Title of Invention

"A PROCESS FOR UPGRADING AN IRON-CONTAINING TITANIFEROUS MATERIAL"

Abstract

A process for upgrading an iron-containing titanferous material to produce a synthetic rutile, including: roasting the titaniferous material at an elevated temperature in an atmosphere and under conditions such that iron in the material is oxidized largely to a ferric state whereby to produce an oxidised titaniferous material; treating the oxidised titantferous material, in an atmosphere containing a reducing gas, at a temperature in the range of 600-900°C so as to reduce the iron in the material largely to metallic iron, whereby to produce a reduced titanferous product; and cooling the product and subjecting the cooled product to further treatments including one or more leaching treatments for separating out metallic iron and other impurities, whereby to produce a synthetic rutile residue; wherein said oxidation roasting is carried out at a temperature sufficiently above 900°C for the titaniferous material to be converted by said roasting from a structure in which MzO3 is the major phase to a structure in which MsO5 is the major phase, whereby to enhance the amenability of the reduced titaniferous product to separation of impurities by said leaching treatment(s), and to increase the TiO2 content of said synthetic rutile residue.

Full Text

Field of the Invention This invention is concerned with the Containing titaniferous matiral process for up grading production of synthetic rutile by low temperature reduction of pre-oxidised titaniferous material, typically but not exclusively ilmenite. Background Art Ilmenite is the most commonly occurring titanium-containing mineral. It is an oxide of titanium and iron, most simply represented as FeTiO3 but often also written as FeO.TiO2- Apart from iron, there are typically a number of other " impurities in much smaller amounts which vary from deposit to deposit, including silicon, manganese, magnesium, aluminium and vanadium. In altered or weathered ilmenites, thorium can also be present at levels which are now considered unacceptable for downstream processing. A number of processes have been proposed for upgrading ilmenite to synthetic rutile, typically having a TiO2 content greater than 90%. Synthetic rutile is a suitable feed for the chloride process route to the production of pure TiOg, a feedstock for pigment and other valuable commodities. The most widely practised synthetic rutile process in Australia, a major . commercial source of ilmenite, is commonly known as the Becher process. In this process, ilmenite concentrate is reduced in a rotary kiln, with coal as reductant and at a temperature typically in the range 1120 -1160°C. The iron in the ilmenite is converted largely to metallic iron. The resultant reduced ilmenite is then subjected to aeration leaching, in which the metallic iron is oxidised to a readily separable form in the presence of a dilute ammonium chloride solution with air sparging. A sulphuric acid leach then removes some of the residual iron, as well as other impurities including manganese and silicon. In the earlier practice of the Becher process, it was thought beneficial to oxidise the ilmenite in air at a temperature around 1000°C but this pre-oxidation step was omitted by all or most processors some years ago. Such pre-oxidation is detailed, for example, in Bracanin et al, 'The Development of a direct reduction and leach process of ilmenite upgrading" 101st AIME Meeting San Francisco, 1972. This paper reported that pseudobrookite was the principal component after a sufficient duration of oxidation, eg. 3-4 hours. Another group of known processes involve a reduction step using a gaseous reductant, typically hydrogen, at a relatively lower temperature, usually around 750-900°C. For example, US patent 4097574 discloses preoxidation in air in a rotary kiln or fluid bed furnace at a temperature in the range of 592-870°C, followed by hydrogen reduction of the iron largely to metallic iron, preferably at a temperature in the range of 787-845°C. An aeration leach is optionally followed by an acid leach. The Murso process is described, eg, in British patent 1225826, and involves a pre-oxidation step similar to that in US4097574, but the gaseous reduction at 850-900°C is predominantly to ferrous iron and is followed by a single hydrochloric acid leach. Another process involving partial reduction is disclosed in Australian patent application 64383/96. In these low temperature processes with gaseous reductant (in comparison to the Becher process with solid reductant), and indeed in the older form of the Becher process, the pre-oxidation has been thought to be beneficial, especially with primary as distinct from altered or weathered ilmenites, by breaking down the larger ilmenite sub-grains in a way which renders the mineral more amenable to subsequent reduction and leaching. It is, furthermore, conventional wisdom in low temperature processes, notwithstanding