Purification of NaCl brine containing iodine

Abstract

The present invention provides a process for separating iodine from a NaCl brine, comprising the following steps: (a) providing said NaCl brine containing iodide, (b) adjusting the pH of said NaCl brine to be no greater than 1.5, (c) adding oxidizing agent, such as chlorine containing oxidizing agent, to said NaCl brine resulting from step (b) to obtain an oxidation-reduction potential in said NaCl brine of from 560 mV to 925 mV, the combination of said pH of no greater than 1.5 and oxidation-reduction potential of 560 mV to 925 mV resulting in the formation of an iodine-chlorine anionic complex, and (d) contacting nonionic adsorption resin and said NaCl brine from step (c) one with the other to adsorb said iodine from this brine, to obtain as a result thereof NaCl brine wherein the iodine content therein is preferably no greater than 100 ppbw, more preferably no greater than 10 ppbw.

Claims

1. Process for separating iodine from a NaCl brine, comprising the following sequential steps: (a) providing NaCl brine containing at least 4 wt % NaCl and containing iodide, (b) adjusting the pH of said NaCl brine from step (a) to be no greater than 1.5, (c) adding oxidizing agent to said NaCl brine from step (b) to obtain an oxidation-reduction potential in said NaCl brine of from 560 mV to 925 mV, the combination of said pH of no greater than 1.5 and oxidation-reduction potential of 560 mV to 925 mV resulting in the formation of an iodine-chlorine anionic complex, and (d) contacting a non-functionalized, nonionic adsorption resin and said NaCl brine from step (c) one with the other to adsorb said iodine from said brine from step (c).

2. The process of claim 1 wherein the NaCl brine of step (a) contains 17 to 25 wt % of said NaCl.

3. The process of claim 1 wherein said adjusting of step (a) is carried out by adding HCl to said NaCl brine.

4. The process of claim 1 wherein said oxidizing agent is alkali or alkaline earth metal hypochlorite.

5. The process of claim 4 wherein said oxidizing agent is sodium hypochlorite.

6. The process of claim 1 wherein said oxidizing is carried out at a temperature of from 15 to 50° C.

7. The process of claim 1 and additionally eluting said iodine from said nonionic adsorption resin.

8. The process of claim 1 wherein the result of step (d) is that NaCl brine thereof has an iodine content therein no greater than 100 ppbw.

9. The process of claim 8 wherein the iodine content of said brine is no greater than 10 ppbw.

10. The process of claim 1 wherein said pH is no greater than 1.4.

11. The process of claim 1 wherein said pH is no greater than 1.3.

12. The process of claim 1 wherein said pH is no greater than 1.2.

13. The process of claim 1 wherein said pH is no greater than 1.1.

14. The process of claim 1 wherein said pH is no greater than 1.0.

Description

DETAILED DESCRIPTION

(1) With respect to step (a), the NaCl brine that is the starting material for the purification process of the present invention, has the following preferred or more preferred characteristics:

(2) The NaCl brine of step (a) contains 17 to 25 wt % of NaCl. The wt % of ingredients in the brine disclosed herein is based on the total weight of the brine.

(3) The iodide content of the brine is no greater than 10 ppmw. The brine will contain at least 1.0 ppmw, more preferably at least 0.5 ppmw. The ppmw of iodide is based on the weight of the brine.

(4) The brine can contain alkali and alkaline earth metals other than Na. Separate removal of these elements (metals) is unnecessary in the practice of the present invention.

(5) The pH of the starting NaCl brine is greater than 6 and is generally around 8, which is characteristic of iodide-containing NaCl brines available for purification and then further industrial use.

(6) The brine is preferably also essentially free of organic material. Preferably the brine contains no more than 20 ppmw of organic material, more preferably no more than 5 ppmw, based on the weight of the brine.

(7) With respect to step (b), the pH adjustment is carried out by adding acid to the NaCl brine to reach the pH desired of 1.5 or lower as described above, most preferably no greater than 1.0. HCl is the preferred acid because other common inorganic acids present problems in subsequent use of the purified brine such as in chlor-alkali production. For other use of the purified brine, sulfuric acid can be used in step (b).

