JPS59164630A - Purification of lithium halide brine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for obtaining high purity lithium halide solutions from resin/aluminate composites. U.S. Patent No. 4,1
16°856; 4,116.858; and 4,15
No. 9,811 contains crystalline LiX・2AUCOH.
)s, where X is a halide, particularly a chloride, and methods for making and using ion exchange resins are disclosed.

When a resin/aluminate composite is used to adsorb Lx+ ions from plines by taking up Li+ into the aluminate crystal, some prine from which rJt+ ions have been adsorbed remains in the gaps of the composite. Other metal ions (
(i.e., ions other than alkali metals) For example, if the prine contains alkaline earth metal ions (A7), then the desired L? : When water washing is performed to elute + ions from the crystal, these other ions that were present not in the crystal structure but in the interstices will also be included in the parent effluent. Using a concentrated pure sodium logefide prine wash before the water wash step used for Li+ leaching ensures that there is no appreciable amount of Li+ leaching in the aluminate crystals and that other metal ions (e.g. alkaline earth) are not leached. It has now been discovered that this results in the washing out of similar metal ions. Therefore, next
When water is used for leaching Li in aluminate crystals, the only other metal ions significantly present in the effluent are those of the sodium halide prine. As a preliminary cleaning before leaching Li+ valuables with water from a composite made of an ion exchange resin containing a crystalline lithium halide aluminate composition,
A concentrated, relatively pure sodium halide prine is used in accordance with the present invention. The lithium halide that is washed out of the interstices of the composite by water leaching is therefore most present in the first part of the effluent, with much less measles present in the subsequent part of the lithium halide solution.

Therefore, a lithium halide solution containing only thorium halide as a significant impurity is obtained.

The "resin/aluminate composite" used in the present invention is preferably a 1-crystalline 11
xX・5-2A/” (011)s (where X is a halide) was incorporated into an ion exchange resin, and Misaki was notified in November 1979.
Pending U.S. Patent Application No. 095,691, filed May 19th
It also includes the large bulking resins described in this issue.

In this Specification-1, "halide" used in the expression 1Nαparite or "LiX" means C1!, BY, or I, and Ce is u-sized.For the sake of simplicity, halide is bromide. With the understanding that iodide is also suitable, I would like to show it as a preferred chloride.

Although the small amount of Li+ in the NaCe prine is beneficial as a relatively pure sodium halide prine (I will refer to the NaC11 prine from now on),...6 halogens other than lithium halide brine It is important to remember that it also has the meaning of ``alkali metal prine''. It is this relatively pure substance that is used for pre-cleaning the lithium-enhanced resin/aluminate composite prior to the water leaching step. The water leaching step removes most of the LZ+ values (but not all of the Ls+ values) from the complex, thus leaving virtually no Sugi1 alloy in the N a CR brine.
This is carried out in order to bring the situation to a "decreased state".This 11174
Thick Na(#) brines are generally at or near saturation, but at concentrations below about 20 percent, a considerable degree of operating efficiency is obtained.

As the concentration further decreases, the amount of +11ψA7 produced by To ■ will gradually decrease. From a practical standpoint to achieve economical and effective operation, the preferred concentration is 24 percent to 26 percent.

The Li1 precipitated aqueous solution or brine solution from which Li+ ions are removed is contaminated with Li+ or metal ions other than alkali metal ions. These other metal ions are usually alkaline earth metal ions such as Mg++, c, 10, etc., but in the present Itq may also be any cations other than alkali metals.

The RIS + accumulating resin/aluminate composite, which has contaminating metal cations other than alkali metal cations in its gaps, absorbs Li + ions from the impure prine and picks up the composite, which is essentially a "diminished decoy". Used for blowing, L
(It is usually induced from the process of increasing the amount of + ions.Of course, Lx ten increase t'y (!ff411
M aluminate composites can also be used in this process. The purpose and intent of this process is to remove contaminating metal cations from interstitial spaces without removing significant amounts of Li+ ions; this task is accomplished with a relatively pure, preferably concentrated NaCIJ pre-clean. , which leaves the Li+ ions in place and leaves the gaps filled with relatively pure NaC11 plines free of the contaminating metal cations.

When water leaching was subsequently used for the separation of Li from the complex, most of the NaCl and L
Some of i+ is washed out. The subsequent portion is essentially a pure Li solution containing no traces of NaCl.

