SPECIFICATION

Background and Description of the Invention

This Is a continuation-in-part of application Serial No. 895,817, filed April 12, 1978.

The present invention generally relates to a moving bed ion exchange apparatus and method, especially one in¬ corporating folded resin flows to significantly reduce the height of the apparatus and thus decrease the amount of head space required. More particularly, this invention achieves folded features in a high capacity countercurrent system having the ability to treat large flows of phosphoric acid liquids and efficiently regenerate and rinse the large move¬ ment of recirculating resin beads needed in order to accommo¬ date the large flows from the filters of commercial wet process phosphoric acid production plants. Countercurrent flow of the regeneration and rinsing solutions is practiced while maintaining a packed bed condition even though the system retains the advantages of a moving bed.

Moving bed ion exchange systems are known to have several advantages, especially improved efficiency, over fixed bed systems, Units such as in Higgins U. S. Patents No. 2,815,322, No. 3,492,092, No. 3,580,842 and No. 3,579,322, and Keller U. S. Patent No. 3,325,011 have a closed loop which incorporates a treating zone through which the liquid to be treated is passed in order to effect an ion exchange,

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as well as a regeneration zone wherein regenerating solution is passed through the resin. Between successive service cycles of these systems, the resin is advanced through the closed loop for providing regenerated resin within the treating zone. Keller, for example, shows a treating zone directly above a regeneration zone, and the resin supply is pumped by compressed air to advance from the regeneration zone to the treating zone to force used resin out of the treating zone and to the pumping location Units such as Levendusky U. S. Patent No. 3,130,151; Yomiyama U. S. Patent No. 3,152,072; Mihara U. S. Patent No. 3,238,125; and Yamashiki U. S. Patent No. 3,378,339, have multiple resin vessels and show resin movement there¬ between, but they do not provide the packed bed condition and efficient resin regeneration, rinsing and movement needed in an ion exchange system having a capacity high enough to accommodate flows from commercial wet process phosphoric acid plants.

While such systems have advantages over fixed-be systems because regenerated resin is continuously supplied even those having multiple resin beds typically have the disadvantages of a loose bed, including development of an out of phase condition, non-laminar movement, and undesir¬ able bed expansion.

The preβent invention retains the general advan¬ tages of moving-bed systems while avoiding the disadvantag of previously known moving-bed systems due to the ability

of the present system to incorporate desirable packed-bed attributes into a moving-bed system. In the present inven¬ tion, when moving the ion exchange resin through and between the various vessels or columns, a need to insure the reten¬ tion of the liquid-to-resin relationship in phase is signi- fleantly reduced; that is, it is not especially critical to be certain the liquid never goes faster than the resin so that the interfaces stay intact and at a constant relation¬ ship to each other. A particularly advantageous property is an especially efficient use of resin within the system, to the extent that high volumes of raw phosphoric acid that is highly loaded with ions can be successfully treated. By the present invention, the resin bed is in a packed con¬ dition at all treatment times.

In another aspect of this invention, the present system unlike prior art systems does not move the entire resin inventory during the resin transfer, which total move¬ ment results in extensive mixing of resin and fluid causing substantial fluid slippage in the direction of resin move¬ ment within a system in which it is critical to maintain good liquid interfaces, whereby the liquid moves faster than the bed so that the liquid and the ion exchange resin material are not in contact with each other for a period of time suf¬ ficient to achieve the desired result, whether that result be an ion exchange or the removal of extrained liquids. When such a unit exhibiting fluid slippage goes back on stream after having been shut down for a significant period of time,

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the chemical efficiency of the unit is lost until the be repacks itself and re-establishes equilibrium conditions, which could take as long as twenty percent of the time required to complete an entire closed loop cycle for short cycles of several minutes.

Another aspect of this invention brings with it an advantageous "stage height" feature which approximates the functional operation of a fractionating tower whereb for example, in the regeneration vessel or column, the purest resin is on contact with the purest regeneration fluid; and, as the resin becomes more contaminated in the lower portions of that column, the regenerating liquid li wise becomes correspondingly more contaminated, with the most contaminated regenerating fluid within the regenera¬ tion reservoir being in contact with the spent ion exchan resin just received from the treating or loading vessel. Such a stage height feature provides the maximum equili¬ brium or mass flow kinetic effect possible in such a system.

A still further aspect of this invention is the fact that the various passageways or distributors of the moving resin bed have a very simple construction and may enhance fluid distribution across the resin bed to elimin ate channelling. In prior art systems, large hydraulic forces are developed, requiring massive reinforced distr butors which caused obstructions to resin flow or requiri a multiplicity of various small distributors at the botto of the loading vessel, often to the point that the cross-

section was almost enitrely screened, which developed points of resin stagnation and resistance to resin flow, thereby inhibiting smooth flow distribution in the vicin¬ ity of the fluid discharge in the resin bed. These dis¬ advantages are avoided with the present invention.

Another problem with previously known moving-bed systems is the need to accomplish additional start up operations after the system has been idle for relatively long periods of time, such as for several weeks. When such previously known systems were left standing idle for long periods of time, the resin would first have to be transferred manually in order to loosen up the resin packed around and obstructing the operation of the valves, this manual opera¬ tion usually having to be followed by running the system through several cycles in order to place the system into proper startup condition before actually proceeding with the ion exchange operation on the liquid to be treated. Some systems incorporate a pulsing circuit to move resin while off stream. In accordance with the present invention, the system, even after having been idle for several weeks and without a pulsing circuit, can be immediately started up anywhere within the total program cycle without having to manually transfer any resin or run through start-up cycles.

