrogen oxides, as well as HF gas. The remaining gas component is directed through a water scrubber in which the HF gas is converted to liquid hydrofluoric acid. The hydrofluoric acid is then admixed with alumina trihydrate to form aluminum fluoride (a commercially useful end product) and water.

The slurry component is rinsed with water to separate a solid fraction containing carbon, and refractory materials such as alumina and silica from a liquid fraction. The solid fraction may be admixed with an alumina/silica mixture and then used as fuel in cement or glass manufacturing. Alternatively, the solid fraction can then be subjected to an elevated temperature in an oxygen-rich atmosphere. This causes the carbon to oxidize to carbon dioxide which itself has utility as a fuel, leaving a refractory material which has commercial utility in forming brick, glass or ceramic tile.

In one aspect of the invention, the remaining liquid portion of the slurry is mixed with alcohol at a preferred ratio of about four parts alcohol to about one part liquid. This step removes in excess of 97% of the salts and leaves a solution of sulfuric acid and alcohol. This solution is then subjected to distillation, with the volatile alcohol being recovered for reuse, and the remaining sulfuric acid available to be added back to the system digester to reduce acid consumption. The filtered salts are then dissolved back in H

2

O and the pH adjusted to a basic pH, e.g., about 12.0 to 12.5, with NaOH. This step holds aluminum in solution as sodium aluminate and precipitates all other impurities. The solution is filtered to remove the impurities containing calcium, iron, magnesium and silicates primarily. The clear solution is then further pH adjusted to an alkaline pH, e.g., about 7.0 to 8.0 pH, to remove Al(OH)

3

, and the remaining solution is then admixed with alcohol to form and precipitate sodium sulfate.

In another aspect of the invention, the remaining liquid portion of the slurry may be treated to form soluble sodium aluminate by adjusting the pH, for example, of the liquid portion. Adjusting the pH causes insoluble salts such as calcium, iron and magnesium salts to form a precipitate which is removed leaving a solution containing soluble sodium aluminate. The insoluble salts are then filtered and reused. The insoluble salts are further processed using acid and heat to form a high purity calcium compound. Also, iron compounds are precipitated and recovered from the remaining liquid portion. In addition, magnesium salts are also precipitated and recovered from the remaining liquid portion. The solution remaining after calcium, iron and magnesium salts are removed is added to the solution containing soluble sodium aluminate. The pH of this solution is adjusted to form alumina trihydrate which can be removed from the solution. The solution remaining may be treated to remove residual Al(OH

3

) before being added back to the digestion step.

Further, the digest may be adjusted to produce a first gas component comprised of at least one material selected from the group consisting of silicon tetrafluoride, hydrogen fluoride, hydrogen cyanide gas and water vapor, and a slurry component comprised of at least one material selected from the group consisting of carbon, silica, alumina, and sodium, iron, calcium and magnesium compounds. The first gas component is removed from the digester and heated to a temperature sufficiently high to convert said silicon tetrafluoride to fumed silica and hydrogen fluoride. Thereafter, the fumed silica is separated from the hydrogen fluoride to recover fumed silica from spent potliner material.

These and other objects of the present invention will become apparent to those skilled in the art from the following detailed description, showing the contemplated novel construction, combination, and elements as herein described, and more particularly defined by the appended claims, it being understood that changes in the precise embodiments to the herein disclosed invention are meant to be included as coming within the scope of the claims, except insofar as they may be precluded by the prior art.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings which are incorporated in and form a part of the specification illustrate complete preferred embodiments of the present invention according to the best modes presently devised for the practical application of the principles thereof, and in which:

FIG. 1

is a flow diagram illustrating the various process steps and byproducts of the present invention.

FIG. 2

is a flow diagram illustrating steps in recovering AlF

3

from spent potliner.

FIG. 3

is a flow diagram illustrating steps in recovering refractory products, (NH

4

)

2

SO

4

and CaCl

2

from spent potliner.

FIG. 4

is a flow diagram illustrating steps in recovering Al(OH)

3

, Na

2

SO

4

and metal chlorides from spent potliner.

FIG. 5

is a flow diagram showing an alternate method of treating calcium, iron and magnesium compounds in spent potliner.

FIG. 6

is a flow diagram illustrating alternate steps for recovering values from spent potliner.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The process of the present invention for the treatment of spent potliner (SPL) waste materials is shown diagrammatically by

FIG. 1

, which process is generally identified by the reference numeral

10

. The input material

12

consists of SPL as its major ingredient, but may also include any other waste stream with similar chemical make-up. One preferred operation is described below, although it will be apparent to one skilled in the art that many of the steps are optional.

