AU611868B2 - Recovery of fluoride values from waste materials - Google Patents

Description

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AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION Form

(ORIGINAL)

FOR OFFICE USE 61 I 6 Short Title: Int. Cl: 0 a 0 C o oo 0000 to 0 00000 o O 0 00 00 0 0 00 0 000000 0 00 0 00 00 0 0 00 00 000000 0 00 0 00 0 00 0 0 0 00000 0 0 Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: COMPLETE-AFTER-PROVISIONAL PH9614 TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: COMALCO ALUMINIUM LIMITED 55 COLLINS STREET MELBOURNE VICTORIA 3000

AUSTRALIA

Actual Inventor: Address for Service: CLEMENT HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

Complete Specification for the invention entitled: RECOVERY OF FLUORIDE VALUES FROM WASTE MATERIALS The following statement is a full description of this invention including the best method of performing it known to me:w ,i i 2 ao o 0 00 0 0 00 0 o .5 0q004a00 o 0 o Q0 00 0 0 001 S0 0 00 0 0000 Co~ 000 This invention relates to a process for recovering fluoride values from material containing fluoride salts together with combustible compounds.

The process of the invention is of particular value in the treatment of waste materials from the electrolytic smelting of aluminium, for example spent cathode liners.

According to a principal aspect of the invention, a process for the recovery of fluoride values from material containing fluoride salts together with combustible components, for example spent cathode liners, comprises combustion of the said components and sulpholysis of the fluoride salts, characterised in that the material is subjected to combustion in a first step to produce a fluoride-containing ash; the fluoride-containing ash is subjected to sulpholysis in a separate step, without an intermediate leaching step, and the sulpholysis produces a gaseous product containing fluoride values.

I yrr gl 3 The process enables a recovery of fluoride values from smelter wastes which is especially favourable i environmentally. Such wastes are frequently dumped on land filled sites so giving rise to potentially considerable environmental damage resulting from leaching, not only of the contained fluorides, but also of cyanides, both of which are highly toxic. A further advantage of the invention is that recovery of the contained fluoride values, initially in i.e form of gaseous fluoride species, may subsequently be treated with alumina to produce aluminium trifluoride, an essential chemical used in aluminium smelting to maintain the required chemical composition of the fused salt baths used. The 0 production of said trifluoride is of significant economic 0 importance.

0ooo0 15 Several methods in the prior art have been proposed o 0 oo for recovering cryolite from spent cathode materials which S00 have included extraction by sodium hydroxide, sodium carbonate, or water. U.S. Patents 1,871,723 and 2,732,283 So 0 teach the treatment of carbon cell lining material with 20 aqueous caustic solutions to yield sodium fluoride and sodium aluminate, which solutions may be processed to precipitate .o.oo cryolite. U.S. Patent 3,106,448 teaches reaction between o 0 O fluoride values in spent liners and a water soluble carbonate to produce water soluble sodium fluoride which may in turn be O° 25 precipitated with sodium aluminate to form cryolite. In ooeo addition, the extraction and recovery of alumina and fluoride values with dilute ammonia solutions is known.

One of the more recent methods for recovery of fluoride and aluminium values involves the pyrohydrolysis of the carbonaceous material, preferably in a fluidised bed reactor. Pyrohydrolysis involves contacting the spent cathode and/or cell lining with water or steam at high temperatures, whereby the water introduced reacts with the fluoride compounds to form HF. However, it has been found that while the pyrohydrolysis of aluminium fluoride is relatively easy, calcium fluoride and, particularly, sodium fluoride are more difficult to react. U.S. Patents 4,113,832, 4,158,701,

A

4 4,160,808, and 4,160,809 all relate to pyrohydrolysis techniques for the recovery of fluoride values from spent cell linings.

However, the processes described in the aforementioned patents require exceptionally high temperatures and excessive quantities of steam.

In a more recent patent to Martin Marietta Corporation 4,355,017) there is described a pyrosulpholysis procedure for the treatment of carbon cathodes waste material which involves high temperature treatment with air, steam, and sulphur dioxide in a single etoo reactor. The reactor may be a fluidised bed, packed bed 0 0oo or closed furnace.