By yet a further aspect of this invention, two or more complete units thereof are coupled together in an appropriate manner whereby there can be accomplished the removal from phosphoric acid liquids of undersirable sub-

stances or diluents as well as the recovery of desirable substances such as uranium or other valuable minerals.

It is, therefore, a general object of the presen invention to provide an improved apparatus and method for conducting ion exchange operations through a moving resin bed.

Another object of the present invention is an improved method and apparatus which accomplishes a high capacity flow of resin throughout the system while maintai ing countercurrent flow to the extent that there is a sig¬ nificant reduction in the criticality that the resin inter faces throughout the system be maintained intact.

Another object of the present invention is to provide an improved moving-bed ion exchange resin system which proceeds through sequential steps during which the liquid being treated moves in a downflow manner, with the upper or initial portion of the loading vessel resin bed being removed therefrom for subsequent regeneration, rins¬ ing, and reuse.

Another object of this invention is to provide a system suitable for either or both removing contaminants a recovering valuable material such as precious metals from phosphoric acid liquid or the like, when high quantities o trace amounts of those contaminants or valuable materials are present in the liquid.

Another object of the present invention is to provide a method and apparatus for treating high capacity flows from the filters of a wet process phosphoric acid

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production plant which includes stripping individual resin beads of fluids adhering to their surfaces in order to en¬ hance their sorption efficiency and in order to facilitate their subsequent movement between vessels.

Another object of the present invention is to pro¬ vide an improved ion exchange resin system which is of the moving-bed type affording sequentially continuous operation but which is and has the advantages of a packed bed system.

Another object of this invention is an improved apparatus and method having a "stage height" or gradient feature similar in end results to that of a fractionating tower whereby the purest resin is in contact with the purest regenerating fluid and progressively more contaminated resin is correspondingly in contact with progressively more con¬ taminated regenerating fluid.

These and other objects of the present invention will be apparent from the following detailed description of this invention, including the various aspects thereof, taken in conjunction with the accompanying drawings wherein:

The Figure is a schematic elevational view of the preferred downflow, folded moving-bed ion exchange system in accordance with this invention.

In the basic operation of the moving-bed system illustrated in the Figure, the raw phosphoric acid feed liquid to be treated passes down through ion exchange resin within a loading vessel 11. Regenerated and rinsed resin enters loading vessel 11 at an inlet 12 as resin transfer

proceeds by movement of the resin interfaces between a loading reservoir 13, a regeneration vessel 14, and a re¬ generation reservoir 15. Regenerant solution enters the system through a pumping means 16, and proceeds through regeneration vessel 14, and out a waste conduit 17. Usual prior to regeneration, air passes through loading reservoi 13 to purge liquid therefrom in order to dry and initially remove regeneration solution from the resin therein to pre pare a semi-dry resin, after which rinse liquor enters the system through a pumping means 18, moves through and then with the semi-dry resin within the loading reservoir 13 and the bottom neck thereof, thereby building up pressure therewithin, which pressure is intermittently released and built up in order to cause residual air entrapped in the semi-dried resin to be removed from this resin and vented out of the loading reservoir 13 to enhance subsequent move ment and ion exchange efficiency of this resin. During re generation, an ion exchange takes place whereby those ions which were sorbed on the resin within the loading vessel 1 are removed from the resin within the regeneration vessel The rinse liquor completes washing away of the regeneratio solution from the interstices between the resin beads in the loading reservoir 13, which washing has been facilitat by reducing surface tension on the surfaces of the beads b forming the semi-dry resin and then removing the residual entrapped air.

With more particular reference to the Figure, th feed liquid to be treated is fed into the system through a

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feed conduit 21 and enters loading vessel 11 through a distributor 22 through a generally closed vessel 11, after which it passes, preferably in a downflow manner, through packed ion exchange resin bed 23 at a loading height B__.. After passing through the packed resin bed 23, the thus purified and ^* treated liquid exits the resin bed 23 through a collecting means 24. Means 24 illustrated in the Figure takes the form of a cylinder of a diffusing material such as screening or a slotted panel which permits the treated liquid to flow therethrough but blocks passage of individual resin beads from bed 23, a particularly suitable diffusing material being a 60 mesh polyester screening. Feed liquid entering the collecting means 24 is phosphoric acid treated in ac¬ cordance with this invention; it passes out of the loading vessel 11 through a product efflux conduit 25.

Treatment of the feed liquid within the packed ion exchange resin bed 23 reduces the ion exchange capability thereof and, in general, substantially exhausts the top interface and upper portion of the resin bed 23, which inter¬ face and upper portion are removed from loading vessel 11 and are later regenerated. In order to maintain the load¬ ing height BLY during ion exchange treatment of the feed liquor, a regenerated and rinsed supply of ion exchange resin enters the loading vessel 11 through the inlet 12 often without disturbing the resin interfaces. Prior to such pas¬ sage through the inlet 12, the resin had been subjected to regeneration of the ion exchange resin and rinsing the re¬ generating solution from the interstices of the moving

packed resin bed.