In preferred operations, input material

12

is pulverized by a crusher

14

to a particulate feed size of 16 mesh or less, although larger particles may be used. One preferred form of crusher operation is a two-stage process in which an initial crusher hopper

14

reduces the SPL material to approximately two-inch size pieces, with the resulting two-inch size pieces then being sent to a second crusher

15

which reduces them to about 16 mesh or less in size. The particulate material from the crushers

14

and

15

is then sent to a magnetic separator

16

which removes iron and any other ferromagnetic particulate metal

17

, and in particular iron, from the particulate feed. A 16 mesh classifier

18

returns any particulate material which is greater than 16 mesh to crusher

14

through a return loop

19

in order to reduce the size of that material to 16 mesh or less, since particulate material larger than 16 mesh is not recommended or preferred.

The resulting particulate feed

20

may be directed initially into a soak tank

22

for a sufficient time, e.g., about 12 to 24 hours, and temperature to remove gases such as ammonia, acetylene and methane gases, the soak tank preferably containing neutral H

2

O and waste water from caustic scrubber

58

used in the polishing step. The feed

23

is then directed into an acid digester

24

containing preferably, sulfuric acid; however, other acids which liberate HF, SiF

4

or HCN gases may be used singly or in combination with sulfuric acid. Particulate feed

23

is preferably fed into digester

24

by a sealed, variable drive, heated screw. The auger digester

24

is preferably maintained under a negative pressure in order to assist in removing gases which are generated within digester

24

. In preferred operations, the digester

24

is maintained at an elevated temperature, for example, up to 300° C. and typically 100° or 135° to 250° C. The speed of the preferred input and output augers are adjusted to allow for an approximately 30-180 minute retention time of the particulate feed material

23

within the digester

24

with longer times not found to be detrimental. Shorter times can be used at higher temperatures. In the digester

24

, the SPL and other materials react with the acid, e.g., sulfuric acid, causing any fluoride to be converted to HF and SiF

4

gas, respectively, which is continuously removed from the digester

24

in a gas stream or gas component

28

. Cyanide material is preferably decomposed instead of being liberated as HCN gas. The remaining solid material is removed from digester as a solid component

30

.

In preferred operations, concentrated or strong acid

32

, e.g., sulfuric acid (approximately 93-98% by weight) is added to the digester

24

at a rate of approximately 1.0 lbs H

2

SO

4

to one pound particulate material, depending to some extent on the soluble portion of the spent potlining. The ratio of acid to particulate material by weight can range from 0.8 to 1.2 for H

2

SO

4

acid, depending on the spent potliner feed composition. While, as noted, H

2

SO

4

is the preferred acid for the digester

24

, it should be understood that other acids such as HClO

4

, HCl, HNO

3

, H

3

(PO

4

) and oleum, or combinations thereof, may also be utilized. The different acids may produce different effluent salts. However, the process can be adjusted to accommodate the different materials. Water is continuously added to the soak tank

22

at a rate to maintain the soak tank level. Water may be added to maintain 0% to about 20% moisture content within the digester

24

. Water is added to digester

24

to enhance reaction of the acid with solid material. In preferred operations, the water added to the digester is purge water

36

from caustic scrubber

58

or deionize water or rinse water from other parts of the process, as described in greater detail below. By thus recycling the purge water, any fluoride salts captured from other parts of the process are recovered, and the water thus provided is at a temperature in the range of from about ambient to 120° F., thereby saving heating energy. The use of purge water also eliminates the need to dispose of the waste stream from caustic scrubber

58

. Also, the recycling of the purge water provides for more favorable economics in the process.

The gas component

26

from the soak tank

22

and the gas component

28

leaving the digester

24

will normally contain silicon tetrafluoride (SiF

4

), and hydrogen fluoride (HF). The gas components

26

and

28

are then heated at heater or oxidizer

38

. In preferred operations, heater or oxidizer

38

is in the form of an art known as electric converter/oxidizer which is designed to heat the gas component

28

to a temperature sufficiently high to oxidize the hydrogen cyanide when present, for example, to approximately 750-850° C. in the presence of air. The HF gas remains unreacted. SiF

4

is oxidized to fumed silica (SiO

2

) and other fluoride-containing gases. The residual gas component

40

is then preferably cooled in waste heat recovery boiler

42

. Typically, the temperature of the gases is reduced to less than 150-200° C. The cooled residual gas component is then directed into a water scrubber

44

. The heat recovered in the boiler

42

is redirected to other stages of the process

10

, as desired, to thereby save energy and enhance the efficiency of the process.