the higher pre-oxidation temperature known to have been adopted in the earlier practice of the Becher process, that the maximum temperature in the oxidation kiln is 900°C if sintering effects are to be avoided: both US4097574 and GB1225826 state an upper temperature limit of 870°C for the pre-oxidation step. A similar process disclosed in example 6 of Australian patent 639089 mentions pre-oxidation "at 900°C" and a reduction temperature "less than 900°C". An objective of all synthetic rutile processes is to maximise the TiOa content of the end-product. Once that content is greater than 90%, even incremental improvements in the TiOa proportion can be reflected in a much higher product price. It is an object of the present invention to obtain a high grade, ie very high TiOa content, synthetic rutile from a primary ilmenite. Disclosure of the Invention The invention entails the realisation that, contrary to the prevailing view in relation to low temperature synthetic rutile processes, the pre^pxidation step can and should be carried out at a higher temperature, specifically above 900°C and preferably in the range 925 to 1000eC, with measurable effect in terms of TiOa content of the synthetic rutile product. The invention accordingly provides in one aspect a process for upgrading an iron-containing titaniferous material to produce a synthetic rutile, which includes roasting the titaniferous material at an elevated temperature in an atmosphere and under conditions such that iron in the material is oxidised largely to a ferric state whereby to produce an oxidised titaniferous material. This oxidised titaniferous material is treated, in an atmosphere containing a reducing gas, at a temperature in the range of 600-900°C so as to reduce the iron in the material largely to metallic iron, whereby to produce a reduced titaniferous product. The reduced titaniferous product is cooled and the cooled product is subjected to further treatments including one or more leaching treatments for separating out metallic iron and other impurities, whereby to produce a synthetic rutile residue. The oxidation roasting is carried out at a temperature above 900°C whereby to enhance the amenability of the reduced titaniferous product to separation of impurities by said leaching treatment(s). Preferably, the temperature of the titaniferous material during said roasting is selected so that the titaniferous material is converted by said roasting from a structure in which M2O3 is the major phase to a structure in which M3O5 is the major phase. It is believed that prior pre-oxidation treatments in lower temperature synthetic rutile processes resulted in a structure in which M2O3 predominated relative to M3O5 ie. in effect oxidation was only partially effected. The aforementioned Bracanin et al paper described pre-oxidation in the context of high temperature processes using coal as reductant, and did observe that pseudobrookite (ie M3O5) was the predominant species after 3-4 hours oxidation. It was not, however, appreciated by those carrying out low temperature synthetic rutile processes with gaseous reductant that the pre-oxidation in these processes was producing a predominant M20a structure. The present inventors have appreciated this fact, and that it is significant, and have further realised that a relatively high temperature pre-oxidation has a beneficial effect on the subsequent low temperature reduction step with gaseous reductant. It is thought that the temperature above which M3O5 becomes dominant varies with the mineral source, but it may typically be in the vicinity of 920-930°C. According to a second aspect of the invention, therefore, there is provided a process for upgrading an iron-containing titaniferous material to produce a synthetic rutile, which includes roasting the titaniferous material at an elevated temperature above 900°C in an atmosphere and under conditions such that iron in 'the material is oxidised largely to a ferric state whereby to produce an oxidised titaniferous material. The oxidised titaniferous material is treated, in an atmosphere containing a reducing gas, at a temperature in the range of 600-900°C so as to reduce the iron in the material largely to metallic iron, whereby to produce a reduced titaniferous product. The reduced titaniferous product is cooled and the cooled product is subjected to further treatments including one or more leaching treatments for separating out metallic iron and other impurities, whereby to produce a synthetic rutile residue. The oxidation roasting is carried out at a temperature selected whereby the titaniferous material is converted by the oxidation roasting from a structure in which M3O5 is the major phase to a structure in which M3O5 is the major phase. Subsequent disclosure is applicable to both aspects of the invention. Preferably, during the oxidation roasting the temperature of the titaniferous material is above 925°C, but less than 1000°C. A higher temperature