CN105217644A - A kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare magnesium based hydrotalcite coproduction boric acid - Google Patents
A kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare magnesium based hydrotalcite coproduction boric acid Download PDFInfo
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Abstract
The present invention relates to salt lake resources field of comprehensive utilization, particularly, the present invention relates to a kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare magnesium base intercalation functional materials coproduction boric acid.The present invention for raw material, adds certain soluble trivalent metal salt with high magnesium lithium salts lake bittern water, makes full use of magnesium resource in salt lake brine with high magnesium-lithium ratio by synthesizing magnesium-base layer-shaped functional materials, utilizes the hydrotalcite mother liquor of low Mg/Li ratio to prepare boric acid afterwards.Magnesium base functional materials provided by the invention and boric acid preparation method effectively can not only solve previous methods complex process, cost is high, salt lake resources utilization ratio is low, " magnesium evil " problem formed in potassium fertilizer production process, the cost preparing boric acid also greatly reduces, and the magnesium resource discarded is fully utilized, reduce the production cost of magnesium base functional materials, achieve salt lake magnesium boron resource high-valued and comprehensive utilization, there is good industrialization prospect.
Description
Technical field
The present invention relates to salt lake resources field of comprehensive utilization, particularly, the present invention relates to a kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare magnesium based hydrotalcite coproduction boric acid, say further, be in a kind of salt lake brine magnesium lithium be separated, the method for magnesium base functional materials and coproduction boric acid.
Background technology
China's salt lake resources is enriched, and its potential value reaches more than a few trillion yuan, wherein particularly abundant with resources such as potassium, sodium, magnesium, lithium, boron.Especially salt lake magnesium, boron resource, have good exploitation prospect, representative with Qinghai Salt Lake resource most.
The exploitation of China to salt lake magnesium resource are more and more paid attention to, and on the one hand, China's salt lake magnesium resource is of high grade, reserves large, be easy to exploitation, is very valuable resource.On the other hand, due to for a long time to the exploitation too one-sidedness of salt lake resources, often concentrate on the development and utilization of single resource, the potash fertilizer that outstanding behaviours is badly in need of in single exploitation China of a large amount of enterprise, the light magnesium of long-term heavy potassium, salt lake magnesium resource does not effectively develop, and causes the magnesium resource of flood tide in salt lake brine to cause " magnesium evil ".For Qinghai Chaerhan salt lakes, its magnesium salts reserves account for 74% of national magnesium salts resource, and have the feature of multiple useful component symbiosis.The annual production of Repone K in 2010 has reached more than 240 ten thousand tons, annual by-product 7,680 ten thousand tons of old halogen, amount to more than 2,640 ten thousand tons, magnesium chloride, not yet effectively utilize so far, this not only causes the waste of magnesium resource, make the increase year by year carrying potassium cost, and salt lake ecotope damaged and is formed " magnesium evil ", salt lake physical environment and mining environment is caused day by day to worsen, have a strong impact on economy and the equilibrium of stock exploitation of the utilizations of resources such as potassium, lithium, boron, become " bottleneck " of salt lake resources comprehensive development and utilization.
Boron resources development and utilization is more and more important for the development of modern industry, also more and more comes into one's own.At present, what China's boron rock can develop mainly contains boron magnesium stone ore and salt lake boron rock, and boron magnesium stone ore is through the exploitation of decades, and close to exhausted, and grade declines day by day.The exploitation of salt lake brine boron resource attract great attention, but the development and utilization research of China to boron resource in salt lake is still in the junior stage, to boracic brine resource strengthening research and exploitation dynamics, the situation of China's boron resource provisioning deficiency can be alleviated, develop more economical, more simply carry boron technique tool and be of great significance.