In the water scrubber

44

, hydrogen fluoride in the residual gas component

40

is converted to liquid hydrofluoric acid

46

which is directed to an alumina trihydrate reaction tank

48

in which it reacts with the alumina trihydrate to form aluminum fluoride and water. Alumina trihydrate

136

is introduced into the reaction tank

48

from another portion of the process as described below. Alumina trihydrate as used herein is meant to include Al

2

O

3

.3H

2

O or Al(OH)

3

and may be referred to as aluminum hydroxide, aluminum hydrate, hydrated alumina or hydrated aluminum oxide. The reaction tank

48

is heated to a temperature to effect reaction between hydrofluoric acid and the aluminum hydroxide to form aluminum fluoride. Preferably, the temperature is in the range of 80° to 250° C. with a typical temperature being about 200° F. for about 3-6 hours. The aluminum fluoride is then filtered at

49

and directed to a dryer

50

where the residual solids are heated to less than 10% moisture. These dried solids are then directed to a calciner or dryer

51

where the solids are flash heated to a temperature in the range of about 400° to 700° C. forming aluminum fluoride

52

. Water vapor

53

is redirected from the dryer

50

and reaction calciner or dryer

51

back to the water scrubber

44

, thereby eliminating a waste stream at this point of the process. Gases

56

from the water scrubber

44

, from which HF has been removed are then passed to a caustic scrubber

58

as a polishing step before release to the atmosphere

60

. In preferred form, the caustic scrubber

58

utilizes NaOH to reach an alkaline or basic, e.g., a preferred, pH in the range of about 6.5 to 8, typically 6.5 to 7.5. In broader aspects, it will be understood that the pH can range from 6.5 to 10. Other alkali or alkaline earth metal hydroxides may be used such as KOH and Ca(OH)

2

, or combinations thereof. Sodium hydroxide is preferred because it causes less complications in other liquid streams of the over-all process. As described above, purge water

36

from the caustic scrubber

58

is redirected back to soak tank

22

for use therein. This eliminates another waste stream in the overall process and also recaptures any residual fluorides which were unreacted with the water scrubber

58

.

The aluminum fluoride

52

which is thus produced is an end product of the process

10

of the present invention, and may be utilized commercially in any number of applications. For example, the aluminum fluoride

52

may be used as a bath additive for bath ratio corrections in the cell. This substantially eliminates any environmental problems caused by the fluoride materials in the SPL, and, as detailed above, provides a substantial cost benefit and savings.

Now returning to the process of the present invention at digester

24

, the solid component

30

from the digester

24

is directed to a first rinse housing

62

which receives input water

64

, and thence through filter

63

to a second rinse housing

66

with additional input water

65

. The first rinse

62

removes water soluble salts from the input slurry

30

. In the preferred process, the slurry

68

from the first rinse housing

62

passes through the filter press

63

, and then the solids

69

are introduced to the second stage water rinse housing

66

for polishing. The solid stream or fraction

70

from the second water rinse

66

includes carbon and refractory materials such as alumina, silica, and, generally, a relatively high concentration of calcium sulfate salt. Due to this high concentration of calcium sulfate level, the solid stream

70

passes through a filter

71

and into a third rinse

72

which is used in the preferred processes to remove the soluble calcium sulfate salts (with the addition of NH

4

Cl) from the solids. In preferred operations wherein refractory material is a desired end product, ammonium chloride is reacted with the calcium sulfate to form ammonium sulfate and calcium chloride as indicated by the reaction formula

CaSO

4

+2NH

4

Cl→(NH

4

)

2

SO

4

+CaCl

2

The ammonium chloride may be introduced as a solution

74

at approximately 20 wt. % and introduced with rinse

72

. It will be appreciated that other concentrations may be used, e.g., from 15 to 50 wt. % NH

4

Cl. The solution containing these two remaining salts (ammonium sulfate and calcium chloride) are filtered at

75

and carried by stream

76

to a storage unit

78

wherein they may later be recovered or reused as a calcium chloride liquid and an ammonium sulfate solid. Regardless of their later use, both of these salts are nontoxic and present no substantial environmental problem.