Crystalline Li
X・2Al! It is preferable not to remove all Li+ from (OH)s. Therefore, it is best that the water used for water leaching contains a small amount (about 80 m or more) of Lffl+ to prevent removal of all Lx+ from the aluminate structure.

It is believed that the higher the concentration of NaCe, the greater the tendency of the crystalline aluminate structure to adsorb and retain Xis decapables. In the process of water leaching, the AhC1 concentration in the interstices of the composite decreases, and as this decrease occurs, Li+ becomes more likely to be expelled from the crystal. Charcoal 11 is one of the methods to remove Li + valuables from the water solution. Lithium (Lj, CO,),! : This is the formation of precipitate. If other metal cations, such as alkaline earth metal cations, are present, they precipitate together with lithium as carbonic IW salts.

Sodium carbonate does not precipitate with lithium carbonate.
Therefore, Race in Li+ solutions does not suffer from the same contamination problems as metal cations. Furthermore, if NaC,g is the only contaminant in the Ls solution, most of the water will be evaporated and NaC11 will be crystallized, resulting in pure, high concentration r,
It is possible to leave an ice solution: this operation is not possible with alkaline earth metals.

The water used for water leaching of Li from the aluminate structure of the composite is substantially free of other metal cations (such as alkaline earth metal cations) except for the small amount of Li that should be present. It should be something. Small amounts of alkali metal cations, -10- such as Na+, are also acceptable. Deionized (softened) water may be used as well as distilled water or other sufficiently pure water, provided that there are substantially no alkaline earth metal or non-alkali metal cations present. .

The following examples are presented to illustrate certain embodiments, and the invention is not limited to the particular embodiments described therein.

In the examples below, the water leaching stage is approximately 68 m Li+
A crude (impure) Li-containing raw material brine from which Li+ ions are to be extracted, substantially saturated with NaCe and for only about 2 s, carried out using deionized water containing ions.
oppm.

Li+ ions and about 6.8% Nα+, about 17
．． 05% ce, -1 about 0.41% niju, about 0.31% yg++, about 3.8% 60 sho, about 0.28% Sr++,
Approximately 0.022 percent B+, approximately 20-807 ypm
I7) Aln+, containing about 20-80 ppm MO++ and about 9-10 ppm Cu++, and its pH
is a mineral prine from the Smackover deposit near Magnolia, Arkansas, where the mineralogy is approximately 5.8. Substantially pure N used for pre-cleaning before water leaching
aCl! Saturate the prine, about 20
0 ppmf) Contains Li+ ions, 6
．． The pH was 3. The resin/aluminate composite is manufactured by The Dow Chemical Company (under the trade name DOW14X A (WA-1).
The Dow Chemica, I Cnm7rany
A weakly basic anion exchange resin commercially available from ) containing crystalline Lice.2 All COH) was used. The container used had a capacity of 120 cr with a jacket for trap circulation fluid for temperature control.
It was a glass ion exchange column.

Example 1 An ion exchange column was packed with a resin/aluminate composite that had been previously water leached to make it a substantially "reduced" composite for the Li content. Approximately 77
The total hardness (yg Q
A special crude raw material pline with the same content (Ca + F, etc.) was passed through the composite bed. A pre-cleaning of a relatively pure and saturated NaC11 prine was then carried out to replace the crude prine remaining in the interstices of the composite; the pre-cleaning was carried out until the hardness of the effluent was less than 0.002Af. , 8.8”/
passed through the column at a speed of min. A water leaching step was then performed with a water flow rate of 8.8 ci/min.

The effluent from the column has density, molar hardness and 7 pm L
Each cut was separated for analysis of i+. Figure 13 shows the elution pattern for one cycle of bulking/prine washing/leaching. Those skilled in the art will readily understand that the complex in its "reduced state" can be subjected to multiple such cycles.

Table I Effluent cut injection 2 50 1.186 - -8 50
1.182 - -4 48 1.190
1.144 -5-- - - 6 - - - - 7 - 1.207 1.156 - Plakan cleaning start 8 50-1.076 - 9 25 1.162 0.504 -1L- 10 - 1 .144 − −1
1 25 1.146 0.082 270
12 25-0.012 21018 25
- 0.002 19014 25
- - 17015 25--
150 Start of water leaching 16 25 --
- 14517 25 -
-1 11518 25 - -
10019 25 - - 18242
0 25 - - 187521
25 - - 67522 2
5 - - 49028 25
- - 88524, 25 -
-- 82025 25 --
- The 290 peak cut (19-24) had very low hardness values, if any at all.