At present, the method extracting, remove boron mainly comprises acidizing crystal, chemical precipitation, solvent extraction, fractional crystallization, reverse osmosis membrane, absorption method etc.Each method cuts both ways.Acidization is applicable to boron rich ore or the boracic brine through evaporating enrichment, otherwise acid consumes comparatively large, the shortcomings such as flow process is complicated, the rate of recovery is low; Although chemical precipitation method is applicable to the high solution of boron concentration, chemical levels is large, throw out needs aftertreatment, and cost is high; Although solvent extration has, technical process is short, speed is fast, treatment capacity is large, rate of recovery advantages of higher, but extraction agent is expensive, and extraction agent, thinner in use can lose and cause cost to increase, this method also has equipment corrosion, the problems such as contaminate environment simultaneously; Fractionation crystallization adopts intermittent operation, repeated multiple times crystallization, and process tedious, yield are low, cost is high, complex operation, labour intensity are large.And Exchange Resin by Adsorption have can Reusability, energy consumption is low, pollution-free, selectivity is better, and the advantages such as the operational cycle is short, carry in boron process and do not introduce new foreign ion, the resin of load boron can be recycled after diluted acid desorb, boron in mother liquor, the boric acid product quality purity obtained through evaporation concentration is high, and quality is good.
The China Patent Publication No. CN1579937A nano magnalium hydrotalcite that utilized salt lake brine to prepare, does not study the Mg/Li ratio in salt lake brine and boric acid preparation." XSC-700 resin is to the absorption of boron in salt lake brine " (Central South University's journal (natural science edition), volume the 6th phase June the 42nd in 2011) once reported that use XSC-700 resin absorption method carried boron, but the elements such as a large amount of magnesium existed in bittern are to the adsorptive capacity of boron, adsorption rates etc. have a certain impact, the final rate of recovery affecting boron, add the cost that ion exchange adsorption prepares boric acid, and the method has only carried out exploratory study to the boron extracted in salt lake brine, do not carry out the exploitation of salt lake magnesium resource and the comprehensive utilization of salt lake magnesium boron resource.China Patent Publication No. CN102994748A, has invented a kind of fixed-bed approach removing boron from the magnesium chloride bittern of salt lake, is applicable to remove boron in the magnesium chloride of salt lake, does not carry out the extraction of boric acid and the comprehensive utilization of salt lake magnesium resource.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare magnesium based hydrotalcite coproduction boric acid is provided
The method utilizing salt lake brine with high magnesium-lithium ratio to prepare magnesium based hydrotalcite coproduction boric acid of the present invention, comprises the following steps:
1) according to Phase Diagram for Aqueous Salt Solutions principle, multistage evaporation is carried out with concentrated salt lake brine to salt lake brine, and reduce Mg/Li ratio by separating out salt, after evaporative crystallization, obtain the old halogen that Mg/Li ratio is 10 ~ 500;
2) Mg in old halogen is regulated
2+concentration, make Mg
2+concentration, at 0.5mol/L ~ 5mol/L, adds soluble trivalent metal salt and is made into mixing salt solution; Wherein, described Mg
2+be 1 ~ 5 with the cationic mol ratio of trivalent metal salt;
3) to step 2) mixing salt solution in add mixed ammonium/alkali solutions, adopt coprecipitation method under temperature is 25 ~ 70 DEG C of conditions, carry out into nuclear reaction; Carry out ageing after nucleation, Aging Temperature 50 ~ 150 DEG C, digestion time is 6 ~ 48h;
4) by step 3) mixed liquor after ageing after filtration, washing and dry, obtain magnesium based hydrotalcite and low Mg/Li ratio mother liquor; The Mg/Li ratio in mother liquor is made to drop to less than 0.1; Wherein wash water used can recycle, make after wherein lithium reaches finite concentration, washing water can with step 7) in effluent liquid be mixed for the preparation of Quilonum Retard;
5) to step 4) low Mg/Li ratio mother liquor in add certain density acid, adjust ph to 7 ~ 10;
6) by the low Mg/Li ratio mother liquor after adjust ph with the ion exchange column by being equipped with effects of boron resin of the flow velocity of 1 ~ 5mL/min, make boron enrichment in the ion exchange column that effects of boron resin is housed, make in effluent liquid that Boron contents is at below 10ppm, the adsorption rate of boron is more than 99%;
7) with a certain amount of distilled water wash ion exchange column, until not chloride ion-containing in effluent liquid, removing residual mother liquor;
8) by concentration be the flow velocity eluent ion exchange column of elutriant with 1 ~ 5mL/min of 0.5 ~ 1.5mol/L, by the boron desorb in effects of boron resin, make the desorption efficiency of boron more than 99%, obtain boron-rich mother liquor;
9) carry out multistage evaporation to boron-rich mother liquor or forced evaporation concentrates, carry out crystallisation by cooling to the mother liquor after concentrated, obtained boric acid, the boric acid quality product mark of acquisition is greater than 99%, and the yield of boron is 50% ~ 90%.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, the Mg/Li ratio in described salt lake brine with high magnesium-lithium ratio is 30 ~ 2000.