The solids

80

which remain after the rinses

62

,

66

and

72

are filtered at

75

and are preferably directed to a mixer dryer

82

and include alumina, silica and carbon. In the alternative, the solids

80

may be directed to a storage unit

83

wherein they may be sold and readily used in cement manufacture or in the glass and ceramics industry. In another example, to the alumina

84

and silica

85

mix at mixer dryer

82

, may be added alumina and/or silica to provide a ratio within mixer dryer

82

at a ratio of about 70% to 30%, by weight, alumina to silica, respectively. The alumina to silica ratio in solids

80

may be adjusted by the addition of alumina and/or silica. The alumina to silica ratio may be adjusted by adding alumina and/or silica to provide 40 to 90 wt. % alumina, the remainder silica on an alumina and silica basis. This alumina to silica mix

86

is then passed into a high temperature vessel

88

in which it is subjected to an elevated temperature to oxidize carbon in the mix. Typically, the temperature is in the range of about 1000° to about 2000° C. in an oxygen-rich atmosphere. This causes any carbon remaining therein to be oxidized to carbon dioxide, while simultaneously vitrifying the alumina and silica into a fused composition of alumina and silica. Typical of the fused composition is mullite

90

which can be of high purity. Mullite

90

is another major solid end product of the process of the present invention. The mullite may be utilized to make furnace brick for use within aluminum reduction cells or for use for other commercial purposes.

In the preferred method, solids

86

are transferred to a high temperature vessel

88

and subjected to an elevated temperature in the presence of an oxygen-rich atmosphere. This causes remaining carbon to oxidize to carbon dioxide thereby providing 8000 to 9000 BTU/lb energy and a usable refractory material

90

, e.g., mullite.

In preferred processes, the oxygen-rich atmosphere within the vessel

88

is maintained by introducing oxygen, preferably in the form of air

92

, to the vessel

88

. Carbon dioxide and heat as well as small amounts of gases, HF and particulates, are removed from the vessel

88

in the form of a heated gas stream

93

and are then directed through a heat recovery boiler

94

to a bag house

95

. In the bag house

95

, the particulates are removed and redirected as bag house catch

96

to the soak tank

22

, while the gases

97

are directed to the caustic scrubber

58

and then back to the soak tank

22

. Thus, the carbon in the SPL is used for useful purposes within the process

10

of the present invention as a fuel source to lower energy costs of the system, rather than remaining as a useless landfill material typical of prior SPL treatment processes or systems.

The liquid fraction

98

form the first and second rinse housings

62

and

66

, respectively, having been filtered at

63

is then directed to an alcohol separator

100

. In the separator

100

, alcohol, for example methanol or ethanol

102

, is admixed with the liquid

98

in a volume ratio of approximately 4:1 alcohol to liquid fraction, for example. The ratio of alcohol to liquid fraction can range from 10:1 to 1:5, for example, depending on the liquid fraction. This step is capable of separating about 97% or more of the salts in the liquid fraction

98

which are filtered out of slurry steam

103

at filter

104

. The liquid stream

106

from the filter

104

includes the alcohol and excess acid from the digester

24

and is directed through a recovery evaporation still

108

wherein alcohol is separated and returned to the alcohol storage source

102

. The remaining sulfuric acid is stored at

110

and eventually returned along line

22

a

to soak tank

22

(

FIG. 1

) for reuse in the digester

24

. In this manner, the use of sulfuric acid and sodium hydroxide in the process

10

can be reduced, while alcohol is recovered and reused, thus enhancing the economics of the process

10

as compared to prior art systems.

The salts

112

from the filter

104

are redissolved in a water bath

114

and then pH adjusted in tank

116

to a basic pH, for example, preferably using sodium hydroxide

118

to a pH of about 12.0 to 12.5. It will be appreciated that any basic pH can be used that is effective in forming a soluble aluminate, e.g., sodium aluminate and insoluble impurities such as metal hydroxides. For example, the pH can range from 11.8 to 13. A pH of 12 to 12.5 is an example of a pH which is effective. Also, sodium hydroxide is an example of a metal hydroxide which can be used. However, any alkali or alkaline earth metal hydroxide may be used and is effective in forming a soluble aluminate or carbonate and insoluble metal hydroxides. For example, KOH, Ca(OH)

2

or Na

2

CO

3

may be used. Thus, this step forms a slurry

120

containing soluble sodium aluminate and insoluble impurities including calcium, iron and magnesium compounds such as calcium hydroxide, iron hydroxide and magnesium hydroxide. The insoluble impurities are filtered at

122

and directed via solids steam

124

to the storage tank

78

.