More particularly, a regenerating solution, of predetermined strength, enters the system through the pumping means lβ, which may be a centrifugal pump, a gear pump, a piston and cylinder arrangement, an air or hydrau cylinder devices, or the like, preferably being capable o metering the flow of regenerating solution into the syste The regenerating solution then enters the regeneration ve sel 14 through a distribution head 26, which may take the form of a cone, a tube, or a pancake cylinder having a re tively fine mesh passageway therethrough for the passage liquid such as the regenerating solution, while preventin individual resin beads from entering the head 26.

During this stage, resin bed 27 of the regenera vessel 14 will be packed to a height A^y, and regeneratin solution flows downwardly through the regeneration vessel because valve 3 of waste conduit 17 is opened, while all other possible exit paths from regeneration vessel 14 are closed by suitable valves. The amount of regenerating so tion utilized for each regeneration cycle can be governed any suitable means, such as the activation of a sensor or metering a predetermined volume of regenerating solution passing through a preselected location, such as a valve 3 In any event, an adequate amount of regenerating solution is passed through regeneration vessel 14, after which the regenerating solution, now a waste liquor, is discharged out of the bottom of vessel 14 by means of a foraminous member or strainer 36 while the valve 28 in the conduit

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between vessel 14 and regeneration reservoir 15 is closed.

Purging means and rinsing means are provided to treat resin bed 37 within the loading reservoir 13, general¬ ly at a height A-r^. Purging means includes a supply of low pressure air or other fluid such as nitrogen or a special liquor passing through opened valve 64, into and through resin column 37, and out conduit 71 by way of open valve 72, to thereby pass an initial volume of regenerating solu¬ tion from out of the resin interstices (about 40$ of the bed's volume) and to regenerating solution reservoir 73, which gives the resin bed 37 a semi-dry character.

Pumping or injection means 18, or alternatively a special rinse liquor injection means 75, then is activated to introduce a fixed amount of rinse liquor, which may be treated liquid, deionized water, and/or as in the illustrate embodiment, the phosphoric acid product refined within the apparatus. Rinse liquor from product storage tank 7 moves into transfer pipe 3 while valve 49 is closed,, the rinse liquor passing through pipe 39, the neck opening 40 of load¬ ing reservoir 13 and into the loading reservoir 13 itself. The semi-dry resin within the neck and the reservoir at firs resists movement by the rinse liquor until the rinse liquor passes through the interstices of the semi-dry resin, while all other passageways out of reservoir 13 remain closed un¬ til a pressure build-up occurs, after which vent valve 65 is opened to release the pressure build-up and remove air from the interstitial volume and force out residual regener¬ ating solution adhering by surface tension to the beads.

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Preferably, vent valve 65 is then closed, usually before the rinse liquor has passed completely through resin bed 37, to again build up pressure within reservoir 13, eventually fol¬ lowed by opening vent valve 65 again to remove further resid¬ ual air and regenerating solution. Repetitionprovides a series of hydraulic forces which pass successive blocks of resin out of transfer pipe 39, through neck 40, and into reservoir 13 while simultaneously exhausting residual air and strip¬ ping residual regenerating solution from the resin beads in bed 37 to fluff the resin for maximizing its regeneration and subsequent ion transfer efficiency by restoring individual resin beads to approximately their properties prior to use. This rinsing means pushes the resin bed 37 upwardly until it reaches level ALR, all while fluffing out residual air, water and regeneration solution to enhance the fully packed condition of the resin bed 37 and consequently of treating resin bed 23.

Thi generating so bed 37, and t remains in lo which is usua generally rem through and d generating so volume that c reservoir 13 systems, the

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In more complex systems, it may be desirable to add amounts that vary depending upon the amount of rinsing needed as determined by a sensor 66 which may be a conductivity probe.

Purging means and rinsing means are preferably provided to treat resin bed 29 within regeneration reservoir 15 in much the same manner that purging means and rinsing means are provided to treat resin bed 37. This purging means includes an open vent valve 55 and open drain valve 68 to permit liquid 32, which is primarily raw feed liquor, to drain from regeneration reservoir 15. Also included is a source of pressurized fluid, preferably air, or a useful liquid such as water, which passes through valve 35, into _nd through resin column 29, and out through valve 68, to thereby pass an initial volume of raw feed liquor from out of the resin intersticies and to the raw feed tank 76, which gives the resin bed 29 a semi-dry character.

Pumping means 69 provides a rinse liquor, usually water, to wash the residual raw feed from the resin and the walls of reservoir 15. Rinse liquor from storage tank 70 passes through pumping means 69 and into regeneration reser¬ voir 15 while all other valves to reservoir 15 are closed, the rinse liquor flowing under pressure into resin bed 29, generally lifting the bed 29 while vent valve 55 is opened to rapidly release pressure that had built up within reser¬ voir 15 and thus expunge much of the air that had been en¬ trapped in the resin intersticies. This sequential operation of the pumping means and the vent valve 55 can be repeated as necessary to fluff the resin and remove substantially

all of the entrapped air and residual liquid clinging to the resin beads by surface tension. Usually, the amount of rinse liquor is limited to the extent that reservoir 15 is not filled. Should excessive rinse liquo be pumped, this can exit through the screened conduit via the vent valve 55.