increases the likelihood of sintering. It is found that the optimum temperature varies with the source of the feed 'material, but is generally in the range 925-975°C. The oxidation mechanism results in the presence of a number of different oxide species, but may be essentially represented by the following equation: (Equation Removed) which may be written: (Equation Removed) where M represents any metal species such as Fe, Mn, Mg, Al or Ti, and in general includes impurities. Preferably, the oxidation roasting is carried out under conditions to discourage accretion formation. A de-agglomerating agent may be added to the oxidation roast step. This may be effected by utilising a circulating fluidised bed for the roasting step. It is believed that the high level of turbulence, and the near 100% material circulation, characteristic of a circulating fluidised bed assist in countering the formation of accretion deposits. In general, either or both of the oxidation and reduction steps are carried out in respective circulating fluidised beds. The oxidation step is preferably carried out in an oxygen containing atmosphere, more preferably air for which steps are taken to control its oxygen potential, eg. either by oxygen enrichment and/or by relying on a raised pressure, eg 10 bar or so, and/or adding diluents. The preferred reductant for the reduction step is an atmosphere which is substantially a hydrogen atmosphere, preferably substantially pure hydrogen. Carbon monoxide is less suitable because iron carbides may be formed during the reduction stage, which adds to leaching costs. The hydrogen may be supplied mixed with a relatively inert gas. Typically with hydrogen reduction a pressure above atmospheric is required, eg. about 10 bar, but possibly lower or higher, to improve process economics. The reduction reactions result in a variety of oxide species. However, the key representative reactions are as follows: (Equation Removed) (Equation Removed) The first of these may be written: (Equation Removed) where M represents any metal species, and in general includes impurities. The preferred temperature range for the reduction step is 750° to 900°C. In general, it should be as low as achievable to optimise the leaching steps, but, as is known, the lower the temperature the lower the water vapour tolerance for the reduction reactions. The selected temperature will therefore be a compromise between these opposing effects. The metallisation of the iron achieved in the reduction step is preferably greater than 80%, more preferably greater than 95%. It is preferred that the leaching treatments include, firstly, an aeration leach to oxidise the iron metal to a readily separable oxide, and then an acid leach, eg. with a mineral acid, to remove a significant proportion of the residual iron and other impurities. The acid may be, e.g. sulphuric acid, depending on the composition of the ilmenite, Alternatively, e.g. hydrochloric acid might be employed. The aeration leach may be conventional eg. similar to that used in the Becher process, employing ammonium chloride as catalyst. The process parameters are preferably such that the TiO2 content of the synthetic rutile produced is greater than 90%, more preferably about 95%. While not wishing to be bound by the following, which is presently merely a theory, applicant's present understanding is that the effect of the higher temperature pre-oxidation, and the predominant M3O5 structure of the oxidised titaniferous material, may be a finer, grain structure which is conducive to enhance the reduction reactions, especially with a gaseous reductant. On conversion as M2O3 in the reduction step to rutile and metallic iron (equation 4 above), the result is a more open rutile lattice with a finer metal phase, both aspects enhancing metal oxidation and separation in the aeration leach and enhanced access to impurities and sites during the acid leaching process. These effects may arise because the residual M203 phase is more finely dispersed within the reduced ilmenite grain, which aids in the removal of impurities by acid leaching. It is further thought that the oxidation mechanism results, after reduction, in a titanate lattice of improved integrity and uniformity, giving reduced production of Ti02 fragments during reduction, aeration and leaching, and so higher TiO2 recovery into the end-product. Accordingly the present invention relates to a process for upgrading an iron-containing titanferous material to produce a synthetic rutile, including: roasting the titaniferous material at as hereines cride above 900 c temperature in an atmosphere and under conditions such that iron in the material is oxidized largely to a ferric state whereby to produce an oxidised titaniferous material; treating the oxidised titantferous material, in an atmosphere containing a reducing gas, at a temperature in the range of 600-900°C so as to reduce the iron in the material largely to metallic iron, whereby to