HCl

125

can be introduced to the tank

78

to react with the metal hydroxides and produce metal chlorides, for example, to produce a mixture

127

of calcium chloride, iron chloride and magnesium chloride, which mixture

127

is a useful product for use in industrial water treatment.

The liquid fraction

126

from the filter

122

is directed to a second pH correction tank

128

wherein an acid

130

, such as sulfuric acid, is added to lower the pH, for example, to about 7.0 to 8.0 to precipitate alumina trihydrate. This step forms a slurry

132

containing soluble sodium sulfate and alumina trihydrate precipitate. It will be understood that other acids may be used to lower the pH. Further, the pH used is a pH which enables separation of the sulfate from the hydroxide.

The alumina trihydrate may be removed from the solution in another way. That is, alumina trihydrate may be precipitated between the range of 11.8 to 12.5 by slowly adjusting the pH of the solution with acid such as sulfuric acid down to pH 11.8 and thereafter allowing the pH to adjust upwardly. This procedure is repeated until the pH will not rise above the pH of 11.8. This precipitates the crystal form of alumina trihydrate instead of the gel form. This is the preferred method for recovering alumina trihydrate.

The slurry

132

is then filtered and rinsed at

134

, and the alumina trihydrate solids

136

are polished at

138

and then redirected as the alumina trihydrate stream

54

to the reaction tank

48

to form aluminum fluoride as previously discussed. The sodium sulfate containing liquid stream

140

from the filter

134

is directed to a second alcohol separation tank

142

wherein alcohol

144

, as noted earlier, either methanol or ethanol, is mixed with the liquid stream in a volume ratio of approximately 4:1 alcohol:liquid stream to precipitate sodium sulfate. The ratio of alcohol to liquid stream can range from 10:1 to 1:5, for example. The precipitated sodium sulfate is filtered at

146

and is then directed to a dryer

148

and then storage

150

, wherein the resultant sodium sulfate is approximately 99.0% pure. The liquid portion

152

is directed from the filter

146

to an alcohol recovery still

154

wherein alcohol is separated and directed via stream

156

back to storage unit

144

for reuse in the process, while the water stream

158

is directed to water recycle storage unit

160

for reuse within the process

10

, such as at

114

.

Alternatively, as shown in

FIG. 5

, liquid fraction

98

resulting from the first and second rinse housings

62

and

66

, respectively, having been filtered at

63

is directed to tank

116

where the pH is adjusted. As noted, the pH is adjusted to form soluble sodium aluminate and insoluble impurities, e.g., calcium hydroxide, iron hydroxide and magnesium hydroxide. The insoluble impurities are filtered and directed to tank

204

where the pH of the liquid in tank

204

is adjusted. In tank

204

, the pH is lowered and the tank heated to precipitate calcium compounds, e.g., calcium sulfate. Typically, the pH is adjusted to a pH less than 1 by the addition of an acid such as H

2

SO

4

. Also, typically the tank is heated to a temperature in the range of 80° to 110° C. The calcium compounds, e.g., calcium sulfate, are filtered at

205

and then stored in storage tank

206

.

Liquid from filter

205

is directed to tank

207

where the pH is adjusted to precipitate iron compounds such as iron hydroxide. Typically, the pH is adjusted upwardly to a pH in the range of 4.5 to 5.5. The precipitate is filtered at

208

and stored in storage tank

209

.

Liquid from filter

208

is directed to tank

210

where the pH is again adjusted to precipitate magnesium compounds such as magnesium hydroxide. The magnesium compounds are precipitated by adjusting the pH to a pH in the range of 10.5 to 12. Thereafter, the magnesium precipitate is removed at filter

211

and stored in tank

212

. Then, liquid stream

213

from filter

211

is directed to tank

116

to enhance aluminum recovery. The three compounds recovered, e.g., calcium sulfate, iron hydroxide and magnesium hydroxide, are relatively pure and thus have good commercial value.

As the result of the above process

10

, spent potliner material is reduced and recycled into commercially useful ingredients, that is, aluminum fluoride; mullite; fumed silica; brick material; and Al

2

O

3

useful in cement or glass and ceramic tile manufacture. Sodium sulfate, calcium sulfate, magnesium hydroxide and iron hydroxide are also recovered.

Referring now to

FIG. 6

there is illustrated preferred steps in another embodiment of the invention for recovering products from spent potliner. In this method, the spent potliner is crushed, soaked and digested as noted earlier with respect to FIG.

