Preparation method and station for non-caking agent solutions

Abstract

Process and dosing station (1) for the preparation of a solution of a non-caking agent, wherein a concentrate of the non-caking agent is circulated in a loop (6) and wherein the concentrate is subsequently diluted by water to obtain the solution. A flow of the concentrate can be drawn from the circulation loop (6) and mixed with a flow of water. The obtained solution can subsequently be fed into a second recirculation loop (12). A flow of solution can be drawn off from the second recirculation loop for being dosed into an amount of salt.

Claims

1. A process for the preparation of a solution of a non-caking agent comprising an iron salt of an organic acid with a ferric component and a ferrous component of less solubility than said ferric component, the process comprising circulating a concentrate of the non-caking agent in a circulation loop adapted to minimize the amount of oxygen introduced into the concentrate, and subsequently diluting the concentrate with water to obtain the solution, wherein the non-caking agent comprises the Fe.sup.3+ salt of meso-tartaric acid (FeMTA).

2. The process according to claim 1, wherein a flow of the concentrate is drawn from the circulation loop and mixed with a flow of water.

3. The process according to claim 1, wherein the obtained solution is subsequently fed into a second circulation loop.

4. The process according to claim 3, wherein a flow of the solution is drawn off from the second circulation loop for being dosed into an amount of salt.

5. The process according to claim 3, wherein the temperature in at least one of the circulation loop or the second circulation loop is below 20 C.

6. The process according to claim 3, wherein at least one of the circulation loop or the second circulation loop have an interior atmosphere with an oxygen content of below 1 vol %, of the gaseous interior content of the at least one of the circulation loop or the second circulation loop.

7. The process according to claim 3, wherein the pH of the solution in the second circulation loop is between 3.5 and 5.

8. The process according to claim 7, wherein the solution is passed via one or more static mixers at least one of in or between or upstream of the circulation loop and the second circulation loop.

9. The process according to claim 1, wherein a flow of the solution is passed via one or more pH measurement stations and wherein the pH is adjusted when the measured pH is outside of the range of 3-5.

10. The process according to claim 2, wherein the obtained solution is subsequently fed into a second circulation loop.

11. The process according to claim 4, wherein the temperature in at least one of the circulation loop or the second circulation loop is below 20 C.

12. The process according to claim 4, wherein at least one of the circulation loop or the second circulation loop have an interior atmosphere with an oxygen content of below 1 vol %, of the gaseous interior content of the at least one of the circulation loop or the second circulation loop.

13. The process according to claim 5, wherein at least one of the circulation loop or the second circulation loop have an interior atmosphere with an oxygen content of below 1 vol %, of the gaseous interior content of the at least one of the circulation loop or the second circulation loop.

14. The process according to claim 5, wherein the pH of the solution in the second circulation loop is between 3.5 and 5.

15. The process according to claim 6, wherein the pH of the solution in the second circulation loop is between 3.5 and 5.

16. The process according to claim 3, wherein the solution is passed via one or more static mixers at least one of in or between or upstream of the circulation loop and the second circulation loop.

17. The process according to claim 6, wherein a flow of the solution is passed via one or more pH measurement stations and wherein the pH is adjusted in case the measured pH is outside a prescribed range.

18. The method of claim 1 wherein the circulation loop has an atmosphere with a reduced level of oxygen compared to air.

19. The method of claim 18 wherein the circulation loop atmosphere is inert with an oxygen level of less than 5 vol %.

Description

(1) The invention will be further explained with reference to the accompanying drawings.

(2) FIG. 1: shows schematically a lay-out of an exemplary embodiment of a dosing station according to the present invention;

(3) FIG. 2: shows schematically an electrolyte cell for use in the dosing station of FIG. 1.

(4) FIG. 3: shows the diffractogram of the sample of Example 2 together with the model fit.

(5) FIG. 4: shows a representation of the structure of {[Fe(C.sub.4H.sub.4O.sub.6)(H.sub.2O).sub.2](H.sub.2O).sub.n}.sub.m

(6) FIG. 5: shows the influence of the pH on the free Fe(III) concentration, wherein the diamonds are the data for the aqueous solution based on FeMTA, and the squares are the data for the aqueous FeCl.sub.3 solution.