As preferably, the present invention, before preparing magnesium base functional materials, can dilute old halogen, make wherein Mg
2+for 0.5mol/L ~ 5mol/L.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, described step 2) soluble trivalent metal salt that adds is cation A l
3+, Fe
3+, Cr
3+, V
3+, Co
3+, Ga
3+or Ti
3+in one or both and negatively charged ion Cl
-, CO
3 2-, NO
3-, F
-, I
-, SO
4 2-, ClO
3 -, OH
-, H
2pO
4 -, WO
4 2-or one or both composition metal-salts in organic sulfonic acid root negatively charged ion.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, described step 2) soluble trivalent metal salt that adds is AlCl
36H
2o, CrCl
36H
2o or FeCl
36H
2one in O.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, step 3) described mixed ammonium/alkali solutions is the mixing solutions of sodium hydroxide and sodium carbonate, CO in mixing solutions
3 2-and OH
-molar concentration rate is 1:10 ~ 1:16.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, step 3) described coprecipitation method is pH static method, pH is between 8 ~ 12.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, step 4) described drying temperature is 60 ~ 120 DEG C, time of drying is 6 ~ 48h.
Step 4 of the present invention) Mg/Li ratio in obtained low Mg/Li ratio mother liquor drops to 0.001 ~ 0.1.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, step 5) described adjustment low Mg/Li ratio mother liquor pH acid used is hydrochloric acid, nitric acid or sulfuric acid, the concentration of described acid is 0.5 ~ 3mol/L.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, step 6) to state effects of boron resin be one in LSC-800, D403, D564 or XSC-700.
According to the method preparing magnesium based hydrotalcite coproduction boric acid of the present invention, preferably, step 8) described elutriant be in hydrochloric acid or sulfuric acid one or both.
Reactive crystallization of the present invention generates purity >=99% of boric acid; The rate of recovery preparing boron in boric acid process is 50% ~ 90%, and the utilization ratio of magnesium is for being greater than 99.98%.
The present invention with high magnesium lithium salts lake bittern water for raw material, add certain soluble trivalent metal salt, Mg content in salt lake brine with high magnesium-lithium ratio is reduced by synthesizing magnesium-base layer-shaped functional materials, magnesium in salt lake brine with high magnesium-lithium ratio is fully utilized, utilizes the hydrotalcite mother liquor of low Mg/Li ratio to prepare boric acid afterwards.Salt lake provided by the invention magnesium resource develop and prepare boric acid method effectively can not only solve previous methods complex process, cost is high, magnesium resource utilization ratio is low, technical barriers such as " magnesium evils ", reduce magnesium ion prepares boric acid interference to ion exchange adsorption, improve the work-ing life of sorbent material, improve adsorptive capacity and the adsorption rate of boron, the cost preparing boric acid is also greatly reduced, and reduce the cost of magnesium base functional materials, make the magnesium boron resource in salt lake be able to comprehensive development and utilization, there is good industrialization prospect.