US 4,444,740 describes a process involving the Sfollowing stages: 0 I The crushing of cathode waste to -1mm; o (ii) Incineration a temperatures between 650 0 C and 950 C (iii) Leaching the resulting ash with a caustic solutio to form a liquor containing fluoride ions; (iv) Reaction of the fluoride containing leachate with r lime, to produce CaF 2 Following filtration and drying, reaction of the resulting CaF 2 with H 2

SO

4 to produce HF in the 0 conventional manner; and (vi) Feeding the HF gas to an alumina dry scrubber to produce a product for recycling to the aluminium reduction cell.

b0 The recovery process involves the following reactions in the waste material Decomposition of cyanides Combustion of the carbonaceous and hydrocarbo material Oxidation of sulphides and nitrides Sulpholysis of the fluoride salts thereby forming HF gas and sulphate salts.

A major disadvantage of using a single reactor is that all reactions take place in the one reactor with the reactants necessarily present in low concentrations which is not conducive to high reaction efficiency. The conversion of sulphur containing reactants particularly tends to create emissions which constitute environmental hazards in addition to those caused by fluorides and cyanides. The variable chemical composition of the feed stocks makes control even more difficult in a single reactor.

By conducting sulpholysis in a separate stage the oOO present invention enables the concentration of the gaseous 0 0 fluoride species to be increased to the maximum extent possible, thereby facilitating their recovery and reducing 00 the magnitude of the gas handling equipment which is o08 required for a given amount of fluoride recovered.

0 0 Recovery of hydrofluoric acid for subsequent production of aluminium fluoride or cryolite or other fluoride chemicals is simpler and more economic from a veto.o concentrated rather than a dilute stream. A further 0oo advantage of increased hydrofluoric levels in the S 0 sulpholysis offgas is gained by the possible use of more 00 highly oxidised forms of the sulphur containing reactants.

*000 The improvements in hydrofluoric acid offgas levels through these changes in reactors and sulphur-containing o°0o feed materials are demonstrated in the following table.

0o0 0 0 e zk~iin ~$X'0 S 000 6 0 0 0 o 0 ao0o o o o. 0 0 0 0 0 06.0 000 *a 1500 0o 0 a o .0 0 0 0 0 o 0 o oQ o a o a o o a o o s fr e O o a 0D o o 0 0o 0 0 0 .o Estimates of Maximum Possible Hydrofluoric Acid Concentration in the Offgas Streams for Various Process Approaches for Pvrosulpholvsis PROCESS APPROACH 1. Combined Combustion and Sulpholysis 2. Combined Combustion and Sulpholysis 3. Combined Combustion and Sulpholysis 4. Separate Sulpholysis Separate Sulpholysis 6. Separate Sulpholysis SULPHUR SOURCE Elemental Sulphur Sulphur Dioxide Sulphur Trioxide or Sulphuric Acid Elemental Sulphur Sulphur Dioxide Sulphur Trioxide or Sulphuric Acid HF PARTIAL PRESSURE, ATM.

0.039 0.047 0.052 0.127 0.274 0.656 Assumptions Used in Theoretical Mass Balances: A. Excess Oxygen for Carbon Combustion of 8. Excess Oxygen for Oxidation of Sulphur or Sulphur Dioxide to Sulphur Trioxide of 100%.

C. Excess Steam for Sulpholysis of 100%.

D. Excess Sulphur, Sulphur Dioxide or Sulphur Trioxide for Sulpholysis of 7 -7- 7 A further important advantage of the multi or two stage process of the invention is the facility of being able to carry out the combustion stage independently of the remainder. This stage could, for instance, be carried out at separate smelters in different locations and the product ash could be shipped to a single site for fluoride recovery. It must be emphasized that such ash will be environmentally less hazardous in transport because its contained cyanides, sulphides and nitrides will have been decomposed beforehand.

Prior to the combustion stage or between the separate combustion and sulpholysis stages, further .0 advantage may be gained through the use of mineral 4090 benefication procedures aimed at separation of oxides, 9Q 0 such as alpha alumina, beta alumina and silica, from the 'o o fluoride containing materials, such as cryolite, sodium 0oo fluoride, aluminium fluoride and calcium fluoride. The procedures may include one or more of such operations as crushing, grinding, density separation, size separation etc. Benefication prior to the combustion stage may also be achieved chemically. These operations will lead to a higher concentration of fluorides in the feed to the 4404 sulpholysis reactor, improved reaction efficiency through Sreduced possibility of a side reaction of sulphuric acid 0O00 with alpha and beta alumina, and improved reaction efficiency owing to a reduced possibility of reaction of 0000 S0 HF with silica to form silicon tetrafluoride and o fluorosilicic acid.