produce a reduced titanferous product; and cooling the product and subjecting the cooled product to further treatments including one or more leaching treatments for separating out metallic iron and other impurities, whereby to produce a synthetic rutile residue; wherein said oxidation roasting is carried out at a temperature sufficiently above 900°C for the titaniferous material to be converted by said roasting from a structure in which M^jOa is the U^L major phase to a structure in which M3O5 is the major phase, whereby to enhance the amenability of the reduced titaniferous product to separation of impurities by said leaching treatment(s), and to increase the TiO2 content of said synthetic rutile residue. Example 1 Samples (120g) of three different ilmenite concentrates were oxidised at temperatures of 850°C, 900°C, 950°C and 1000°C in a bubbling fluidised bed utilising a 12.5% 02 and 87.5% N2 gas mixture as fluidising/oxidising gas, at a total flow rate of 6 l/min at STP. The gas velocity was 0.8 m/sec. Analyses (wt%) of the samples are set out in Table 1. The reaction was allowed to run to completion of oxidation. PXRD patterns were recorded for grab samples from the oxidation runs. Quantitative phase analyses were made in the final oxidation runs, and the results are presented in Figures 1, 2 and 3. It will be seen that, in each case, there is a sharp onset of a conversion from a structure in which M2O3 dominates relative to M3O5. and the converse. This occurs at a temperature between 900°C and 950°C. The proportion of TiO2 also declines. The fourth phase depicted is an intermediate species indicated as "HT239", ie. Fe2Ti3Oe. This is largely eliminated by oxidation at 1000°C. The figures reveal how prior pre-oxidation carried out at temperatures typically around 850°C in fact produced little conversion of the M203 structure to M3O5 and that temperatures above 900°C, and preferably in the region of 950°C, are needed to ensure predomination of M3O5 relative to M2O3. It might be expected, then that previously predicted benefits of pre-oxidation to the reduction step would not be seen unless pre-oxidation was effected above 900°C. This is indeed demonstrated by the next example. Table 1 - Analyses of llmenite Samples (Table Removed) Example 2 The oxidation products (65g samples) of Example 1 for the Capel primary and CRL concentrates were mixed with limestone (2g) and reduced with hydrogen at 850°C in a bubbling fluidised bed and at a linear gas density of 0.6m/sec. Grab 'samples were taken at 5, 10, 15 and 30 minutes. The lime was separated from the reduced ilmenite (Rl) by magnetic separation and metallic iron content of the Rl was measured by Satmagan. The results are set out in Table 2. The results in Table 2 show that the pre-oxidation temperature has an effect on metallisation rates. The influence is greater for the CRL concentrate, where an increase in pre-oxidation temperature from 850 to 950eC gives a 25% increase in average metallisation rate. Further increase of the oxidation temperature to 1000°C causes the metallisation rate to decrease slightly, possibly due to sintering effects. Table 2. Metallic iron (wt%) in Capel and CRL grab sample Rl's corresponding to different pre-oxidation treatments (Table Removed) Example 3 The reduced ilmenites (Rl's) from the eight reduction runs of Example 2 were demetallised in 5% H2SO4 and then leached in refluxing 15% (w/w) HCI for 2 h, with regular withdrawal of solution aliquots for analysis. The procedure entailed heating a starting volume of 85 ml of the chosen strength acid to boiling point in a round bottom 250 ml glass reactor fitted with a mechanical stirrer (run at 500 rpm) and a condenser, then adding 10 g of demetallised Rl sample. After different selected time intervals, the stirrer was turned off, the slurry was allowed to settle for a few seconds, and then a 5 ml aliquot of solution was withdrawn using a pipette. The solution was transferred to a volumetric flask and made up to 250 ml with dilute nitric acid, then analysed for Fe, Ti, Mg and Mn by ICP-AES (atomic emission spectrosoopy) analysis. Calculations of the metal atom removal into solution after each time interval were corrected for the aliquots previously ^removed. At the end of the leaching (2 to 8 h), the remaining leach solution with suspended solids was decanted and filtered. The fine solids on the filter paper were washed with 3 x 100 ml water and 2 x 50 ml ethanol and dried at 100°C. The coarse solids were washed progressively with 2 x 50 ml ethanol 10% HCI, 3 x 400 ml water and 2 x 50 ml ethanol, then dried at 100°C and combined with the fines for XRF analyses. The XRF analyses of Rl's, DP's (demetallised products), and leach products (ie synthetic rutile SR) for both Capel and CRL samples are given in Table 3. Results on the extraction of Fe, Mn, Mg and Ti from the solution analyses are reported in Table 4. The grade increases with increasing pre-oxidation temperature, from 95.6 to 