The present invention compared with prior art has the following advantages:
(1) in the concentrated brine of salt lake, magnesium resource utilization ratio is low, waste resource, is even formed " magnesium evil ".The present invention makes full use of salt lake magnesium resource and has prepared the magnesium-base layer-shaped functional materials of high-quality, while reducing magnesium-base layer-shaped functional materials cost, for the comprehensive utilization of salt lake magnesium resource provides support.
(2) this invention greatly reduces the Mg content in high magnesium lithium salts lake bittern water, improve the utilization ratio of magnesium, reduce the impact of magnesium elements on boron adsorption rate and adsorptive capacity, the boron rate of recovery of raising, improve the work-ing life of sorbent material, reduce the production cost of boric acid.
(3) the invention provides the method for salt lake magnesium boron comprehensive utilization of resources, achieve the comprehensive utilization of salt lake magnesium boron resource, improve the utilization ratio of salt lake resources, reduce the cost of salt lake magnesium boron resources development and utilization, for the high-valued of salt lake magnesium boron resource and comprehensive utilization provide new thinking and approach.
(4) present invention process is simple, easy to operate, water consumption and soda acid amount few, cost is low, improves economic benefit; Whole reaction process is nontoxic, harmless, pollution-free, and universality is strong.
Embodiment
Set forth the present invention further by the following examples, these embodiments are only presented for purposes of illustration, do not limit the scope of the invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition.
Embodiment 1
Get Qinghai East taigener salt-lake bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 1, and wherein Mg/Li ratio is 12.Get the old halogen of 1L, regulate wherein Mg
2+concentration be 5.5mol/L, add 175.6gAlCl
36H
2o is made into mixing salt solution; Take 700.4g sodium hydroxide, 116g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 11mol/L, coprecipitation method is adopted to synthesize magnesium aluminum-hydrotalcite when temperature 25 DEG C, pH are 8, the hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 50 DEG C of Water Under thermal aging 6h, by hydrotalcite product dry 6h under 60 DEG C of conditions, namely obtain magnesium aluminum-hydrotalcite product, product purity is 99%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.015.Adding 0.5mol/L hydrochloric acid regulates the pH of the hydrotalcite mother liquor obtained to be 7, afterwards to obtain hydrotalcite mother liquor with the flow velocity of 1mL/min by being equipped with the ion exchange column of LSC-800 resin, in the effluent liquid obtained, Boron contents is 10ppm, make boron enrichment in ion exchange resin, with a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of hydrochloric acid washings with 1mL/min of 0.5mol/L afterwards by concentration, by the boron desorb in resin, desorption efficiency is 99.01%, obtain boron-rich mother liquor, forced evaporation-crystallisation by cooling is carried out to boron-rich mother liquor and obtains boric acid product, its purity is 99.12%, the boron rate of recovery is 50%.
Table 1 embodiment bittern composition (unit: g/L)
| Bittern title | Mg 2+ | Li + | B 2O 3 | Na + | K + | SO 4 2- | Cl - |
| The old halogen of East Platform | 85.47 | 6.75 | 15.77 | 10.42 | 7.69 | 29.58 | 251.60 |
Embodiment 2
Get Qinghai East taigener salt-lake bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 1, and wherein Mg/Li ratio is 12.Get the old halogen of 1L, regulate wherein Mg
2+concentration be 1.8mol/L, add 246gFeCl
36H
2o is made into mixing salt solution; Take 436g sodium hydroxide, 116g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 5.5mol/L, pH static method is adopted to synthesize Mg-Fe ball when temperature 35 DEG C, pH are 9, the hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 60 DEG C of Water Under thermal aging 12h, by hydrotalcite product dry 12h under 70 DEG C of conditions, namely obtain Mg-Fe ball product, product purity is 99.2%, and the low Mg/Li ratio mother liquor Mg/Li ratio of acquisition is reduced to 0.008.Adding 1mol/L nitric acid regulates the pH of the hydrotalcite mother liquor obtained to be 8, afterwards to obtain hydrotalcite mother liquor with the flow velocity of 2mL/min by being equipped with the ion exchange column of D403 resin, in the effluent liquid obtained, Boron contents is 8ppm, make boron enrichment in ion exchange resin, with a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of sulfuric acid scrubbing liquid with 2mL/min of 1.0mol/L afterwards by concentration, by the boron desorb in resin, desorption efficiency is 99.13%, obtain boron-rich mother liquor, forced evaporation-crystallisation by cooling is carried out to boron-rich mother liquor and obtains boric acid product, its purity is 99.03%, the boron rate of recovery is 65%.