After these regeneration and rinsing procedures, a block of fresh resin from the loading reservoir 13 is ready for passage into the neck opening 40, through the transfer pipe 39, and out the inlet 12, the resin levels the beginning of this particular stage being the levels A ^A LR, ^A RV' ^{and A} RR ^{J wnicJl are} illustrated by cross-hatchin in the Figure. During this resin transfer state, the liq to be treated preferably does not pass into the system through the distributor 22. Instead, a bypass valve 46 i opened, an exit valve 47 is closed, and the feed liquid simply returns to its feed well 76 through bypass conduit

Resin transfer can proceed when a resin valve 4 which is of the type that permits passage of packed resin but resists damage thereby, such as a ball valve or a spe cially designed butterfly valve, is opened and pneumatic means initiate passage or resin therethrough. A source o pressurized fluid, liquid or air under low positive pres¬ sure, can be introduced by means of a valve 51 into the u per portion of the regeneration vessel 14, which exerts pressure upon the diluted regeneration solution liquid remaining on top of the packed resin bed 27. A resin val 53 can be opened to provide passageway between the regen-

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eration vessel 14 and the loading reservoir 13, with the result that the pressurized fluid or air which is exerting a pneumatic force on the liquid 52, which transmits that force to the resin within the upper portion of the regenera¬ tion vessel 14, causes this resin to pass through the open resin valve 53 and into the loading reservoir 13, ^' which in turn exerts pressure upon the packed bed 37, and the entire packed bed 37 will move downwardly to about level B---,, the movement being one of laminar flow and one that is in phase with the interstitial liquid contained in the resin bed 37, to the extent that a block of purged and rinsed resin moves through the transfer pipe 39 by way of the open resin valve 49 and into the bottom of the loading reservoir 13 through the inlet 12, thereby upwardly pushing the packed ion ex¬ change resin bed laminarly upwardly and in phase with the interstitial liquid within bed 23 until level B _L y is reached. The amount of resin that can be thus transferred into the loading vessel 11 is a fixed amount that is controlled by means of a vent 63 and/or the screened distributor 22 which functions as a resin dam or by suitable sensors at strategic locations within the loading vessel 11 and/or the loading reservoir 13. *or safety reasons, it may be desirable to add a screened trap 67.

Preferably, especially since a large volume of resin is transferred by this apparatus, and should it be decided that an additional liquor is needed to especially condition the resin with a particular media such as an acidic or a basic one to provide optimum conditions for

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resin exchange in resin bed 23, valve 53 is closed, and valve 64 is opened to permit low pressure air or special liquor to enter above liquid layer 4l and build up in pr sure, after which valves 46 and 49 are opened so the buil pressure will force the block movement of the purged and rinsed resin into bed 23. When the resin reaches level B _j y pressure build-up will reoccur to signal closing of 64 and thus fluid flow into reservoir 13, after whic another valve 65 is opened to vent or to remove special liquor, the resin level being at about BJJ-,.

At this stage, if resin had been transferred f the top of bed 27 and into bed 37 for filling bed 23, the top surface of the packed resin bed 27 will be at a leve B _R y, which generally takes a somewhat conical shape such that illustrated in the Figure, with the liquid 52 stand above the level B^y, and pressurized air at about 2-20 ps preferably 3-10 psi, remaining above liquid 52 until it released by opening a vent valve 51 after resin transfer to the loading vessel 11, at which time resin valve 49 a resin valve 53 are then closed, thereby locking the respe tive resin beds at approximately level B _j rr, A _j ^ and B^y.

If the preferred means for transferring resin bed 23 is utilized, it is necessary to subsequently activ the transfer means needed to move resin into loading rese voir 13 to return its resin height from about B^-, to abo A---,. Transfer valve 53 and vent valve 65 open, as does valve 4 by which low pressure air or other pressurized fluid such as regenerating solution from tank 73 exerts

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pressure upon liquid 52, such pressure being transferred to resin at level A _R y to push that resin until level B _j ,-- is reached, usually after all resin between levels A _R y and B-,-- have moved, along with liquid 52, into loading reservoir 13.

Next, the regeneration vessel 14 will be refilled with packed resin from the regeneration reservoir 15 so that the level of the packed resin bed at 27 will return approxi¬ mately to level A _R --. Vent valve 51 remains open, and com¬ pressed air, at about 2 to 20 psi, preferably 3-10 psi, enters by valve 3 to pressurize liquid 32 which in turn exerts a pneumatic force downwardly on the packed resin bed 29 to move it down to level C-^ as the lower portion of packed resin bed 29 moves laminarly downwardly and through the pipe and valve 28, to move the packed resin bed 27 la¬ minarly upwardly until it approximates level A _R y. Valve 35 closes and the compressed air supply ceases at a predeter¬ mined time such as when the liquid 52 is contacted by a sensor 56 within the regeneration vessel 14, after which the vent valve 1 also closes, and vent valve 55 opens to release the compressed air from the regeneration reservoir 15, thereby equalizing the pressure on the resin bed surfaces within the regeneration vessel 14 and within the regeneration reservoir 15.