96.3% Ti02 for the CRL samples and from 96.7 to 98.0% TiOa for the Capel samples. The higher grades at the higher pre-oxidation temperatures are due mainly to lower residual iron levels. This was evident already in the demetallised products, where a decrease or more than 1% in the total residual iron was observed in response to decrease in the pre-oxidation temperature. An inspection of the XRD patterns of the demetallised products showed that this is due to a decrease in residual metallic iron. XRD patterns of the SR products also showed more than twice as much residual metallic iron in samples derived from the lower temperature pre-oxidations. Thus the lower pre-oxidation temperatures promote the metallisation of some of the iron in regions inaccessible by the leaching solution. The effect of pre-oxidation temperature on leaching kinetics was also plotted for these experiments. The time to achieve 50% removal of both Mg and Mn was found to be approximately halved by increasing the pre-oxidation temperature from850to1000°C. Table 3. XRF analyses (wt%) on Capel and CRL Rl's, DP's and 15% HCI SR's. (Table Removed) Table 4. Element extraction in 15% HCI leaching or CRL and Capel OP's (Table Removed) Example 4 The experiments of Examples 1, 2 and 3 were repeated on samples from the Monto Goondicum (abbreviated as Monto G.) ilmenite deposit in Queensland. The analysis of the samples is set out in Table 5. The Monto Goondicum concentrate has a particularly high magnesia content. The Mg substitutes for Fe in the ilmenite lattice. Relatively pure MgTiO3 with the ilmenite-type structure occurs naturally as the mineral geikelite. An additional set of tests was therefore added for a pre-oxidation temperature of 1050°C, to assist in the breakdown of the Mg-rich ilmenite. The metallic iron analyses (Satmagan) on grab samples for the reduction step are given in Table 6. A comparison with Table 2 shows that the rates of metallisation of the Monto G. concentrate are twice as high as those obtained for the Capel and CRL samples. This is due to the effect of the higher hydrogen flow (2 m/s c.f. 0.6 m/s) in a flow regime where gas starvation is important. The significant effect of pre-oxidation temperature on metallisation kinetics is seen to be at temperatures between 900 and 950°C. XRD patterns on the oxidation products showed that the greatest change in the oxidation phase assemblage occurs in this temperature interval. AT 900°C, ilmeno-hematite plus rutile were the major oxidised phases while at 950°C, M3O5 (pseudobrooktte) became the major oxidation product. An XRD pattern of the oxidised product obtained at 1050°C showed almost pure pseudobrookite, with only small amounts ( The demetallised products from the fluid bed reductions were leached in refiuxing 15% HOI, with withdrawal of solution samples for analysis as described in Example 3. Total leaching times of 4 h were used, compared to only 2 h for the CRL and Capel samples. XRF analyses on the Rl's, DP's and SR products, as well as on the original concentrate, are reported in Table 7. The DP analyses in Table 7 show a high level of residual iron (7.7% expressed as Fe2Oa) in the sample from the 900°C pre-oxidation, with a progressive decrease in residual iron as the pre-oxidation temperature is increased. This is consistent with lower degrees of metallisation in Rl's obtained from the lower-temperature pre-oxidised samples, and is confirmed by the metallic iron contents of the Rl's, shown in Table 7. The lower metallisation levels for the 900 and 950°C pre-oxidation samples in Table 7 compared to those given for the final grab samples in Table 5 are due to the slower reduction kinetics in the runs where grab samples were not removed and thus the average hydrogen-to-solids ratio remained lower. The XRF analyses of the SR products in Table 7 show that the process of the invention is effective for treating a high-magnesia concentrate. Grades of +95% TiO2 were obtained and the grade improved significantly (95% to 97% TiOa) wrth increase in the pre-oxidation temperature used. The leaching curves had not plateaued after 4 h leaching with refluxing 15% HCI and thus higher grades could be obtained with further leaching. Table 5. Analysis (wt%) of Monto Goondicum concentrate (Table Removed) In table 5, total iron has been reported as Fe2O3, and hence the total is greater than 100%. Table 6. Metallic iron (wt%) in grab samples of Monto G. fluid bed Rl's corresponding to different pre-oxidatlon conditions (Table Removed) Table 7. Analyses of Monto G. Rl's, DP's and SB's from 15% HCI reflux leaching (Table Removed) Example 5 A sample of 100 grams of Boodanoo (WA) ilmenite was oxidised in a laboratory reactor using a 12.5% Qz and 87.5% N2 gas mixture as fluidising/oxidising gas, at a total flowrate of 6 l/min at STP. The oxidation conditions are detailed in Table 8 below. At the end of oxidation, the gas mixture was replaced with N2 to prevent further reaction. 