(8) With respect to step (c), the temperature desired at which the oxidation will be carried out is established for the NaCl brine prior to addition of the oxidizing agent to the brine. This addition is accompanied by mixing. The amount of addition is monitored by a ORP (oxidation-reduction potential) meter to obtain the oxidation-reduction (redox) potential for forming the iodine-chlorine anionic complex under the condition of the pH of the NaCl brine already established. The combination of pH and redox potential is effective to oxidize the iodide to form the stable anionic iodine-chlorine complex. Thermodynamically, at the pH and ORP conditions established in steps (b) and (c), the identity of the iodine-chlorine complex is (ICl.sub.2).sup.−

(9) The preferred oxidizing agent used in step (c) is sodium hypochlorite.

(10) With respect to step (d), the contacting of the NaCl brine with nonionic adsorption resin one with the other is preferably carried out after addition of the desired amount of oxidizing agent and the ORP of the brine has stabilized at the desired potential, but before the anionic iodine-chlorine complex can start to decompose.

(11) The non-ionic adsorption resin can be used in either gel or in bead (granular) form to carry out the adsorption function. The beads can be small in the gel resin type or larger in the engineered resins designed for high flow rate applications. The preferred resin is styrene/divinylbenzene polymer and is available from multiple suppliers in different bead diameters and pore size. Another resin that can be used as the adsorbent is polyacrylic resin.

(12) The preferred embodiment for a flow through system such as would be employed at commercial scale is a granular form to facilitate the operation of the bed of adsorption resin. A range of commercially available adsorption resins is available. The preferred selection will be based on engineering requirements. Smaller beads and higher pore volumes are generally more expensive and will have a higher pressure drop in the fixed bed. For high iodine-feed concentration solutions, such as 10 ppmw iodine, smaller beads will be preferred to provide higher capacity for the same size bed. For lower iodine-feed concentration solutions, larger beads can be used, balancing the improved pressure drop with lower capacity from the lower pore volumes.

(13) Because the density of non-ionic (non-functionalized) adsorption resins is very low relative to strong base anion exchange resins and brine solutions, the non-functionalized resins can be employed in an upflow bed instead of the more common downflow beds used in brine purification.

(14) With the low density of the non-functionalized resin, the beads will float even in a static system with low concentrations of NaCl present such as 4% NaCl. This feature extends the range of usefulness beyond applications for purification of salt solutions produced from dissolving dry NaCl for direct use in industrial applications such as chlor-alkali production. When dry NaCl is dissolved for a feedstock, a consistent high concentration NaCl solution is typically produced, such as 24% NaCl, with a high uptime to fix the designs of production. Such design parameters are found in the more common brine softening applications. However, NaCl solutions can also be present as a side product from other industrial processes. Since these NaCl solutions are not the primary products, the NaCl solution is typically not close to saturation and can often be highly variable. Using an upflow, floating system allows additional flexibility in a process purifying a solution which operates at variable NaCl concentrations and might have low uptime which would require times for the bed to remain static with no brine flow. Designing a system using a strong base anion exchange resin with variable density or low uptime would be more complicated and difficult to operate.

(15) The nonionic nature of the resin arises from the resin (polymer) being free of functional groups, i.e. being non-functionalized. The resin is also preferably free of organic groups, which can be non-ionic, that are not part of the monomers forming the polymer that is the non-ionic adsorption resin used in step (d), but instead are added later such as by reaction with the polymer or adsorption into the pores of the adsorption resin.

(16) Thus, the non-ionic adsorption resin used in the present invention is preferably that which consists of the polymer backbone. The non-ionic adsorption resin is also hydrophobic.

(17) To entrap the iodine-chlorine anionic complex in the pores of the non-ionic adsorption resin, the beads of the resin can be mixed with the NaCl brine after formation of the anionic complex or the beads of the resin can be formed into a fixed bed through which the brine containing the anionic complex passes. The process of the present invention can be conducted batchwise or as a continuous process.