In order to refill the regeneration reservoir 15 with resin and remove spent or exhausted resin from the upper portion of the loading vessel 11, a resin slurry transfer conduit 57 is provided. It is preferred in large capacity units that the resin slurry transfer conduit 57 pass resin

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while the feed liquid being treated is circulating into t packed ion exchange resin bed 23 within the loading vesse 11 while valve 47 is closed. During such flow passage, there is a pressure drop of several pounds down through t resin bed 23, which pressure drop will enhance slurry for mation and will pass the resin from out of section 58 of vessel 11 and through the resin slurry transfer conduit when a further resin valve 59 is opened. Spent resin lea through an orifice 6l within the section 58, the resin be pushed or pulsed therethrough by feed or other liquid fro the distributor 22. Actually, the material passing throu resin transfer conduit 57 is a slurry of spent resin and liquid. This resinous slurry enters the regeneration res voir 15 at aperture 62, which slurry displaces much of th air remaining in the regeneration reservoir 15 on top of liquid above resin level C _j ^, the air being displaced thr the opened vent valve 55, while the resinous slurry enter through aperture 62 continuously raises the level C _j ^, ge erally until it reaches a height approximating the level with the liquid from this slurry passing into the regener tion reservoir 15 until a preset occurrence, such as when sensor 33 is activated to generate a signal to close the sin valve 59 and the vent valve 55. Alternatively, exces liquid also could exit through vent valve 55 and be saved for further processing. Typically, the transferred resin will be allowed to settle within regeneration reservoir 1 At this stage, all of the resin levels will hav been returned to their respective levels A_-_, A _LR , A _R y

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and A _RR so that the system will be ready for the next resin transfer sequence.

When it is desired to produce a final liquid product that has both cation and anion removal means, one or more additional treatment systems 80 may be provided, whereby the structure shown in the Figure is 'substnatially repeated, and the transfer conduit means 25 or the storage tank 74 is connected by a suitable conduit such as 81 for communication with a conduit on the order of feed conduit 21. In such a plural system, the resin movement in each system is substantially the same as that in the single system, with the units being synchronized so that each of the cation and the anion loading vessels are off stream at that point where the freshly regenerated resins are transferred into each vessel. For example, a vessel containing an anion resin for recovering uranium when it exists in anionic form can be downstream of cation vessel conduit 25 which removes dilu¬ ents, especially calcium and magnesium, from wet process phosphoric acid. Other entire systems could likewise be lined up in series for tasks such as using cation resin to recover cationic forms of uranium.

In proceeding with the method in accordance with this invention, substances are removed from a feed liquid of wet process phosphoric acid from the filters of extract¬ ing equipment, the substances being generally in the ionic form, but they may also be complexed ions in a weakly ionic form, to thereby either clarify the feed liquid and/or re¬ cover valuable materials therefrom, whereby large volumes

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or trace amounts can be removed in either case-. The met proceeds in a folded manner to avoid the requirement of ing extensive head space to accomplish the method. Pack resin beads are recycled in the manner of a moving bed, various liquids pass therethrough. The method substanti eliminates concern for maintaining constant relationships between the numerous interfaces of liquids and the resin, while still enhancing and maximizing the ion exchange pr so that it approaches stoichiometric ratios. Additional as a consequence of some laminar and packed bed movements no resin bed expansion is experienced which would bring it a consequent loss of the packed bed effect and its att dant superior ion exchange properties. Furthermore, the od includes rapidly washing large volumes of resin beads enhanced efficiency in order to remove residual fluids f around the beads which would reduce the ion exchange cap bilities of the beads.

In general, since the feed liquid being treated a relatively high concentration of ions or complexed ions be removed therefrom, a moving resin bed of a large volu relative to that of the feed liquid will be circulated re tively frequently. Due to the high concentration of ions wet process phosphoric acid, having about 5 weight percen of total diluents, each volume of resin must treat a rela tively low volume of phosphoric acid when compared with c ventional ion exchange methods. This invention is capabl of satisfactorily clarifying as low as 1/2 volume of phosphoric acid for each volume of resin, although ratios

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this low begin to require equipment sizing that becomes cumbersome and uneconomic. Typically, a ratio range of between 1 and 30 volumes of raw acid per volume of resin will be most satisfactorily practiced, with a most advan¬ tageous range being between 2 to 5 volumes of raw acid for each resin volume.

The ion exchange operation within the loading vessel 11 sorbs the ions to be removed and/or collected into the packed ion exchange resin bed, such ions releasing and replacing other ions which had been in the sites located in the resin beads in order to effect a beneficial exchange of ions. This exchange phenomenon requires that the resin beads have a greater affinity for the ions to be removed from the feed liquid than for the ions in the fresh resin, which calls for an appropriate selection of resin beads, which appro¬ priate selection can often be in accordance with principles known in the art and published specifications on particu¬ lar resin beads. Preferably, the raw feed is treated while hot from phosphoric acid production filters, usually at a o temperature of about 100 to 160 F. Temperature maintenance can be facilitated by jacket 77.

While a raw acid or other pulsing liquid flow takes place, an upper portion of the resin beads having undergone this ion exchange are passed in slurry form with pulsing liquid from out of the top of the packed resin bed or column and into a regeneration reservoir column for a purging and washing step prior to a regeneration step, those contaminat¬ ing or valuable ions which were sorbed into the resin beads

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within the loading column being exchanged by means of a regenerating liquor with fresh ions for subsequent exchang with other contaminating or valuable ions in the moving re in bed or column. Utilizing both a regeneration reservoir column and a regeneration column contributes to the abilit to carry on this method as a folded one, within a relative low location. It also facilitates purging and washing the spent resin just prior to regeneration.