Embodiment 3
Get Qinghai Chaerhan salt lakes bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 2, and wherein Mg/Li ratio is 312.Get the old halogen of 1L, regulate wherein Mg
2+concentration be 1.58mol/L, add 421.6gCrCl
36H
2o is made into mixing salt solution; Take 569.6g sodium hydroxide, 150.8g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 4.75mol/L, pH static method is adopted to synthesize magnesium chromium hydrotalcite when temperature 45 C, pH are 10, the hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 70 DEG C of Water Under thermal aging 18h, by hydrotalcite product dry 24h under 80 DEG C of conditions, namely obtain magnesium chromium hydrotalcite product, product purity is 99.13%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.006.Adding 1.5mol/L sulfuric acid regulates the pH of the hydrotalcite mother liquor obtained to be 9, afterwards to obtain hydrotalcite mother liquor with the flow velocity of 3mL/min by being equipped with the ion exchange column of D564 resin, in the effluent liquid obtained, Boron contents is 5ppm, make boron enrichment in ion exchange resin, with a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of sulfuric acid scrubbing liquid with 3mL/min of 1.5mol/L afterwards by concentration, by the boron desorb in resin, desorption efficiency is 99.20%, obtain boron-rich mother liquor, forced evaporation-crystallisation by cooling is carried out to boron-rich mother liquor and obtains boric acid product, its purity is 99.09%, the boron rate of recovery is 73%.
Table 2 embodiment bittern composition (unit: g/L)
| Bittern title | Mg 2+ | Li + | Na + | K + | SO 4 2- | Cl - |
| The old halogen of Cha Er Han | 115.43 | 0.37 | 1.06 | 0.6224 | 11.83 | 331.46 |
Embodiment 4
Get Qinghai Chaerhan salt lakes bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 2, and wherein Mg/Li ratio is 312.Get the old halogen of 1L, regulate wherein Mg
2+concentration be 1.19mol/L, add 531.6gAlCl
36H
2o is made into mixing salt solution; Take 569.6g sodium hydroxide, 150.8g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 3.56mol/L, pH static method is adopted to synthesize magnesium aluminum-hydrotalcite when temperature 55 DEG C, pH are 11, the hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 80 DEG C of Water Under thermal aging 24h, by hydrotalcite product dry 36h under 90 DEG C of conditions, namely obtain magnesium aluminum-hydrotalcite product, product purity is 99.32%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.006.Adding 2mol/L hydrochloric acid regulates the pH of the hydrotalcite mother liquor obtained to be 10, afterwards to obtain hydrotalcite mother liquor with the flow velocity of 4mL/min by being equipped with the ion exchange column of XSC-700 resin, in the effluent liquid obtained, Boron contents is 9ppm, make boron enrichment in ion exchange resin, with a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of hydrochloric acid washings with 4mL/min of 1.0mol/L afterwards by concentration, by the boron desorb in resin, desorption efficiency is 99.00%, obtain boron-rich mother liquor, forced evaporation-crystallisation by cooling is carried out to boron-rich mother liquor and obtains boric acid product, its purity is 99.25%, the boron rate of recovery is 82%.