Comparative Example This example is NaC7? This is an example of the effect of pre-cleaning/omission. The exchange column bed had a volume of 170C, substantially similar to that produced by the process disclosed in co-pending U.S. patent application Ser. No. 095,961.
A resin composite containing tJ·2Ae(Off)s crystalline material in a highly concentrated state was used, and the temperature of the column was 90°C. The procedure was carried out substantially according to the method of Example 1, except that the flow rate was 2.5% per column bed per minute and the wash water (for leaching) was approximately 607) m 1ii+. did.

After passing sufficient smack-over brine through the resin/aluminate composite to “bulk” the composite with fix+values, Na, CI! The water leaching step was carried out without prewashing of the solution. As you can read from the following table■'s LZ
The "peel" cut with + density had a fair degree of hardness value.

Table ■ Effluent cut 1 50 1.29 850 Water leaching start 2 10 1.29 850 8 10 1.80 850 4 10 1.81 850 5 5 1.29 850 6 5 1.29 . 400 7 5 1J4 450 8 5 1.82 700 1 5 1.14 2700 10 5 0.75 625011 5
0.42 760012 5 0.24
690018 5 0.14 600014
5 0.07 500015 5 0.0
6 485016 5 0.05 880
017 5 0.08 880018 5
0.02 800 17- Example 2 This example was carried out substantially in the same manner as Example 1. DOWEX until the effluent reaches the same fix+ concentration as the raw material.
Smackover brine was pumped down a bed of 120Cr, which had lithium chloroaluminate dispersed in MWA-1 resin; Li+ concentration was measured by standard atomic absorption. The pure saturated q]INac8 brine was passed through the bed at a rate of 2.75% per bed volume per minute as a prewash. After pre-cleaning approximately 0.83 bed volumes, the bed was
1.66 beds with deionized water containing 0 ppm Ls+;
During l'+'t, the effluent was collected after each cut by flushing. The flow of smackover brine was resumed at a flow rate of 8.2% bed volume per minute to refill or "rebulk" the resin complex with the filtium. Table 111 shows the elution data.

=18- Table III Effluent cut volume Li+ 1 10 1.128 802 Saturated NaC, e pre-wash 2 10 867 8 10 375 4 10 877 5 10 1.148 877 6 10 1.020 876 7 10 0.670 424 8 10 0.482 408 9 10 0.272 506 1o t6 0.188 582 11 10 0.144 511 Start of water washing (2
80ppmmL6+) 12 10 0.108 527 18 10 0.072 518 14 10 0, Oa6 496 15 10 0.048 479 16 10 0.028 815 17 10 0.072 1650 18 Ill 00052 4 97519 10
0.028 4275 20 10 0.020 8575 2110 - 2825 22 10 0.012 242528 10
0.002 207524 10 0.006
18002510 - 1525 2610 - 1875 2710 - 1250 2810 - 1175 29 10 ~ 1075 80 10 0.006 99282 10
0, L108 100088 10 0.008
92884 10 0.008 79835
10 1), 184 88B86 10
0868 18887 10 0.496
4588 10 0.640 848
9 1 (10,78628 401110,81624) and had low hardness and was taken as a product cut.The remaining cuts were used as below J'J, and most were used for the concentration cycle.The data are shown in the table. Shown in ■.

Cuts 1-6 were recirculated to the raw material tank, Cut 7.8
and 9 were combined to flow the resin/aluminate bed to "thicken" the Li+ into the resin. Cuts 10-18 were merged and passed through the resin bed. c) 14-15 were combined and passed through the resin bed. Next, 33 cr of new type up brine was passed through to replace the portion of 7-15 that was already missing or taken during sample collection.

Cuts 16 and 17 were combined and passed through the bed with NaCr saturation. C) 18-21 was kept as a product.

Cuts 22-28 were merged and passed through the floor. 28 O
ppmLi+ deionized water makeup 1f (84
Ce) was passed through the bed.

The data are shown in Table ■.