Spent resin beads enterin the regeneration rese voir column are most advantageously purged and rinsed of r phosphoric acid and its contaminants prior to attempting t regenerate the beads within the regeneration column. Purg ing fluid is first passed through the column to remove the bulk of the phosphoric acid within the intersticies of the beads. When air or other gas is used, the beads and raw a are subjected to a low gas pressure of about 10 to 15 poun per square inch gauge which also compacts the beads and ca them to stick together due to surface tension forces creat by residual liquid. To alleviate this situation, purging is followed shortly by pressure-release rinsing or fluffin preferably upwardly, to remove air and residual liquid in order to enhance the movability of the resin as well as to clean off the surface of the beads from substances, such as the raw phosphoric acid, that would interfere with the sub sequent regeneration and sorption. Multiple purging, for example an air purge followed by a water purge, can be es¬ pecially advantageous, particularly for high volume flows.

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Pressure release rinsing subjects a closed off resin column to pressurized fluid and then that resin column is opened up to rapidly release the pressure, thereby exert¬ ing short duration, high momentum forces on the resin to "fluff" it free from entrapped air and overcome surface tension forces to remove residual phosphoric acid from the beads, which can be observed as bubbles or a froth within the rinse liquor. This pressure release rinsing simulates or approximates the ideal rinsing conditions of a free flow or fall of the resin beads through a long column of liquid to the extent that above 80 of the beads ' surface area is free for sorption, but does so much more rapidly and in a much more compact form than required of a free flow.

The regeneration step includes pumping a regener¬ ating solution, such as nitric acid or sulfuric acid, through at least a large portion of the regeneration column which in¬ cludes closely packed resin beads being recycled. The regen¬ erating liquor continues until it passes through a screen or membrane which prevents resin passage, at which time the used regenerating solution, having been turned into a waste liquid, is allowed to pass out of the system.

A purging and a rinsing or washing step is also accomplished on the regenerated resin in a manner generally similar to purging and rinsing of the regeneration reservoir column. Time savings can be realized by conducting the purging and rinsing of both columns generally simultaneously. Loading reservoir column purging with air or other fluid is accomplished in much the same manner as purging of the

regeneration reservoir column to semi-dry the beads. Duri rinsing, the regenerated, semi-dry resin bed at below A _τtJ ^■ within a loading reservoir column is washed with a rinse liquor by one or more passage of the rinse liquor, eventua ly together with a plug of semi-dry resin, into the loadin reservoir column near its bottom end, thereby raising the level of resin within the loading reservoir column while a the same time passing the rinse liquor eventually through entire column for movement through and with the interstiti liquid remaining within this semi-dried column in order to strip remaining liquid from beads and dilute with rinse li this highly diluted liquid remaining between and often abo the resin beads. ^τ he rinse liquor used in this step may b a portion of the feed liquid that has been treated by pass through the loading resin bed or column, or it may be de¬ ionized water or the like.

After the liquid to be treated flows through the packed ion exchange resin loading bed or column, the loadi column moves generally upwardly in a laminar manner and the top portion thereof is removed therefrom in order to replac the most extensively spent resin beads with freshly regene ated resin beads within the packed loading column.

The resin transfer operation basically includes four resin movement steps. Prior to these resin movement steps, when beginning after feed liquid treatment, the respective resin columns will be at levels B-- _v , A _LR , A _RV a C _RR depicted in the Figure.

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Beginning the present discussion with resin move¬ ment after feed liquid has been processed through the load¬ ing column, the first step will be movement of the spent resin of the packed ion exchange resin loading bed or column to near the top of the regeneration reservoir column for subsequent regeneration and rinsing thereof. This step may be accomplished simultaneously in association with the passage of the feed liquid into the loading column which brings about a pressure drop of several pounds from its inlet location to its outlet location, the amount of the pressure drop being dependent upon the average size of the inlet compared with the average size of the outlet, the height of the resin bed, and the temperature and viscosity of the incoming liquid, the raw acid being very viscous.

A usual minimum pressure drop for small capacity unit is 2 psi. Preferably, the flow should be as gentle as possible to minimize resin attrition brought about by resin bead breakage at fast flow rates while being fast enough to keep the down time at a minute or less. Generally, for example, at flux of about 25 to 3° gallons/minute/square foot and at room temperature, the effective pressure drop will be about 5 psi for each foot of depth of the effective height of the loading column resin bed, up to or above 10 feet, for example. Such pressure drop will cause a transfer of a fixed volume of resin slurried with feed liquid from the load¬ ing column to about level A _L y after passageway therefrom is provided to the regeneration reservoir column, generally until it reaches its original level A _j y,, at which level

liquid in the slurry is separated from the resin beads and the regeneration resin column is later compacted by the fluid purging step.

In the next such step, regenerated and rinsed re is transferred into the bottom of the packed ion exchange resin loading bed or column by pneumatic action of a suit¬ able pressurized fluid, such as air compressed to a pres¬ sure of about 2 to 20 pounds per square inch upon the di¬ luted regenerating liquid mixture above the loading reser¬ voir column, which pneumatic action passes resin to level BLR to move that column downwardly in laminar fashion and into the packed ion exchange resin loading column to urge this loading column upwardly in a laminar fashion until it reaches level BLy. This step generally transfers the resi in a fixed amount, and the extent of the movement is regu¬ lated by a time and air pressure relationship, for example, for passing the correct amount of pressurized fluid into the top of the loading reservoir column. Thereafter, the compressed air is released to complete this step of the resin transfer operation. Since fresh resin has now fille the loading vessel, processing of the raw phosphoric acid liquor therethrough can resume.