Embodiment 5
Get Qinghai West Platform salt lake brine to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 3, and wherein Mg/Li ratio is 56.Get the old halogen of 1L, regulate wherein Mg
2+concentration be 0.79mol/L, add 1047.2gCrCl
36H
2o is made into mixing salt solution; Take 471.6g sodium hydroxide, 124.8g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 2.36mol/L, pH static method is adopted to synthesize magnesium chromium hydrotalcite when temperature 70 C, pH are 12, the hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 150 DEG C of Water Under thermal aging 48h, by hydrotalcite product dry 48h under 120 DEG C of conditions, namely obtain magnesium chromium hydrotalcite product, product purity is 99.53%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.003.Adding 3mol/L nitric acid regulates the pH of the hydrotalcite mother liquor obtained to be 8, afterwards to obtain hydrotalcite mother liquor with the flow velocity of 5mL/min by being equipped with the ion exchange column of LSC-800 resin, in the effluent liquid obtained, Boron contents is 5ppm, make boron enrichment in ion exchange resin, with a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of hydrochloric acid washings with 5mL/min of 0.5mol/L afterwards by concentration, by the boron desorb in resin, desorption efficiency is 99.18%, obtain boron-rich mother liquor, forced evaporation-crystallisation by cooling is carried out to boron-rich mother liquor and obtains boric acid product, its purity is 99.06%, the boron rate of recovery is 90%.
Table 3 embodiment bittern composition (unit: g/L)
| Bittern title | Mg 2+ | Li + | Na + | K + | SO 4 2- | Cl - |
| The old halogen of West Platform | 96.56 | 1.71 | 5.87 | 1.19 | 12.79 | 291.12 |
Certainly; the present invention can also have various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art can openly make various corresponding change and distortion according to of the present invention, but these change accordingly and are out of shape the protection domain that all should belong to claim of the present invention.
Claims (10)
1. utilize salt lake brine with high magnesium-lithium ratio to prepare a method for magnesium based hydrotalcite coproduction boric acid, comprise the following steps:
1) according to Phase Diagram for Aqueous Salt Solutions principle, multistage evaporation is carried out with concentrated salt lake brine to salt lake brine, and reduce Mg/Li ratio by separating out salt, after evaporative crystallization, obtain the old halogen that Mg/Li ratio is 10 ~ 500;
2) Mg in old halogen is regulated
2+concentration, make Mg
2+concentration, at 0.5mol/L ~ 5mol/L, adds soluble trivalent metal salt and is made into mixing salt solution; Wherein, described Mg
2+be 1 ~ 5 with the cationic mol ratio of trivalent metal salt;
3) to step 2) mixing salt solution in add mixed ammonium/alkali solutions, OH in mixed ammonium/alkali solutions
-volumetric molar concentration is Mg
2+2 ~ 3 of volumetric molar concentration, adopts coprecipitation method to carry out into nuclear reaction under temperature is 25 ~ 70 DEG C of conditions; Carry out ageing after nucleation, Aging Temperature 50 ~ 150 DEG C, digestion time is 6 ~ 48h;
4) by step 3) mixed liquor after ageing after filtration, washing and dry, obtain magnesium based hydrotalcite and low Mg/Li ratio mother liquor;
5) to step 4) low Mg/Li ratio mother liquor in add acid, adjust ph to 7 ~ 10;
6) by the low Mg/Li ratio mother liquor after adjust ph with the ion exchange column by being equipped with effects of boron resin of the flow velocity of 1 ~ 5mL/min, make boron enrichment in the ion exchange column that effects of boron resin is housed, make in effluent liquid that Boron contents is at below 10ppm, the adsorption rate of boron is more than 99%;
7) distilled water wash ion exchange column is used, removing residual mother liquor;
8) by concentration be the flow velocity eluent ion exchange column of elutriant with 1 ~ 5mL/min of 0.5 ~ 1.5mol/L, by the boron desorb in effects of boron resin, make the desorption efficiency of boron more than 99%, obtain boron-rich mother liquor;
9) multistage evaporation is carried out to boron-rich mother liquor or forced evaporation concentrates, crystallisation by cooling is carried out to the mother liquor after concentrated, obtained boric acid.
2. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, the Mg/Li ratio in described salt lake brine with high magnesium-lithium ratio is 30 ~ 2000.
3. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, described step 2) soluble trivalent metal salt that adds is cation A l
3+, Fe
3+, Cr
3+, V
3+, Co
3+, Ga
3+or Ti
3+in one or both and negatively charged ion Cl
-, CO
3 2-, NO
3-, F
-, I
-, SO
4 2-, ClO
3 -, OH
-, H
2pO
4 -, WO
4 2-or one or both composition metal-salts in organic sulfonic acid root negatively charged ion.
4. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 3, is characterized in that, described step 2) soluble trivalent metal salt that adds is AlCl
36H
2o, CrCl
36H
2o or FeCl
36H
2one in O.
5. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, step 3) described mixed ammonium/alkali solutions is the mixing solutions of sodium hydroxide and sodium carbonate, CO in mixing solutions
3 2-and OH
-molar concentration rate is CO in mixing solutions
3 2-and OH
-molar concentration rate is 1:10 ~ 1:16.
6. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, step 3) described coprecipitation method is pH static method, pH is between 8 ~ 12.
7. the method preparing magnesium base function intercalation material coproduction boric acid according to claim 1, is characterized in that, step 4) described drying temperature is 60 ~ 120 DEG C, time of drying is 6 ~ 48h.
8. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, step 5) described adjustment low Mg/Li ratio mother liquor pH acid used is hydrochloric acid, nitric acid or sulfuric acid, the concentration of described acid is 0.5 ~ 3mol/L.
9. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, step 6) described effects of boron resin is one in LSC-800, D403, D564 or XSC-700.
10. the method preparing magnesium based hydrotalcite coproduction boric acid according to claim 1, is characterized in that, step 8) described elutriant be in hydrochloric acid or sulfuric acid one or both.
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| CN109264737A (en) * | 2018-11-14 | 2019-01-25 | 启迪清源（北京）科技有限公司 | Recycling lithium and the method for producing high-purity boric acid or borax |
| CN110078102A (en) * | 2019-04-12 | 2019-08-02 | 中国科学院青海盐湖研究所 | The recoverying and utilizing method of salt lake bittern lithium liquor |
| CN111362285A (en) * | 2020-03-29 | 2020-07-03 | 衢州学院 | Method for utilizing boron resource in salt lake brine |
| CN113371737A (en) * | 2020-02-25 | 2021-09-10 | 中国科学院青海盐湖研究所 | Method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid |
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| CN1579937A (en) * | 2003-07-31 | 2005-02-16 | 北京化工大学 | Method for preparing nano-level magnesium-aluminium hydrotalcite using bittern as raw material |
| CN101659418A (en) * | 2009-09-02 | 2010-03-03 | 达州市恒成能源（集团）有限责任公司 | Method for preparing boric acid in boracic sodium chloride and potassium chloride saturated bittern solution containing boron |
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| CN102491379A (en) * | 2011-12-10 | 2012-06-13 | 中南大学 | Method for preparing high-purity magnesium oxide with high boron salt lake brine |
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| CN109264737A (en) * | 2018-11-14 | 2019-01-25 | 启迪清源（北京）科技有限公司 | Recycling lithium and the method for producing high-purity boric acid or borax |
| CN110078102A (en) * | 2019-04-12 | 2019-08-02 | 中国科学院青海盐湖研究所 | The recoverying and utilizing method of salt lake bittern lithium liquor |
| CN113371737A (en) * | 2020-02-25 | 2021-09-10 | 中国科学院青海盐湖研究所 | Method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid |
| CN111362285A (en) * | 2020-03-29 | 2020-07-03 | 衢州学院 | Method for utilizing boron resource in salt lake brine |
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