(7) FIG. 1 shows a dosing station 1 for the preparation of a solution based on the Fe.sup.3+ salt of meso-tartaric acid (FeMTA), for use as a non-caking agent for salt.

(8) The dosing station 1 comprises a first reservoir 2 connected or connectable to a concentrate source 3 via a supply line 4 comprising a pump 5. The first reservoir 2 stores an aqueous concentrate of the non-caking agent. The reservoir 2 forms part of a first circulation loop 6. The FeMTA based concentrate is constantly circulated through the loop 6 by means of a circulation pump 7.

(9) A discharge branch 8 branches off from the loop 6 for transporting part of the concentrate flow to a static mixer 9. Upstream of the static mixer 9 a water supply line 10 opens into the discharge branch 8 to supply demineralized water. At this point, the flow of concentrate is mixed with the flow of demineralized water before the mixture enters the static mixer 9. The flow velocities of the concentrate flow and the water flow are controlled in such a way that a diluted aqueous solution is obtained with the desired concentration of non-caking agent by means of density control unit 30. The water flow can for instance have a flow velocity of 1-7 times higher than the flow velocity of the FeMTA based concentrate.

(10) After passing the static mixer 9, the solution is transported to a second reservoir or buffer tank 11 forming part of a second circulation loop 12. The diluted aqueous solution of non-caking agent is continuously circulated through the loop 12 by means of two parallel circulation pumps 13, 14. Two pumps or more are used to provide a continuous flow to the dispensing unit. The pumps are arranged in such a way that the failure of one pump will trigger the other one to take over.

(11) In the exemplary configuration shown in FIG. 1, the second loop 12 is connected to four discharge lines 15, for transportation of the solution to four respective dispensing units 16. Each discharge line 15 is closable by means of a valve 17. The dispensing units 16 spray or pour the aqueous solution of the non-caking agent over an amount of salt, which can for instance be guided along the respective dispensing units 16 by means of a conveyor or similar transport line.

(12) A number of pH measurement stations 18, 19 are arranged in the first loop 6 and the second loop 12, respectively. At these pH measurement stations 18, 19 the pH is adjusted in case the measured pH is outside the range of 3.5<pH<4.0 for the concentrated solution, and 4.0<pH<4.5 for the diluted solution.

(13) As described above, during storage of the concentrated and diluted aqueous solutions based on FeMTA, in particular concentrated and diluted aqueous FeMTA solutions, part of the Fe.sup.3+ content will be reduced to Fe.sup.2+. Subsequently, the Fe.sup.2+ will precipitate from the solution as Fe(II) mesotartrate complex. To reduce this risk, the aqueous FeMTA based solution is subjected to an electrolytic oxidation step carried out with one or more electrolytic cells. FIG. 2 shows an exemplary embodiment of such an electrolytic cell.

(14) The electrolytic cell 21 comprises an anode 22 and a cathode 23. The anode 22 and the cathode 23 are separated by a non-porous ion exchange membrane 24.

(15) A catholyte is circulated between a catholyte reservoir 25 and the catholyte space 26 between the cathode 23 and the membrane 24. In the shown example the catholyte comprises a 1-3 M HCl aqueous solution.

(16) Similarly, an aqueous FeMTA based solution is circulated between an anolyte reservoir 27 and the anolyte space 28 between the anode 22 and the membrane 24.

(17) An electric power supply unit 29 provides an electric potential difference between the anode 22 and the cathode 23. At the cathode 23 hydrogen ions (H.sup.+) are electrochemically reduced to form hydrogen (H.sub.2). Chloride (Cl.sup.) ions migrate from the catholyte space 26 via the ion exchange membrane 24 and the anolyte space 28 towards the anode 22. At the anode 22, ferrous (Fe.sup.2+) ions are oxidized to ferric (Fe.sup.3+) ions.

(18) Oxidation of Fe.sup.2+ reduces the Fe.sup.2+-content and consequently the precipitation of Fe(II)mesotartrate. This way, the FeMTA content in the aqueous solution is stabilized.

(19) The FeMTA based solution can be discharged from the reservoir to be dosed to an amount of salt, if so desired, and the FeMTA solution can be replenished with a fresh supply.