Meanwhile, the depleted loading reservoir column can be returned to about level A by passage of resin

LR thereinto from the regeneration column at a level of about Ap>y until it reaches approximately level Bp>y, the movement being accomplished by pressurized fluid such as air or re¬ generation fluid upon the regeneration column. If air is

used, a liquid layer should be present between the air sup¬ ply and the resin to be moved in order to provide necessary conditions for an incipient resin slurry to be maintained, thereby facilitating resin transfer. Once transferred, the resin will settle within the liquor now present in the load¬ ing reservoir column. This column will then be subjected to the purging and rinsing operations in order to make it ready for eventual transfer into the loading column.

At the completion of the previous step, the resin in regeneration column is depleted, and the next step re¬ plenishes the column to about its original level A _RV by passing resin from the bottom of the regeneration reservoir column into the bottom of the regeneration column. This passage is accomplished by injecting compressed air into the top portion of the regeneration reservoir column, which creates a pneumatic force on residual liquid above the resin in this column to thereby move the resin therein down to about level C-^-, while that in the regeneration column is raised to about level A-,-..

It has been found that resin requirements are optimized by including about half of the total system resin volume within the loading column and its reservoir and the other half in the regeneration vessel and reservoir, accept¬ able volume ratios being about 10:1:10:1 for the columns as viewed from left to right in the Figure.

Throughout some resin transfer step, the resin transfer proceeds without disturbing the interfaces or stage heights of the loading or regeneration beds or columns, with

the exception that the volume of resin actually transferred from column to column will be mixed to some degree as it passes through the appropriate passageways. The preferred downflow passage through the loading column or vessel has a important advantage over an upflow passage therethrough by automatically maintaining a packed bed condition therewithi even as attrition of the resin beads takes place. Any at¬ trition will merely lower the levels A^y and B^y, rather than cause gaps to develop in the loading vessel and conse¬ quent undesirable channelling as will occur in an upflow un unless it is attended for the purpose of adding resin into the system to make up for attritions.

By the preferred moving bed system, the regenerat resin entering the loading column has been regenerated to 80 or more as an average of its initial, unused condition to bring about ion transfer on the order of a fresh, fixed bed. This is especially important when deep downflow loading columns are involved since acidic conditions increa down the depth of the column, which acidic conditions tend to bring about undesirable reverse ion exchange, this tendency being decreased significantly under equilibrium conditions having only about 20$ at most of inactive resin rather than about °$ inactive resin for prior systems.

The following specific examples will more precise ly illustrate the invention and teach the procedures pre¬ sently preferred for practicing the same, as well as the improvements and advantages realized thereby.

_0Λ.PI

_ ^'

EXAMPLE I Hot raw phosphoric acid from the filters of a commercial phosphoric acid plant was treated within an appa¬ ratus on the order of that shown in the Figure and having a 6-foot high loading vessel with a diameter of 4 inches, a regeneration vessel having an effective height of about 10 feet and a diameter of 3 inches, a loading reservoir having a 4-inch diameter and an effective depth of about 3 feet, and a regeneration reservoir having a 3-inch diameter and an effective depth of about 3 feet, the volume of resin with - in the loading vessel and its loading reservoir being about the same as the total resin volume of the regeneration veε- s el and its reservoir. The approximately ^' 30$ crude or raw phosphoric acid was fed at a rate of about 5 flux (gallons/ minute/square foot) at its off-filter temperature of about 140°F. and containing total diluents of about 5 weight per cent was analyzed from a standing tank to include: 26.15 weight per cent P ₂ °5, and the following cationic diluents: 0.8l weight per cent Fe ₂ 0 , O.87 weight per cent AI2O3, O.74 weight per cent CaO, and 0.49 weight per cent MgO. HCRW (Dow Chemical ^C ompany) strong cationic resin, which is of the gel, or microreticular, type was used throughout the system, it was regenerated with 20$ nitric acid, and was washed with the product phosphoric acid. Several runs through the apparatus were analyzed, the make¬ up of product phosphoric acid leaving conduit 26 being re¬ ported in the Table:

TABLE ^p 2°5 Fe ₂ 0 ₃ A1 ₂ 0 ₃ CaO Mg

Run No. (wt. S.) (wt. j.) (wt. % (wt. $) ( t

1 24.90 0.95 0.44 0.05 0.0

2 27.80 1.13 0.57 0.05 0.0

3 24.85 0.94 0.40 O.05 0.0

4 28 ^, 35 1.10 O.56 0.05 0.0

5 25.85 0.98 0.47 0.05 0.0

6 26.65 1.00 0.48 0.05 0.0

7 24.85 0.67 0.61 0.03 0.0

8 25.80 0.55 O.63 0.03 0.0

9 24.85 0.47 0.62 0.09 0.0

Calcium and magnesium removal was excellent, as can be seen from the Table and from analyses of the stripp regeneration solution waste stream passing out of the re¬ generation vessel through conduit 17, found to include an average of 1.06 weight per cent CaO and an average of O.79 weight per cent MgO. It was found that the particular ex¬ change resin utilized was not especially effective for iro and aluminum sorption and removal, although the stripped regeneration solution waste stream was found to contain an average of about O.33 weight per cent Fe^^ and of about 0.42 weight per cent Al _j sO^.