(18) When the adsorptive capacity of the non-ionic adsorption resin is reached, the non-ionic adsorption resin and the remaining NaCl brine are separated from one another, such as by passing the brine containing the resin though a screen thorough which the brine passes, but not the beads of the resin. In the flow system, the iodine-containing brine is passed through the resin bed at a fixed flow rate until the adsorptive capacity of the non-ionic adsorption resin is reached. The resultant NaCl brine then preferably contains no more than 100 ppbw of iodine, more preferably no more than 10 ppbw. The ppmw and ppbw of iodine and other ingredients disclosed herein in the NaCl brine are on a weight basis (ppbw). When the goal product quality can no longer be achieved, the resin is regenerated.

(19) The resin can then be regenerated by washing with a conventional elution liquid that removes the adsorbed iodine-chlorine complex from the pores of the resin. The resin is then useable again in the practice of the process of the present invention.

EXAMPLES

(20) The oxidation-reduction potentials disclosed with respect to the present invention are referenced to an Ag/AgCl electrode.

(21) In the Examples, the adsorptive capacity of non-ionic (non-functionalized) adsorption resin will be compared with that of anionic adsorption resin.

Example 1

Non-Functionalized Adsorbent Resin

(22) A large aliquot of fresh Dow XAD1600N resin, which is a non-functionalized adsorbent resin, was placed in a solution of 20% NaCl solution to equilibrate overnight. XAD 1600N is characterized in its product sheet as (a) a macromolecular cross-linked aromatic polymer with no added functional groups, (b) being useful in a fixed bed, (c) having a harmonic mean bead size of 400±50 μm, a uniformity coefficient of 1.25, a surface area of >700 m.sup.2/g, a porosity of 1.4 cc/g, and a bulk density of 660 g/L and specific gravity of 1.015-1.025. Overnight, the resin volume shrank slightly as it equilibrated with the NaCl solution. After equilibration, the resin was filtered from the NaCl solution and placed moist into Erlenmeyer flasks (4) to prepare for isotherm testing. The weight of the resin added to each flask is reported in the first column of Table 1.

(23) A solution of 20% NaCl was prepared from crystallized dry NaCl and lab grade deionized water and had a pH of 8. This NaCl solution was not purified to remove Ca or Mg which were present in the dry NaCl. The NaCl solution was adjusted to a pH of 1 by addition of aqueous 20% HCl solution. And then 21.9 ppmw iodide was added as potassium iodide. The ORP of the NaCl/iodide solution was adjusted with dilute NaOCl solution to a stable value of 900 mV. The resultant solution was then immediately portioned into 500 mL aliquots, and an aliquot was added to each of the four Erlenmeyer flasks containing the moist resin.

(24) The solutions were each mixed with the moist resins for 24 hours. After cessation of mixing, the resin floated to the top of the solution and was filtered, and the remaining iodine concentration in the solution was measured. From the results given in Table 1, an equilibrium capacity of 35 g I/L resin was calculated for a 1 ppm I solution.

(25) TABLE-US-00001 TABLE 1 Summary of Isotherm Experimental Results Using Non- Functionalized Resin as the Adsorbent (Dow XAD1600N) Starting Resin Measured I End Measured Calculated weight concentration I concentration capacity (g) (ppm) (ppm) (g I/L resin) 0.1224 21.9 6.26 48.15 0.2639 21.9 0.412 30.68 0.5056 21.9 0.185 16.18 1.0073 21.9 0.131 8.14

Comparison Example 1

Lanxess Lewatit S6368A, Strong Base Anion Exchange Resin

(26) The S6368A resin is characterized in its product sheet as a strong base anion exchange resin with a quaternary amine group. The resin used in this Comparison Example is shipped in the chloride form (type 1). It is further characterized as being engineered for use in flowing beds, with the resin being in bead form having a mean bead size of 0.62±0.05 mm, a uniformity index of 1.1, a bulk density of 640 g/L and a density of 1.06 g/mL.

(27) The procedure of Example 1 was then repeated for this Comparison Example, with the exception that 6.03 ppmw of iodide was added to the acidified NaCl solution. The proximity of the density of the resin beads and the density of the acidified NaCl solution resulted in some of the beads suspending in the solution. The amount of the beads added to each flask is reported in the first column of Table 2, which shows the results of this Comparison Example.

(28) From the results given in the table, an equilibrium capacity of 5.3 g I/L resin was calculated for a 1 ppm I solution.