(20) The present invention is further illustrated by the following examples.

EXAMPLE 1

(21) An electrochemical reactor was constructed in the form of a glass beaker with two graphite anode rods (diameter 10 mm50 mm high) vertically positioned and a 20 mm diameter glass tube with a glass frit in the bottom and containing platinum cathode wire gauze. An Ag/AgCl/saturated KCl reference electrode was positioned in the anode compartment near one of the graphite anodes. An aqueous solution based on FeMTA produced according to Example 4a of WO 2010/139587 with 15 hours of boiling was filtered prior to electrolysis to remove any precipitated Fe(II)mesotartrate. The electrochemical reactor was filled with an amount of the FeMTA based solution. The level of the catholyte compartment was maintained lower than the level in the anolyte compartment by means of pumping out catholyte in order to create a net flow of FeMTA based solution from the anolyte compartment via the glass frit into the catholyte compartment. The anode and cathode were connected to a DC power supply and an electric potential was applied between the anode and the cathode in such a way that the measured potential between anode and reference electrode was between +0.85 and +0.97 volts. The Fe(II) content of the solution was measured in samples taken during electrolysis and the results are shown in the table. The treated anolyte remained clear after more than one week, indicating that the FeMTA is stabilized by the electrochemical treatment.

(22) TABLE-US-00001 Time Anode Potential Fe(II) content [min] [volts] [wt % of total iron] 0 Not measured 1.74 110 0.85 1.38 220 Not measured 0.96 330 0.953 0.61 480 0.973 0.39

EXAMPLE 2

(23) An aqueous solution based on FeMTA was produced as described in Example 1. The pH of the solution was set at 4.35. It was used for metering onto an amount of salt using a dosing unit as described in EP2012/074188. After a while, greyish solids precipitated in the concentrated FeMTA buffer tank. A sample of these solids (Sample A) was analyzed with X-ray Diffraction (XRD) and Inductively Coupled Plasma Emission Spectrometry (ICP-ES) and chromatography.

(24) More particularly, XRD investigations were performed in order to study the presence of crystalline phase(s) and to determine their chemical and structural composition. The diffractogram has been recorded on a Bruker D8 diffractometer, using a standard sample holder.

(25) Settings: Cu K irradiation, 28 range: 5-75, 0.02 steps, 16.5 sec integration time per step, a variable divergence slit of 20 mm and a detector slit of 0.6 mm. A graphite monochromator was used to suppress fluoresce, a lower background signal thus being obtained.

(26) The diffractogram was analyzed using the Topas software package from Bruker. A quantitative assignment of the crystalline phase(s) observed was made by Rietveld refinement using reference diffractograms taken from the ICDD, ICSD and/or COD database (ICDD, International Centre for Diffraction Data, Powder Diffraction file, Full File 2007, ICSD, International Crystal Structure Database, http://www.fiz-karlsruhe.de/icsd.html, COD, Crystallography Open Database, http://www.crystallography.net/).

(27) The crystalline phase(s) of the sample could be identified with one single compound fitting all the measured diffraction positions. This structure was adopted from a similar Cobalt complex (COD-2204721). See also Dai-Xi Li, Duan-Jun Xu and Yuan-Zhi Xu, Acta Crystallographica, Section E 60(12) (2004) 1982-1984). Because iron and cobalt are adjacent in the periodic table, are both divalent, and have a comparable atomic radius (156 and 150 respectively), the element replacement is justified.

(28) The diffractogram of the sample is given in FIG. 3, together with the model fit. The diffractogram of the model fitted the measured data very well, only slight discrepancies in measured and modelled intensity could be observed which were caused by the measurement method which used a model to describe the beam and diffractometer geometry. The difference of the fit from the measured data is shown below the curves in grey.

(29) The bruto formula of the complex was {[Fe(C4H4O6)(H2O)2](H2O)n}m.

(30) A representation of the structure is given in FIG. 4. The compound is an iron polymeric complex, where an iron atom is coordinated by two tartrate dianions and two water molecules in an octahedral geometry. The hydroxyl oxygen atom and one oxygen atom of each carboxyl group chelate to the iron atom, but the other oxygen atom of this carboxyl group is uncoordinated. The polymeric chains are linked to each other via hydrogen bonds to form cavities which are filled with solvent water molecules.