0 Overall separate reactors and separate control for each stage enable maximum optimisation of each stage of the process, something which is not possible in a single reactor.

The accompanying Figures 1 and 2 are flowsheets for preferred aspects of the invention.

i 1 i 8 In this preferred embodiment, spent potlining (SPL) is first crushed and screened to the desired size fraction and S then beneficiated and/or fed directly to the combustion unit.

A number of reactions proceed concurrently, including the oxidation of carbon, aluminium metal, dross and carbide, destruction of cyanide and elimination of nitrides, sulphides and acetylene. The oxidation reactions are highly exothermic in nature.

It is desirable to control the combustion temperature within the range 700-875 C, for the following reasons S**0 Below 700 C, unacceptably low rates of carbon 'o0 0 combustion and cyanide destruction are 00 al o C experienced.

Above 875 C agglomeration may occur, owing to the 0 4 o presence of low melting point salts in SPL.

Agglomeration can result in catastrophic reactor shutdown or, in less severe cases, restricted 0 o carbon combustion through the formation of a 0 000 o 0 20 non-permeable coating around individual SPL particles.

,oot Temperature may best be controlled through the 0 0 o control of SPL and air addition rates. As a further aid to the control of SPL agglomeration, certain inert additives, S0, 25 such as kaolin clay, have been found to be effective at Smoderate levels. The use of such additives is known.

A number of different reactor devices may be suitable for the combustion of SPL, including (i Rotary kiln, (ii) Circulating fluid bed, (iii) Fluidized bed, (iv) Multiple hearth incinerator, Moving grate furnace, (vi) Open hearth furnace, (vii) Torbed reactor.

9 Each reactor type has specific advantages and disadvantages; the preferred combustor type in a given case will be that best equipped to handle the agglomerating tendency of SPL, which will be reflected in its ability to control combustion temperature.

The solid product resulting from the combustion treatment of SPL is a mixture principally of oxide and fluoride salts resulting from both the original materials of cathode construction, as well as materials absorbed into the cathode structure during the operation of the cell. Depending on the exact design of the cathode, details of its operating experience and life and possible other factors, the exact chemical composition of the SPL, as well as that of the ash product resulting from the combustion of SPL can vary over a 15 very broad range. Typically any or all of the following materials may be present Fluorides: Cryolite Na AIF 6 0O O 00 00 0 0 0 a 0 o o0 02 00 4 a 20 Sa oOO a00 0 0 Chiolite Aluminium Fluoride Sodium Fluoride Calcium Fluoride Lithium Fluoride Magnesium Fluoride Various Mixed Fluorides Na5Al3F14 A1F 3 NaF CaF 2 LiF MgF 2 Oxides: a Alumina Al 2 0 3 0 $00 Alumina Na 2 0.(Al 2 0 3 Silica SiO Various silica aluminates, sodium silicates and sodium aluminium silicates.

In certain instances, an advantage may be gained through the use of pretreatments prior to direct sulpholysis treatment. The purpose of such pretreatments is a separation of the fluoride and oxide constituents so as to produce a feed stock of upgraded fluoride content. Such pretreatments may include the steps of particle size reduction by grinding and crushing, and either physicel separation usually on the basis w i~e 0 t 0 r 0 00 0 lot.

00 00 a c 0 0r *t 0 *t 0 0 00) 00004 o 0 0404 000 0000 0000 4 00 4000O 0 10 of differences in densities of the various phases, Pretreatment to a feedstock of upgraded fluoride content has the advantages of a reduced mass of material needing to be treated for a given amount of fluoride to be recovered and of less chance of wasteful side reactions with oxides.