1

. Sulfuric acid is preferred in this aspect of the invention for use in digester

24

. Further, gases

26

from soak tank

22

and gases

28

from digester

24

are treated generally as noted with respect to FIG.

1

.

In this embodiment, exhaust gases

26

containing ammonia, hydrocarbons and water vapor from soak tank

22

and particulate from the feed are maintained heated, e.g., about 180° C., to prevent condensation and transported to dust collector

39

. Also, in this embodiment, exhaust gases

28

from acid digester containing HF, SiF

4

, and minor amounts of SO

2

, HSO

3

, water vapor and particulate are heated, e.g., about 180° C., and are combined with the exhaust gases from the soak tank for conveying to dust collector

39

. Particulate collected in dust collector

39

is returned along line

37

for reprocessing in soak tank

22

and digester

24

. As noted, purge water

36

from caustic scrubber

58

is recirculated to soak tank

22

. The purge water contains sodium fluorides and sodium sulfates collected from the exhaust gas stream by the scrubbing action of the sodium hydroxide solution in scrubber

58

. The scrubbing preferably is controlled to provide sufficient water for soak tank

22

. The recycling of the purge water avoids a waste stream and recaptures any residual fluorides and sulfates unreacted in water scrubber

44

.

In this embodiment of the invention, thermal oxidizer

38

heats the gases from soak tank

22

and digester

28

to a temperature sufficiently high to oxidize ammonia and hydrocarbons and to convert SiF

4

to fumed silica and HF. Any HSO

3

in the gas stream is converted to SO

2

. For purposes of forming fumed silica, thermal oxidizer

38

is preferably gas fired using natural gas, propane, or a hydrogen-oxygen mixture. As noted, gas stream

40

from oxidizer

38

is cooled in heat recovery boiler

42

preferably to a temperature of about 140° to 200° C. to recover heat for use in other stages of the process.

After cooling, the gases are passed through dust collector

43

to collect fumed silica produced in oxidizer

42

. The fumed silica (about 98% SiO

2

) is removed along line

45

and recovered as a valuable product of the process.

Water scrubber

44

captures HF and remaining SiF

4

gases as hydrofluoric and fluorosilic acids. These acids are transferred to alumina trihydrate reaction tank

48

. Make-up water from scrubber

44

is water returned from aluminum fluoride tri-hydrate filter

49

or de-ionized water is added. Water scrubber

44

circulating liquid has a sufficiently high concentration of hydrofluoric acid that the scrubber does not remove SO

2

in the stream. Gases exhausting from scrubber

44

along line

56

may contain trace amounts of HF and SiF

4

not captured in the scrubber. However, caustic scrubber

58

removes such trace amounts before the gases are exhausted to the atmosphere and purge water is returned to soak tank

22

.

Aluminum hydroxide produced in other stages of the process is introduced to the fluoride containing acids

46

in aluminum hydroxide reaction tank

48

. The aluminum hydroxide reacts with the hydrofluoric and fluorosilic acids to form soluble aluminum fluoride and precipitate silicon as SiO

2

which is filtered out of the aluminum fluoride solution. The aluminum fluoride solution is heated in aluminum hydroxide reaction tank

48

to precipitate aluminum trifluoride trihydrate (AlF

3

.3H

2

O) crystals. Typically the solution is heated to a temperature in the range of about 80° to 210° F. with a typical temperature being about 200° F. for a period of about 3-6 hours. The aluminum trifluoride is filtered from solution by filter

49

and processed as noted earlier and recovered as a valuable product.

In this embodiment of the invention as set forth in

FIG. 6

, digested spent potliner

30

is directed from digester

24

to rinse tank

62

. In rinse tank

62

, the digested spent potliner is mixed with three to ten parts by weight of water and preferably heated to a temperature sufficiently high, e.g., 50° to 100° C., preferably 70° to 100°° C. to dissolve the soluble sulfates in the digested spent potliner. The water used for this stage of the process can be distilled water, non-fluoride containing rinse water from other steps of the process, water from caustic scrubber

58

, or a combination of these. The amount of water used to dissolve the sulfates is adjusted to compensate for concentrations of other chemicals added and to maintain a concentration of sulfate salts which can be handled satisfactorily but not sufficiently dilute as to require extra energy for concentration purposes. Once the soluble salts are dissolved in rinse tank

62

, the resulting slurry is removed to filter

170

to remove insoluble carbon and refractory materials which are comprised of calcium aluminum silicate, aluminum oxide and minor amounts of silicon oxide. The solids are removed to refractory calciner

172

. The liquid containing dissolved salts is pumped to pH correction tank

174

.