(31) Inductively Coupled Plasma Emission Spectrometry (ICP-ES) experiments were performed by digesting a sample of the solids by a closed vessel micro-wave destruction using nitric acid. The element concentrations were measured by radial viewed ICP-ES (Spectro Arcos NT). Scandium was used as internal standard.

(32) The results are reported in Tables 1 and 2.

(33) TABLE-US-00002 TABLE 1 Main element concentrations as determined by ICP-ES. Element Solids from (% m/m) Sample A Fe 21-22 Mn 0.39-0.41

(34) TABLE-US-00003 TABLE 2 Minor and trace element concentrations as determined by ICP-ES. Element LOD* (mg/kg) Sample A (mg/kg) Al 8.8-11 1 As <10 10 B <2 2 Ba 3.2-3.9 0.1 Be <0.05 0.05 Ca 140-140 1 Cd <0.2 0.2 Co 32-32 1 Cr 3-3 1 Cu 64-67 1 Fe see Table 1 1 K <10 10 Li <0.5 0.5 Mg 330-340 0.1 Mn see Table 1 0.5 Mo <5 5 Na 790-810 10 Ni 16-17 2 P 41-43 5 Pb <10 10 S 62-64 5 Sb <10 10 Se <20 20 Si 30-37 5 Sn <10 10 Sr 0.1-0.2 0.1 Ti 12-13 0.5 V <2 2 Zn 42-44 1 Zr <2 2 *LOD is level of detection

(35) Sample A was also analyzed via chromatography using as column a stainless steel tube, length 300 mm, internal diameter 7.8 mm, IOA 1000 Organic Acids, as supplied by Alltech (No. 9646), and as mobile phase sulphuric acid, c(H2SO4)=0.01 mol/l.

(36) The results of the determination of meso-D,L-TA and impurities are shown in table 3.

(37) TABLE-US-00004 TABLE 3 Results of the determination of TA and impurities in solid sample from mTA dosing Meso-TA Oxalic acid Di-hydroxy Mono-hydroxy (0 aq) D,L-TA (0 aq) malonic acid malonic acid Acetic acid (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Sample A 54.9 n.d. 0.1 <0.1 0.1 <0.1 Remark: n.d. = not detectable;
Conclusions:

(38) The bruto formula of the complex is {[Fe(C4H4O6)(H2O)2](H2O)n}m. The compound is an iron polymeric complex, where an iron atom is coordinated by two tartrate dianions and two water molecules in an octahedral geometry. The iron is in the 2+ state. The solids consist for 54.9 wt % of tartrate in the meso-form (the remainder being iron, water, and some minor impurities). Tartrates in the D or L form were not detected. Side products were also not detected. Sample A contained a large amount of iron (22 wt %) and a small amount of manganese (0.4 wt %). Some trace metals like calcium and magnesium were detected.

EXAMPLE 3

(39) An aqueous solution based on FeMTA was produced as described in Examples 1 and 2. The original pH 3.8 of this solution was decreased to 3.5 by the addition of 1M HCl and subsequently further in steps of 0.5 pH unit to ultimately pH 1. For comparative reasons a diluted (0.7 wt % Fe) aqueous solution of FeCl.sub.3 was subjected to stepwise pH increase by addition of a diluted NaOH aqueous solution. At all these various pH values the free Fe.sup.3+ concentration was measured using an EG&G Instruments potentiostat/galvanostat model 263A.

(40) As shown in FIG. 5, at a pH higher than 2.5, precipitation of Fe(OH).sub.3 is observed. In the presence of meso-tartaric acid, at a pH above 2.5, Fe.sup.3+ remains in solution as it forms a complex with the meso-tartaric acid. If the pH increases over 4.5, however, this complex starts to break down and Fe.sup.3+ starts to precipitate from the solution as Fe(OH).sub.3.

