Method for treating pickling acid residue

Abstract

A novel process for treating pickling acid residue and recovering sulfates and nickel therefrom has been developed. By lowering the pH of a magnesium compound slurry to 4-5.5 with sulfuric acid containing pickling acid residue in the presence of ammonium sulfate, both magnesium sulfate and nickel sulfate are solubilized. Magnesium sulfate and nickel sulfate solution is separated from the solids by filtration and an iron hydroxide and chromium hydroxide residue is obtained as a precipitate. Magnesium sulfate and nickel sulfate are then separated from the solution.

Claims

1. A method for recovering sulfates and nickel from a sulfuric acid containing pickling acid residue comprising the steps of: slurrying under continuous stirring at least one magnesium compound selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate, and combinations thereof into water; adding sulfuric acid containing pickling acid residue (PAR) under continuous stirring to obtain a Mg/PAR-slurry with a stable pH of 4-5.5 at a temperature between 70° C. and 90° C.; continuing continuous stirring of the obtained Mg/PAR-slurry for at least 30 minutes at the temperature between 70° C. and 90° C.; adding ammonium sulfate at any stage before filtration of the obtained Mg/PAR-slurry; separating an iron and chromium-containing residue by filtration and obtaining a solution of nickel sulfate and magnesium sulfate as a filtrate; and recovering sulfates and nickel from the nickel sulfate and magnesium sulfate solution filtrate.

2. The method for recovering according to claim 1, wherein the sulfates are recovered as magnesium sulfate solution by separating the nickel from the nickel sulfate and magnesium sulfate solution filtrate by adsorbing nickel on an ion exchange resin and nickel is recovered as nickel sulfate from the ion exchange resin by elution with sulfuric acid.

3. The method for recovering according to claim 1, wherein the magnesium compound is magnesium oxide.

4. The method for recovering according to claim 1, wherein the magnesium compound is magnesium hydroxide.

5. The method for recovering according to claim 1, wherein the magnesium compound is magnesium carbonate.

6. The method for recovering according to claim 1, wherein the magnesium compound is a combination of magnesium oxide, magnesium hydroxide, and magnesium carbonate.

7. The method for recovering according to claim 1, wherein the at least one magnesium compound is added in dry form.

8. The method for recovering according to claim 1, wherein the concentration of the ammonium sulfate in the Mg/PAR-slurry is between 0.5 and 5% (w/V).

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1. A schematic process scheme; one embodiment of the process according to the invention

(2) FIG. 2. Elution of Ni-loaded resin with 20 wt-% sulfuric acid. Sample size 10 ml (Example 3)

DETAILED DESCRIPTION OF THE INVENTION

(3) Typically, pickling acid residue i.e. PAR contains metals such as nickel, chromium and iron in the form of sulfates and free sulfuric acid. Sulfate content can be up to 60% of the total weight, out of which half is free sulfuric acid. The nickel content is typically in the range of 1-5 wt-%, while iron content is typically in the range of 10-15 wt-% and chromium content in the range of 1-5 wt-%.

(4) According to the present invention separation of nickel and sulfates from the other components in pickling acid residue is accomplished by adjusting pH of a magnesium compound(s) slurry i.e. Mg-slurry to pH 4-5.5 in the presence of ammonium sulfate using sulfuric acid containing pickling acid residue. At this pH range iron and chromium are insoluble hydroxides and can be separated by filtration from the soluble sulfate salts; nickel as nickel sulfate and remaining sulfates as magnesium sulfate.

(5) In the method according to the invention, first at least one magnesium compound selected from the group consisting of magnesium oxide, magnesium hydroxide and magnesium carbonate or any combination thereof, is slurried in water under continuous stirring to obtain a Mg-slurry. The final Mg-slurry is adjusted to contain between 10-70 g/l magnesium, preferably 30-60 g/l.

(6) The at least one magnesium compound selected from the group consisting of magnesium oxide, magnesium hydroxide and magnesium carbonate is preferably magnesium oxide. The magnesium compound can be magnesium hydroxide. It is also possible to use magnesium carbonate as the magnesium compound. Magnesium oxide, magnesium hydroxide and magnesium carbonate can also be used as a combination.

(7) The at least one magnesium compound or the combination of magnesium oxide, magnesium hydroxide and magnesium carbonate can be used in dry form or as a water slurry.

(8) Depending on the magnesium compound or the mixture of magnesium compounds used, the dissolution time varies. For example, with magnesium carbonate the dissolution time is longer than with magnesium hydroxide.

(9) Then sulfuric acid containing pickling acid residue, which contains nickel, chromium and iron as sulfates as well as free sulfuric acid is added under continuous stirring to the Mg-slurry to lower the pH to 4-5.5 and to obtain a Mg/PAR-slurry, adjusting until pH is stable. Pickling acid residue can be added as solid or as a water slurry.

(10) Ammonium sulfate is added to the Mg/PAR-slurry to improve filtration to a concentration between 0.5 and 5% (w/V), preferably 2-3% (w/V). Ammonium sulfate can be added at any stage before filtration.

(11) Temperature is kept between 70° C. and 90° C. during the addition of PAR. After the addition of PAR is completed i.e. stable pH between 4 and 5.5 is obtained, mixing i.e. continuous stirring of Mg/PAR-slurry is continued for a minimum of 30 minutes and up to 6 hours, preferably 3-5 hours at a temperature between 70° C. and 90° C.