(29) TABLE-US-00002 TABLE 2 Summary of Isotherm Experimental Results Using Anion Exchange Resin as the Adsorbent Starting Calculated Measured I End Measured capacity Resin concentration I concentration (g I/L weight (g) (ppm) (ppm) resin) 0.2786 6.03 1.09 6.45 0.5629 6.03 0.667 3.47 1.2551 6.03 0.449 1.62 2.6873 6.03 0.389 0.76

(30) Comparison of the results reported in Table 1 vs. those reported in Table 2 shows a significant improvement in the adsorptive capacity of the non-functionalized resin vs. the anion exchange resin. For example, the resin weight of 0.2639 g of non-functionalized resin in Table 1 is shown to reduce the I concentration in the NaCl solution from 21.9 ppm to 0.412 ppm, which corresponds to an adsorptive capacity of 30.68 g I/L for the resin. In contrast, the resin weight of 0.2786 g reported in Table 2 is shown to reduce the I concentration from 6.03 ppm to 1.09 ppm, corresponding to an adsorptive capacity of the anionic exchange resin of only 6.45 g I/L. The adsorptive capacity of the non-functionalized resin is almost 5×that of the anion exchange resin. Similar superiority is revealed by comparing the results for 1.0073 g of non-functionalized resin (Table 1) with 1.2551 g of anion exchange resin (Table 2), resulting in adsorptive capacities of 8.14 g I/L vs 1.62 g I/L, respectively.

(31) The calculated capacity in each table is determined by subtracting the end measured I concentration from the starting measured concentration, which is the amount of iodine removed in each experiment. These amounts are converted from g/500 mL to g/L. Next, the weight of resin in the first column of the Table, based on the density of the resin, is converted to volume of resin. The adsorptive capacity of the resin is the ratio of the g/L of I removed per the volume of the resin doing the removal.

(32) The comparison of adsorptive capacities can be made more precise by standard methodology for comparing resin adsorptive capacity, which involves plotting (xy plot) the calculated adsorptive capacity of the resin against the end measured ppm of I in the acidified NaCl solution. The four adsorptive capacity determinations reported in each of Tables 1 and 2 provide a curve, from which the adsorptive capacity for each resin can be read at the same I concentration for each curve, e.g. a concentration of 1 ppm I in solution. For example, in Table 1, the adsorptive capacity equation is given as y=9.639ln(x)−34.112, wherein x is the I amount in the solution and y is the adsorptive capacity of the resin, giving an adsorptive capacity of 35 g/L for the non-functionalized resin reported in Table 1.

Comparison Example 2

Importance of pH

(33) The procedure of Example 1 was repeated using the same non-functionalized resin, except that the pH was adjusted to 2 and 28.9 ppmw of iodine as potassium iodide was added. The results are reported in Table 3.

(34) TABLE-US-00003 TABLE 3 Summary of Isotherm Experimental Results Using Non- Functionalized Resin as the Adsorbent at pH (NaCl solution) of 2. Starting End Calculated Measured I Measured I capacity Resin concentration concentration (g I/L weight (g) (ppm) (ppm) resin) 0.1218 28.9 23.0 18.33 0.2504 28.9 22.3 9.97 0.5134 28.9 22.5 4.72 1.043 28.9 22.4 2.36

(35) As is apparent by comparing the end measured I concentration in the acidified NaCl solution with the starting measured I concentration, very little I was adsorbed by the resin at the solution pH of 2.

Example 2

Flow System

(36) A bed of the XAD1800N non-functionalized adsorbent resin of Example 1 was prepared in a small laboratory column following standard procedures. Due to its specific gravity of 1.015-1.025, the resin sinks when loaded into the column in water and then floats as NaCl solution is introduced into the bed. The column was prepared to run upflow.

(37) After preparation and settling of the bed was completed, a solution prepared from dry NaCl and deionized lab water was prepared at a concentration of 20% NaCl. No additional purification to remove Ca and Mg or other impurities was conducted. The solution was adjusted to a pH of 1 with 20% HCl solution. Then 800 ppb I was added as potassium iodide to the NaCl solution. The ORP was then adjusted to 880 mV by NaOCl addition. This solution was fed upflow at 5 bed volumes/hr producing outlet quality brine averaging 10 ppb I.