In refractory calciner

172

, heat is applied to burn the carbon and thus separate carbon from the refractory solids. Refractory calciner

172

is operated at about a temperature of 1000° to 1400° C. Once the carbon is burned, a useful refractory product

76

comprised mainly of calcium aluminum silicate, aluminum oxide and silicon oxide is recovered. The heat generated by burning the carbon can be recovered and used in other parts of the process.

The liquid from filter

170

, introduced to pH correction tank

174

, is acidic and typically has a pH in the range of about 0.6 to about 1.4. Sodium hydroxide, or another basic material, e.g., KOH or Ca(OH)

2

, Na

2

CO

3

is introduced to pH correction tank

174

to increase the pH to a pH in the range of 9 to 14, e.g., to greater than 11 and preferably greater than 12.5. One source of sodium hydroxide is barium reaction tank

200

as will be explained later in the process. In pH correction tank

174

, both liquids are agitated and heated to maintain a temperature preferably in the range of 80° to 95° C. As the pH is increased, the metal salts dissolved in the liquid are converted to metal hydroxides. All the metal hydroxides except sodium hydroxide, sodium aluminate and sodium sulfate precipitate out of solution. The slurry from pH correction tank

174

is transferred to filter

178

to separate the precipitated metal hydroxide from solution. In filter

178

, the metal hydroxides precipitate are removed or separated from the solution. The metal hydroxide precipitate is then directed to metal chlorides reactor

188

. In metal chloride reactor

188

, the metal hydroxides are dissolved by the addition of hydrochloric acid to provide a dissolved chloride solution; preferably, the hydrochloric acid has a concentration in the range of about 2.87 to 13.1 normal and typically 10 to 40% by weight. Thereafter, the pH of the resulting solution is raised to a pH in the range of <1 to 4.5, and preferably 3.5 to 4.5. The pH may be raised by the addition of a carbonate, e.g., CaCO

3

, MgCO

3

, Na

2

CO

3

and Li

2

CO

3

, with a preferred carbonate being calcium carbonate. Also, alkali or alkaline earth hydroxides may be used, e.g., hydroxides of these materials may be used. The addition of the carbonate operates to precipitate iron oxide hydrates and form metal chlorides. The iron oxide hydrate is separated from solution by filter

190

and thereafter the iron oxide hydrate is sent to kiln

196

. When calcium carbonate is used, a calcium chloride product is formed. The calcium chloride product comprises about 85 to 95 wt. % calcium chloride at about a 25% to 35% concentration. The calcium chloride is a valuable product which finds many uses, for example, in water treatment systems.

The iron oxide hydrate is calcined in kiln

196

at a temperature in the range of 300° to 700° C. to remove water and convert it to FeO. When the water is removed, a high purity iron oxide product is obtained that is valuable, for example, as a feed stock in the production of high purity iron and steel.

The solution from filter

178

contains dissolved sodium aluminate and after separation of the metal hydroxides, the solution is transferred to pH adjustment tank

180

in order to precipitate alumina trihydrate. This may be accomplished with the addition of acid. Thus, preferably, sulfuric acid is used to lower the pH of the solution to a pH in the range of 10 to 12 and preferably in the range of 10.5 to 12. Typically, sulfuric acid having a concentration of about 10 to 25% is used. The sulfuric acid can be used from oleum scrubber

222

and may be diluted to the desired concentration. Upon completion of the precipitation, the alumina trihydrate precipitate is separated from the liquid by filter

182

. Then, the alumina trihydrate precipitate is sent to alumina trifluoride trihydrate reactor

48

for preparation of aluminum fluoride as described previously.

The liquid remaining after filtering step

182

contains primarily sodium sulfate with minor or trace amounts of dissolved sodium aluminate. The sodium sulfate containing solution is conveyed to tank

184

where the pH of the solution is lowered from about 10.5 to 11.5 to a pH of about 6 to 8, typically 6.5 to 7.5 to precipitate any remaining alumina trihydrate. The resulting slurry is filtered by filter

186

to remove the precipitated alumina trihydrate. The alumina trihydrate is filtered as a gel, removed from the sodium sulfate solution and returned to first rinse tank

62

for reprocessing. The sodium sulfate solution is forwarded to barium reaction tank

200

for sodium hydroxide recovery.