(12) Nickel sulfate and magnesium sulfate are both solubilized during the mixing step. After stirring the slurry is filtrated and a nickel sulfate and magnesium sulfate solution is obtained as a filtrate (Ni/Mg sulfate solution filtrate). FeCr residue, containing iron hydroxide and chromium hydroxide, is obtained as a precipitate.

(13) In the final step of the process according to the present invention, sulfates and nickel are recovered i.e. separated from the solution.

(14) Sulfates can be recovered as magnesium sulfate by adsorbing nickel from the solution with an ion exchange resin, creating a magnesium sulfate raffinate. Ion exchange resin functional groups can be imino di-acetate (IDA) or bis-picolyl amine (BPA). Nickel is eluted from the resin as a nickel sulfate eluate using sulfuric acid as eluent.

(15) Magnesium sulfate and nickel sulfate can be separated from the Ni/Mg sulfate solution filtrate also by other applicable hydrometallurgical routes e.g. precipitation.

(16) Next, the invention is described with reference to the following examples, which are not intended to limit the scope of the invention.

EXAMPLES

(17) The composition of the pickling acid residue (PAR) used in the disclosed Examples 1 and 2 is shown in Table 1. Metal content was determined by MP-AES (microwave plasma atomic emission spectrometer, Agilent Technologies), and sulfate content was determined by titration with NaOH/EDTA as titrant. Balance is moisture.

(18) TABLE-US-00001 TABLE 1 Composition of PAR in disclosed examples. Element mg/kg Al   <300 Ca   <600 Co   <600 Cr  16 300 Cu    712 Fe 106 000 K   <600 Mg   <200 Mn   1040 Na   <1000 Ni  11 700 Zn   <500 SO.sub.4.sup.2− 620 000

Example 1

(19) 110 g of magnesium oxide (MgO) (93 w/w % MgO content) was slurried in 900 ml H.sub.2O together with 30 g ammonium sulfate. PAR was added gradually during 2 hours under continuous stirring until pH was stable at 4. Total required amount of PAR was 355 g. The temperature during the addition of PAR was kept at 80° C. The mixing i.e. continuous stirring at 80° C. was continued for an additional 30 minutes and the mixture was then filtered using a Buchner funnel. The filtrate, containing nickel- and magnesium sulfate, was analyzed for metal content with MP-AES. The results are presented in table 2.

(20) TABLE-US-00002 TABLE 2 Composition of the filtrate. Element mg/l Yield Mg 52 700 81% Ni  2400 50% SO.sub.4.sup.2− 212248 96%

(21) Sulfate yield was high, having solubilized nickel and magnesium to 50% and and 81% respectively. It is possible that while there are enough sulfates available, the short reaction time means it is still in the form of free sulfuric acid.

(22) Nickel and magnesium were separated using chelating ion exchange resin containing iminodiacetic acid functional groups. 20 ml of Lanxess TP208 MDS resin was loaded into a 150 ml drip column and washed with 50 ml H.sub.2O before use. The resin was in sodium form.

(23) 200 ml of nickel- and magnesium sulfate solution filtrate from step 1 was passed through the resin bed and 10 samples of 20 ml were collected. Solution was passed through at a rate of 4 BV/h (BV:Bed Volume, 20 ml). Resin was washed with 50 ml water, and then eluted with 20 ml of a 20 w/V % sulfuric acid solution. All samples were analyzed with MP-AES (tables 3 and 4).

(24) Analysis of raffinate solution from column shows selective binding of nickel (table 3).

(25) TABLE-US-00003 TABLE 3 Metal content of the raffinate solution at 4 BVs (80 ml). Element mg/l Mg 46 400 Ni <50     

(26) The metal content of the eluate solution is presented in table 4.

(27) TABLE-US-00004 TABLE 4 Metal content of the eluate solution. Element mg/l Mg 4290 Ni 9010

Example 2

(28) Procedure in Example 1 was repeated but mixing time after addition of PAR was increased from 30 minutes to 3 hours. The filtrate was analyzed for metal content with MP-AES and the results are presented in Table 5. Sulfate content was calculated according to metal content.

(29) TABLE-US-00005 TABLE 5 Metal content and calculated metal yields of the nickel- and magnesium sulfate solution. Element mg/l Yield Mg  58 500  94% Ni  3150  70% SO.sub.4.sup.2− 236402 100%

(30) Using a longer reaction time, the nickel yield was 70% and magnesium yield was 94% (table 5). Sulfate yield was also increased to 100%.

Example 3

(31) Nickel and magnesium sulfate solution from Example 2 was passed through 50 ml chelating resin (Tulsion CH-90, IDA functional group) with a pump in upflow mode. Total 300 ml of solution was passed through the column and 3×100 ml samples were collected and analysed.

(32) Analysis of the 100 ml sample solutions show initial binding of magnesium and then slowly releasing it when replaced by nickel (table 6).

(33) TABLE-US-00006 TABLE 6 Metal content of the raffinate (ppm) at given volumes Element 100 ml 200 ml 300 ml Mg 41 700 59 200 65 300 Na 21 400 <1000     <1000     Ni <50      254     431    

(34) Sodium is released from the resin in initial stages as magnesium enters the system, and then on continuation of the trial nickel slowly replaces magnesium.

(35) Elution of the resin shows release of nickel and a small amount of magnesium, indicating nickel had not yet fully replaced magnesium in the resin (FIG. 2).