21- Table ■ Effluent cut 1 10 1.120 350 Previous cut in bed 211) -392 81g 1.164 401 41 (1-408 5El 1.182 418 610 - 429 7 11) 0.888 447 8 10 '0.71) 0 4719 111
l), 524 51410 11) o, aso
58811 ill 11.296 565
12 10 (1,282565 18Ill 11.164 57914 10 0
．． 128 571 15 ] (117,080575 1611111,1164564 1711) (1,052578 18100,076781 22- 24 10 0.012 290025 10
0.106 257526 10 0, O+
38 282527 10 0.008 2250 28 10 0.008 2075 29 10 0.008 200080 10
0.248 81431 10 0.472
84682 10 0.612 178
Example 3 In this experiment, an appropriate cut is selected from the cuts shown in Table 1 to demonstrate further enrichment of Ls+ valuables by performing multi-step adsorption and desorption of Lt+ valuables. This preferred method of operation therefore consists of utilizing a portion of the effluent of the sequential run. This could be accomplished by storing the effluent in coils or in series of tanks to create a gradient. Therefore, the only "new" material needed for each elution cycle was a make-up volume of fresh deionized water (containing a small amount of Li+) equal in volume to the product cut;
NaCe f is sufficient to resaturate the gradient section called
) I was so angry. In multi-stage operations using Li-containing cuts from previous runs, the product concentration increased over that obtained in a single cycle.

Looking at the cuts in Table 2, the first six cuts had relatively low hardness and low Li content, so they were recycled to the smack-over prine raw material. Cuts 7, 8 and 9 were combined into the first solution and pumped onto the column for equal volume smack-over-prine elution. cut 10
, 11 and 12 were combined and pumped after the 7.8.9 mixture. This is a solution prepared by mixing 13, 14, 15, and 16 (In, 11 and 12 mixture)]
I had NaCI chase after me;
) and pumped into the column. c)20,
21, 22 and 23 were reserved as products. c) 24-80 were combined and allowed to follow the "reflux" mixture of 17.18.19. Next (product cut (!:
The mixture was followed with 24-30 mL of deionized water containing an equal volume of 28 OyypmLi. All effluent from this run was collected separately per cut as before for use in the next concentration cycle. This method was repeated until the fifth cycle. Product cutting was performed at 8912 ppmLi+ (1st
The concentration was increased to 5581 ppmLi+c (fifth cycle).

125 = Procedural amendment (method) % formula % 1. Indication of the case Patent Application No. 36089 of 1988 2. Title of the invention Lithium halide prine 8 product 3. Person making the amendment Relationship to the case Patent applicant Name The Dow Chemical Company Akasaka Taisei Building (
Phone 582-7161) Handwritten Myopongi attached to Ganpei 1

Claims (1)

[Claims] (1) A method for leaching Li'-values from a porous resin/aluminate composite containing contaminated brine, wherein the resin/aluminate composite contains crystalline LiX.2A.
ICOH)s (wherein Pre-cleaning with a concentrated alkali metal fluoride solution substantially cleans contaminated lines from the complex without stripping away the Li+ valuables, and water leaching substantially cleans the contaminated alkali metal fluoride solution. leaching out a substantial amount of the Li+ valuables from the composite with a compound solution to leave a complex in which the Li+ valuables are substantially reduced but not completely eliminated; Leaching method. 2. The method according to claim 1, wherein X is chloride. 3. The method according to claim 1 or 2, wherein the alkali metal halide solution is a saturated sodium chloride solution. 4. The concentration of sodium chloride solution is 20%.2
9. The method of claim 8 within 6 percent. 5. The water used for water leaching is 801 pmJJ, the above Li+
1.2.8.4. 6. The method according to any one of claims 1.2 and 8.4.5, wherein the concentrated alkali metal halide solution used for pre-cleaning contains a small amount of lithium halide. 7. Lithium halide content is low and lI: is obtained from the pre-cleaning stage of one previous weight-loss cycle and/or from the 9th floor of water immersion. Method. 8. The claim that the alkali metal halide solution containing a small amount of fit halide is prepared by adding NaCe to at least a portion of the eluent of the water leaching stage of the previous increase-decrease cycle. The method described in Section 6. 9. The method according to any one of claims 1 to 6, characterized in that the composite in a substantially reduced state is a contaminated brine containing Li and valuables.