5 grams of limestone (CaCOa) was then added. The N2 was then replaced by a 2:1 mixture of Ha:N2 at a total flowrate of 12 l/min at STP. Reduction was carried out at 850°C for the times shown in Table 8 below. The resultant product was then leached in dilute 5% sulphuric acid to remove the metallic iron that was formed on reduction (this was used to simulate the effect of an aeration leach). The demetallised product was then leached using 20% HCI for 2 hours under reflux conditions to produce the SR product. Table 9 below contains the analysis for the four samples after the demetallisation and final 'leach stages. DP and SR indicate demetallised and post leaching synthetic rutile product respectively. The higher Ti02 grade is apparent in comparing the two pairs of results for 900°C, then 1000°C pre-oxidation. Table 8 - Oxidation and Reduction of Boodanoo Ilmenite (Table Removed) Table 9 - XRF Results for Leaching of Reduction Products (Table Removed) WE CLAIM: 1. A process for upgrading an iron-containing titanferous material to produce a synthetic rutile, including: roasting the titaniferous material at an elevated temperature in an atmosphere and under conditions such that iron in the material is oxidized largely to a ferric state whereby to produce an oxidised titaniferous material; treating the oxidised titantferous material, in an atmosphere containing a reducing gas, at a temperature in the range of 600-900°C so as to reduce the iron in the material largely to metallic iron, whereby to produce a reduced titanferous product; and cooling the product and subjecting the cooled product to further treatments including one or more leaching treatments for separating out metallic iron and other impurities, whereby to produce a synthetic rutile residue; wherein said oxidation roasting is carried out at a temperature sufficiently above 900°C for the titaniferous material to be converted by said roasting from a structure in which MzOa is the major phase to a structure in which MaOs is the major phase, whereby to enhance the amenability of the reduced titaniferous product to separation of impurities by said leaching treatment(s), and to increase the TiO2 content of said synthetic rutile residue. 2. A process as claimed in claim 1, wherein during said roasting the temperature of the titaniferous material is above 925°C. 3. A process as claimed in claim 1 or 2, wherein during said roasting the temperature of the titaniferous material Is less than lOOQoC, 4. A process as claimed in claim 1, wherein during said roasting the temperature of the titaniferous material is in the range 925- 975°C. 5. A process as claimed in claim 1, wherein said roasting temperature is the vicinity of 920 to 930°C. 6: A process as claimed in any preceding claim, wherein said roasting is carried out under conditions to discourage accretion formation. 7. A process as claimed in any preceding claim utilising a circulating fluidised bed for the roasting step. 8. A process as claimed in any preceding claim wherein said roasting is effected in an oxygen containing atmosphere. 9. A process as claimed in claim 8 controlling the oxygen potential of said oxygen containing atmosphere. 10. A process as claimed in any preceding claim wherein said reduction step is carried out in a circulating fluidised bed, 11. A process as claimed in any preceding claim wherein the reduction step atmosphere is substantially a hydrogen atmosphere. 12. A process as claimed in claim 11 wherein said atmosphere consists substantially of pure hydrogen. 13. A process as claimed in claim 11 or 12, wherein said treating step is effected at a pressure above atmospheric pressure. 14. A process as claimed in any preceding claim wherein the reduction step treatment is effected at a temperature in the range of 150°Cto900°C. 15. A process as claimed in any preceding claim wherein the metallisation of the iron achieved in the reduction step is greater than 80%. 16. A process as claimed in any preceding claim wherein the metallisation of the iron achieved in the reduction step Is greater than 95%. 17. A process as claimed in any preceding claim wherein said leaching treatments include, firstly, an aeration leach to oxidise the iron metal to a readily separable oxide, and then an acid each to remove a significant proportion of the residual iron and other impurities. 18. A process for upgrading an iron- containing titanferous material substantially as hereinbefore described with reference to the accompanying drawings.

Documents:

914-del-1999-abstract.pdf

914-del-1999-assignment.pdf

914-del-1999-claims.pdf

914-del-1999-correspondence-others.pdf

914-del-1999-correspondence-po.pdf

914-del-1999-description (complete).pdf

914-del-1999-drawings.pdf

914-del-1999-form-1.pdf

914-del-1999-form-13.pdf

914-del-1999-form-19.pdf

914-del-1999-form-2.pdf

914-del-1999-form-3.pdf

914-del-1999-form-5.pdf

914-del-1999-form-6.pdf

914-del-1999-gpa.pdf

914-del-1999-petition-137.pdf

914-del-1999-petition-138.pdf