EXAMPLE II

Raw phosphoric acid having a P 0,- content of abo 30 weight per cent was passed hot from the filters of a commercial wet-process phosphoric acid production plant in a holding tank and maintained at a temperature of about l4 after which several runs were made through an anionic exch resin in a moving bed of a type generally on the order of shown in the Figure, with a view toward recovering uranium from the raw, untreated acid. The resin used was IRA-900 (Rohm & Haas) a macroreticular strong anionic type, the

regeneration solution was 20$ nitric acid, and the rinsing liquor was 3N sulfuric acid. Analyses for uranium in the raw acid and in the product phosphoric acid after treat¬ ment were as follows:

Raw Acid Treated Acid

150 ppm 8 ppm

120 ppm 7 ppm

150 ppm 8 ppm

125 ppm 8 ppm

Also, colored organic materials were removed from the raw dark brown acid to the extent that the product phosphoric acid had but a strong brownish tint and the ani¬ onic resin had very little brown organic matter left thereon after regeneration and rinsing.

EXAMPLE III Example II was generally repeated except the re¬ generation solution used was a blend of 20$ nitric acid and IN ammonium nitrate. Analyses for uranium were as follows:

Raw Acid Treated Acid

150 ppm 7 ppm

135 ppm 8 ppm

125 ppm 8 ppm

EXAMPLE IV Tap water was treated with an apparatus on the order of that shown in the Figure and having a loading vessel di¬ ameter of 6 inches, a regeneration vessel having a diameter of 3 inches, a loading reservoir having a 3-ineh diameter and a half-sized effective depth, and a regeneration reser¬ voir having a 3-inch diameter and a half-sized effective depth

so that the volume of resin within the loading vessel is about the same as the total resin volume of the other thre vessels combined. The cold tap water was fed at a rate of 7.7 flux (gallons/minute/square foot) at its tap temperatu of about 40 F. and was analyzed to include 116 ppm Calcium, 40 ppm Magnesium and 70 ppm Sodium. After treatment the analysis indicated zero Calcium, zero Magnesium, and trace Sodium. Used as the hydrogen cycle ion exchange resin was a strong cation resin HCRW (Dow Chemical Company). The re generating solution was 10$ hydrochloric acid which flowed for about 45 seconds at a rate of 2.61 grams/minute on a 100$ HC1 basis, which was 5$ above the stochiometric ratio in order to provide a safety cushion. Decationized water was the rinse liquor having a flow time of 45 seconds. Th apparatus was set for a cycle of 3 minutes, having a 3° second down time for resin movement, the feed time through the loading vessel being 2 1/2 minutes.

A particularly high regeneration level was attai the regenerated resin having a capacity of 1.8 out of 2 equivalents per liter of resin, or at 90$ capacity even th the regenerating solution utilized was at approximate stoc metric ratio to the resin. By comparison, other moving-be systems, such as those according to Higgins U.S. Patent No 2,815,322, operate in the field at a capacity of about 0.8 1.0 out of 2 equivalents per liter of strong cation resin, at about 40$ to 50$ capacity.

-33-

EXAMPLE V To the tap water treated in Example IV was added 3200 ppm Nickel as Ni; 48 ppm Calcium as Ca; and 148 ppm Sodium as Na. It was passed through the apparatus of Example IV set for the same 3-minute cycle having a down time of 30 seconds, the analyses being 1.0 ppm Ni; zero Ca; and 3 ppm Na. A total of 40 cc of the regnerating solution of 10$ hydrochloric acid was needed to regenerate the HCRW resin, which was 4$ over the stochiometric ratio. The capacity was 1.8 out of 2 equivalents per liter.

EXAMPLE VI A double structured deionized unit repeating the structure of Example IV was used in a field test for lead removal from a printed circuit rinse liquor at a temperature of about 33 F. The loading vessels had diameters of 8 inches, the cycle time was 15 minutes, including a 30 second down time and a flow through time of 14 1/2 minutes, and the rate was 25 flux (gallons per minute per square foot) . Before treat¬ ment, the anlyses were 0 ppm Copper as Cu; 15 ppm Lead as Pb; and 70 ppm Calcium as Ca. After treatment they were each an¬ alyzed at 0.05 ppm. On the cationic side HCRW strong cationic resin was used, the regenerating solution was 10$ hydrochloric acid, and deionized water was the rinse liquor. On the ani¬ onic side, the resin used was a strong anionic resin called SPR (Dow Chemical Company),, a 4$ caustic was used to regener¬ ate, and the rinse liquor was deionized water. To provide a safety leeway, the regenerants were added at 10$ above

stochlometric resin treatment levels. No capacity analyses were made.

EXAMPLE VII An apparatus similar to that of Example IV was run at cycles varying between about 10 to 15 minutes, each having a 3°-second down time in order to recover uranium that was leached with HC1 as a 1000 ppm 0g complex. Sorption was accomplished at a flux of 20 gallons per minu per square foot. Increasing the flux to 35 gallons per minute per square foot permitted a 100 ppm break through of the uranium complex. A ^* high capacity of regeneration was observed.

EXAMPLE VPII Example VII was substantially repeated, except the uranium ore had been subjected to a carbonate leach an the sorption was accomplished at approximately a 1000 ppm 3 0g level.

EXAMPLE IX

Uranium ore leached with sulfuric acid was treat substantially as in Example VII. Sorption was accomplishe at about 1000 ppm of U 0g break through.

It will be apparent to those skilled in this art that the present invention can be embodied in various form accordingly, this invention is to be construed and limited only by the scope of the appended claims.