The SPL ash and/or fluoride upgraded feed is then subjected to sulpholysis treatment for the liberation of hydrofluoric acid vapour. Sulpholysis treatment involves the treatment of fluoride containing feed with chemical feedstocks capable of producing sulphuric acid to achieve chemical reactions of the general form below 2 /n)MFn H 2

SO

4 M(2/n)S0 4 2HF where M metal.

Reactions may be carried out at elevated temperatures in the range of 120 0 C to 900 0 C. The preferred range of temperature is dependent on the nature of the fluoride bearing species. In the case of feeds containing alumina, the preferred range of temperature is between 7700 to 870PCat which temperatures aluminium sulphates are known to decompose above which certain bath constituents become molten. Furnace reactors including the following may be used.

Rotary Kiln Hirschoff furnace Rotary hearth furnace Fluid bed reactor Circulating fluid bed reactor Torbed reactor 11r lOa Commonly used feed stocks for producing sulphuric acid include Concentrated sulphuric acid Dilute aqueous solutions of sulphuric acid Mixtures of concentrated sulphuric acid and sulphur trioxide (Oleum) Mixtures of sulphur trioxide (oleum) and steam Mixtures of sulphur dioxide, air and steam Mixtures of elemental sulphur, air and steam t 04 G 4 at 0 Sa 9 0 a 0 00 o 99 00 a 000 at o ,jLI/bV -1 r .)I

P'

rUy~L~ 11 The relative proportions of the components of the above described mixtures are selected for the optimal degree of sulphuric acid equivalent.

The calculated values presented in the following Table 1 illustrate the advantages gained by two-stage treatment over the single stage treatment in which combustion and sulpholysis are carried out in one reactor. As stated, a very significant advantage of two-stage treatment is that the total volume of gaseous material is reduced while the concentration of HF in that volume is increased. Further advantages in reducing total gaseous volume and increasing HF 0 concentration are achieved in choosing more highly oxidized a forms of sulphur as-feedstock for the sulpholysis reaction.

o0 In essence, the use of the more oxidized forms reduces the 0 0 s 15 need for reactant oxygen and minimises the diluting effect of C, nitrogen co-present with oxygen in air. Dilution with d nitrogen could be eliminated altogether through the use of pure oxygen with the less oxidized forms of sulphur 0 feedstocks, however, at some cost penalty to the process.

0 0 0 00 00004 a 00 b a 2

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-rrun r -F 12 TABLE 1 ESTIMATED OFFGAS FLOWRATES AND HF PARTIAL PRESSURES FOR VARIOUS PYROLSULPHOLYSIS OPTIONS* Process Sulphur Source Exit Gas kg moles/ HF Partial/ hr Pressure (atm) Combustion Sulpholysis Combustion Sulpholysis Sulphur Sulphur Dioxide Sulphur Trioxide Sulphur Sulphur Dioxide Sulphur Trioxide 218 183 166 153 65 30 13 0.038 0.045 0.050 0.127 0.275 0.656

I

Il t 25 is Basis 1 tonne SPL/hr Preferred aspects of the invention will be further illustrated by the following non-limiting examples, in which Examples 1 and 2 relate to combustion and Examples 3 and 4 relate to sulpholysis.

__.ram 13 Example 1 A 1kg sample of SPL was crushed and screened to less than 300 microns, and used as feedstock to a laboratory scale rotary kiln. The following test conditions applied: Kiln Set Point Temperature 750 C Air Flowrate 30 1/min.

Solids Residence Time 30 min.

Kiln Rotation Rate 8 to 10 rpm Solids Feed Rate 10 to 15 gm/min.

The thermal response of the kiln was closely 0. monitored with time, and is shown in Table 2. No evidence of 0 o o, o SPL agglomeration was detected, with a total of 660 g of ash oo recovered. The sample of SPL ash was subsequently analyzed, 00 Do 0 o with pertinent results shown in Table 3. High levels of 0 1 cyanide destruction and carbon combustion were achieved under 00", these conditions.

o00 TABLE 2 0o o o THERMAL RESPONSE OF ROTARY KILN EXAMPLE A °0 °0 Kiln Air Flow Rate 50 1/min. 00 0o 00 "O Time (Minutes) Temperature 0 0 T=0 750 C 25 775 0 C a oooa 0 25 50 787 0

C

0 0 S75 7900C 100 800°C 125* 820 0

C

150 810 0

C

*Feed Addition Stopped.