(41) In FIG. 5, the influence of the pH on the free Fe(III) concentration is shown, wherein

(42) .diamond-solid. is used for the aqueous solution based on FeMTA

(43) .square-solid. is used for the aqueous FeCl.sub.3 solution

EXAMPLE 4

(44) An aqueous solution based on FeMTA was produced as described in Examples 1-3. The total iron content was 3.75 wt %, based on the total weight of the solution. This solution (Experiment 4.1) was stored in a closed vessel at room temperature. The Fe(II) content in the solution was measured over time relative to the sum of the Fe(II) and Fe(III) content using cyclic voltammetry (CV) (using an EG&G Instruments potentiostat galvanostat model 263A). Cyclic voltammetry is conducted using a three electrode system with platinum working electrode, a Ag/AgCl reference electrode and a platinum counter electrode. To a glass beaker with 100-120 ml of 1 molar HCl, 250 microliter of the sample solution is added. A potential sweep is conducted starting from +0.65 volts up till +0.80 volts, down till +0.10 volts and back to +0.65 volts (all voltages vs Ag/AgCl ref electrode) at a scan rate of 25 mV/s. The electric current is measured during this sweep. The average of the second and the third scan was used for calculating the Fe(II) content. The relative Fe(II) content (wt % of total iron) is calculated by dividing the signal of Fe(II) (i.e. the absolute value of the average limiting electric current of Fe(II) oxidation) by the sum of the signal of Fe(II) and the signal of Fe(III) (i.e. the absolute value of the average limiting electric current of Fe(III) reduction). The Fe(II) content of a sample (in absolute wt %) is calculated based on the electric current that is obtained of a CV measurement of that sample and of the CV measurement of a FeCl3 reference solution that contains 3.75 wt % of total iron. As of the fourth day, a precipitate was formed. In Table 4, results are summarized. The Fe(II) content increased up to around 0.1 wt %, based on the total weight of the solution.

(45) Another aqueous solution based on FeMTA was produced as described in Examples 1-3. The total iron content was 3.75 wt %, based on the total weight of the solution. This solution was stored for several months and after that precipitate was formed. A portion of this solution was filtered using a 150 micron candle filter to remove solids. This filtered solution (Experiment 4.2) was circulated in a loop and subjected to an electrolysis step using a electrolysis circulation system as indicated in FIG. 2. The electrolysis conditions were as follows based on FIG. 2: an electrolysis cell with packed bed anode (0.04 m.sup.2 Pt/Ti electrode with a 1.5 cm thick layer of graphite granulate) and a 0.04 m.sup.2 Pt/Ti electrode was used with an anion exchange membrane to separate the catholyte (approx. 2 M HCl) from the anolyte (FeMTA solution). The anolyte and catholyte solutions were circulated over the corresponding vessels and the electrochemical cell using two pumps. The applied electric potential difference between anode and cathode was 1 volts. The current density depends on the Fe(II) content and decreases during the process. Samples were taken and the Fe(II) content as measured using CV as described.

(46) The results are summarized in Table 4.

(47) The Fe(II) content for Experiment 4.2 was measured as indicated for Experiment 4.1. Within 2 days, the Fe(II) content was reduced to less than 0.01 wt %, based on the total weight of the solution.

(48) The last sample taken for Experiment 4.2 was stored in a closed vessel at room temperature (this was Experiment 4.3). The Fe(II) content was again measured over time as indicated for Experiment 4.1. As expected, after 50 days, the Fe(II) content has increased to around 0.05 wt %. These results are also summarized in Table 4.

(49) TABLE-US-00005 TABLE 4 series-1 no treatment samples standing at room temperature days Fe(II) content [wt %] 0 0.041% 4 0.056% precipitation 11 0.060% 18 0.075% 25 0.082% 32 0.090% 39 0.104% 45 0.109% 59 0.104% 67 0.096% 82 0.094% 124 0.102% 187 0.086% Fe(II) formed spontaneously precipitation observed after 4 days serie-2 electrolytic oxidation Days Fe(II) content [wt %] 0.0 0.053% 0.9 0.040% 1.2 0.025% 1.9 0.007% Fe(II) oxidized to <0.01% no precipitation observed series-3 after electrolytic oxidation samples standing at room temperature days Fe(II) content [wt %] 2 0.007% 51 0.054% 63 0.052% 83 0.065% 97 0.078% Fe(II) formed spontaneously no precipitation observed yet