In barium reaction tank

200

, the sodium sulfate is treated with barium hydroxide to form insoluble barium sulfate and soluble sodium hydroxide. The barium hydroxide is added in an amount sufficient to form the sodium hydroxide depending to some extent on the amount of sulfate present. Typically, the barium hydroxide is added as a liquid at a concentration of about 20 to 40% w/w, The barium sulfate is separated from the sodium hydroxide solution by filter

224

. The sodium hydroxide solution may be concentrated by evaporation, for example, to a 50% solution before being removed from the system as a valuable product. Part of the sodium hydroxide solution may be used in pH correction tank

174

to raise the pH. Preferably, barium sulfate is removed to kiln

226

.

In kiln

226

, the barium sulfate is decomposed to SO

3

and barium oxide. Typically, to decompose the barium sulfate, kiln

226

is heated to a temperature in the range of about 1300° to 1600° C., preferably 1350° to 1550° C. The barium oxide resulting is mixed with water to form barium hydroxide. The concentration can be adjusted to about 20 to 40% w/w for use again in barium reaction tank

200

. The SO

3

gaseous product is first treated in heat recovery boiler

228

to recover heat therefrom to cool the gaseous product to about 200° C. The cooled gaseous product may be filtered to remove entrained barium oxide before being transferred to an oleum scrubber

222

.

In oleum scrubber

222

, a sulfuric acid solution, typically about 93 to 96% w/w sulfuric acid, is recirculated to collect SO

3

gaseous product obtained from kiln

226

. As SO

3

is collected in scrubber

222

and the sulfuric acid concentration increases, water, e.g., de-ionized water, is added to maintain sulfuric acid in the range of about 93 to 96%. Preferably, the recirculating acid in the scrubber is maintained at a temperature, e.g., 150° to 180° C. which permits efficient collection of the SO

3

gaseous product. In addition, a stream of sulfuric acid is removed and stored in storage tank

32

for use in acid digester

24

. In addition, as noted earlier, sulfuric acid can be supplied from oleum scrubber

222

to pH adjustment tank

180

to precipitate aluminum hydroxide.

As can be seen from the above, the present invention provides a highly efficient process for not only treating the significantly hazardous spent potliner material from aluminum reduction cells, but also serves to convert the components of the SPL to useful end products. Moreover, there are no significant amounts of solid waste material from the process of the present invention which must be subsequently disposed of in landfills or stored, as previously required in other processes and practices for treating spent potliner material. In addition, the process of the present invention efficiently recycles water and heat and produces refractory material which can be used in the fabrication of new aluminum reduction cells, thereby providing a highly efficient and economic process without a liquid or noxious gas waste stream. The primary end products of aluminum fluoride, refractory material, fumed silica and sodium sulfate are all usable, either in the actual manufacture of aluminum reduction cells or in other commercial endeavors. The stored impurities of calcium sulfate, iron hydroxide, magnesium hydroxide, ammonium sulfate and calcium chloride are all benign, and are all treatable in accordance with conventional processes and may be reclaimed for a wide variety of commercial uses since they include no environmentally hazardous materials, such as for water treatment to recover fluoride and solids. As a result, it is seen that the present invention is a highly efficient process and very economical in both its operation as well as its yield. Further, it avoids having to deposit fused solid material containing environmentally hazardous components into landfills or storage.

The following example is further illustrative of the invention.

EXAMPLE

Sixty tons per day of SPL feed, including caked materials and sweepings, is continuously introduced to the crusher

14

and is processed through the steps of the process

10

as described above. Utilizing this process, the 60 tons/day SPL input

12

yields approximately 13 tons/day aluminum fluoride end product, approximately 10 tons/day of a refractory material, 6 tons fumed silica and approximately 50 tons/day of reusable salts, e.g., sodium sulfate, for a total of about 79 tons of recycled solid materials, with the balance of the starling materials being converted to harmless gases and salts. In processing this 60 tons/day of SPL input

12

, substantially all of the cyanides contained therein are destroyed, and substantially all of the fluorides are converted to aluminum fluoride as a useful end product. Thus, these highly environmentally damaging materials are either eliminated or converted to useful products.

The foregoing exemplary descriptions and the illustrative preferred embodiments of the present invention have been explained in the drawings and described in detail, with varying modifications and alternative embodiments being taught. While the invention has been so shown, described and illustrated, it should be understood by those skilled in the art that equivalent changes in form and detail may be made therein without departing from the true spirit and scope of the invention. It should be further understood that the scope of the present invention is to be limited only to the claims except as precluded by the prior art. Moreover, the invention as disclosed herein may be suitably practice in the absence of the specific elements or steps which are disclosed herein.