14 TABLE 3 SPL ASH EX ROTARY KILN 0 00 0 0 0 00 000 0 00 00 00 0 0 0 0 000000 0 0 0 00 00 0 0 00 0 0 0 000 0 00 0 000000 0o 0 0 0 00 0 0 4 o o 0o000 S o 15 Species SPL Ash SPL Ex Kiln Feedstock (wt%) C 1.7 18.7 S 0.17 0.24 Si 1.40 1.12 Na 10.0 Ca 1.45 Fe 1.21 Al 26.1 CN (ppm) 860 %F 14.1 12 *Limit of analytical procedure.

Example 2 20 A further sample of SPL, taken from a different location, was crushed and screened to -300 micron, and fed to the rotary kiln. Kiln conditions were identical to those used in Example 1. In this case a strong exotherm was observed, with the kiln temperature rising to 9000C. Severe agglomeration resulted, with the material forming pellets up to 5mm in diameter. The exotherm was subsequently moderated by reducing air flowrate to the kiln.

A temperature profile for this experiment is shown in Table 4 and is in contrast to that obtained in Example 1.

In addition to carbon combustion, other oxidation reactions apparently contribute to the extremely exothermic nature of this material. As mentioned previously this may be related to the relative amounts of aluminium metal, dross or carbide in this sample.

7 15 TABLE 4 THERMAL RESPONSE OF ROTARY KILN EXAMPLE 2 Time (minutes) Temperature Kiln Air Flow Rate (1/min) CC 1 1 19 9919 I o 19 0 o 00 00 09 0e 91 1999 e C T 0 750 975 50 910 75 890 100 880 0 125* 825 0 150 785 0 *Feed Addition Stopped.

As illustrated in the following Examples 3 and 4, the reaction between ash from combustion treatment of SPL and sulphuric acid has been studied in several fashions. Certain of these experiments have involved low temperature processing of ash and acid prior to thermal treatment, and others have involved direct addition of acid and ash to a high temperature reactor. Details of both types of experiments are described in the following Examples 3 and 4.

Example 3 (Pre-mixing) Concentrated sulphuric acid (98% H2SO4) and ash obtained in Example 1 were added to a "Heligear" mixer prior to any thermal treatment. The first experiment involved an estimated stoichiometric addition of acid while the second involved an amount of acid estimated as four times stoichiometric. In the first experiment, acid was added to the mixer in increments of 40ml at intervals of about 1 16 minutes. In the second, increments of 50ml were added in intervals of 5 to 15 minutes. Details of both experiments are outlined in Table TABLE EXPERIMENTAL DETAILS 0 00 000 0 00 S0 0 0 0 000 a 0 00 00 0 0 0 0 0 10 0 0 0 00 o oo So00 0 0 0 000 0 00 0 00 0 0 0 00O 00 0 0 15 Experiment 1 2 Mass of Ash, g 600 970 Assumed Fluoride Content of Ash, Wt% 13.6 13.6 Volume of Acid Added, cm 3 120 750 Mass of Acid Added, g 216 1350 Total Weight Added, g 816 2320 Total Weight Recovered from Mixer, g 751 1114 Weight Loss, g 65 1206 Weight Loss, 8 52 In both experiments the mixer was externally heated to a temperature of about 200 C prior to acid addition. When 20 acid was added there was a copious liberation of heat with fume evolution. Glass sight ports on the mixer body were heavily etched by the fume indicating that a portion of the fume contained hydrofluoric acid. The remainder of the fume probably consisted of sulphuric acid vapour, sulphur trioxide 25 and water, none of which are known to etch glass. When added to the ash, the acid.initially lead to the formation of sticky lumps, with a consistency similar to wet beach sand. With continued mixing these broke down into fairly free-flowing powder. In addition to the fume as a principal cause of weight loss, an additional factor was the stickage of a portion of the solids to the walls and blades of the mixer.

Although a portion of the fluorides were apparently released during the low temperature premixing, as evidenced by the etching of the glass sight port, more complete reaction 17was achieved by thermal treatment of the premixed solids in a rotary kiln operating at a temperature of 800 C. Chemical analyses of kiln feed and products are shown in Table 6.

TABLE 6 ACID TREATMENT OF SPL ASH Material Wt% F 0 60 oa B a oo a 000 0 0 0 0 a o a O a 00 0 a 0a *00011 0 0 0 I 15 Feedstock (SPL Ash) 14.1 Stoichiometric (xl) Premixer product Kiln product Stoichiometric (x4) Premixer product 0.9 Kiln product 0.6 Example 4 (Direct Addition) SPL combustion ash from Example 1 and concentrated sulphuric acid were fed directly to a laboratory sized, 20 externally heated rotary kiln. The kiln was heated to a temperature of 800 0 C prior to the addition of acids and solids. Solids were fed to the kiln from a hopper using a screw feeder. Solids feed rates were in the rate of 10 to g/min. Sulphuric acid was fed to the kiln with a peristaltic 125 pump. When near stoichiometric levels of acid were added with the solids, a very pasty mixture which adhered to the kiln wall resulted. This problem could be lessened by multiple passes of solids through the kiln using acid additions of less than estimated stoichiometric requirements in any one of the passes. Results of experiments performed on this basis are reported in Table 7.

-7 18 TABLE 7 ACID TREATMENT OF SPL ASH Pass No. F Acid Added Stoichiometric (cm 3 cumulative) Requirement SPL Ash 14.1 1 13.7 14 13 2 12.0 46 41 3 9.1 75 91 4 8.3 82 100 5 6.9 105 128 6 3.9 105 128 It will be clearly understood that the invention in its general aspects is not limited to the specific details referred to hereinabove.

o 00 0 0 4 o 0 0000 00 00 0 0 0 D 0 000000 o 0 0 00 S00o 00oo 00 0 00 Q O 000000 0 0 0 0 0 00 0 00 0 0 0 oOOOO0 0 0 0 0 000000 0 0

Claims (6)

1. 2. Process according to claim 1 in which the combustion step is carried out at temperatures in the range 700 to cc o a 9 875 0 C and the sulpholysis is carried out at temperatures in the range 120 to 900 0 C.
2. 3. Process according to claim 2 in which the sulpholysis is carried out at temperatures in the range 770 to 870 0 C.
3. 4. Process according to any preceding claim in which the sulpholysis is carried out using a chemical feedstock chosen from the group consisting of concentrated sulphuric Se acid; dilute aqueous solutions of sulphuric acid; mixtures tot, of concentrated sulphuric acid and sulphur trioxide; flt mixtures of sulphur trioxide and steam; mixtures of sulphur dioxide, air and steam; mixtures of elemental sulphur, air and steam. Goo 5. Process according to claim 1 for recovery of fluoride values from spent potlining (SPL) characterised in that SPL is crushed and screened to a suitable size fraction and fed to a combustion reactor in which it is subjected to oxidation at temperatures in the range 700 to 875'C to produce an SPL ash, and the SPL ash is subjected to sulpholysis in a separate reactor at temperatures in the range 120 to 900' C to produce a gaseous product containing fluoride values. S1- 20
4. 6. Process according to claim 5 in which the the SPL is subjected to a mineral benefication procedure or chemical treatment to increase the concentration of fluorides therein prior to the combustion step.
5. 7. Process according to claim 5 or 6 in which the sulpholysis is carried out at temperatures in the range 770 to 870 0 C.
6. 8. Process according to any of claims 5 to 7 in which the sulpholysis is carried out using a chemical feedstock chosen from the group consisting of concentrated sulphuric acid; dilute aqueous solutions of sulphuric acid; Cc mixtures of concentrated sulphuric acid and sulphur trioxide; mixtures of sulphur trioxide and steam; mixtures of sulphur dioxide, air and steam; mixtures of elemental I sulphur, air and steam. 1 material containing fluoride salts to eZhe.t with combustible components sub lally as described with reference to ccompanying drawings and in Example 1 or Eam anR Fxamp1 3 nr Fxample 4 hertin. 060000 0 0 0000 0 0 0 a0 0 O"O 0 DATED THIS 10TH DAY OF APRIL 1991 oooo COMALCO ALUMINIUM LIMITED By its Patent Attorneys: o co GRIFFITH HACK CO. o Fellows Institute of Patent Attorneys of Australia. 0 0 Attorneys of Australia.