CN103588217A - Preparation method of boron-10 acid - Google Patents

Preparation method of boron-10 acid Download PDF

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CN103588217A
CN103588217A CN201310583193.3A CN201310583193A CN103588217A CN 103588217 A CN103588217 A CN 103588217A CN 201310583193 A CN201310583193 A CN 201310583193A CN 103588217 A CN103588217 A CN 103588217A
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acid
boric
boron trifluoride
boron
solidliquid mixture
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CN103588217B (en
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徐姣
张卫江
王楠楠
张雷
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Tianjin University
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Tianjin University
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Abstract

The invention relates to a preparation method of boron-10 acid. The preparation method of the boron-10 acid comprises the following steps: heating a prepared lithium carbonate-water solid-liquid mixture to be at 40-80 DEG C, inflating boron trifluoride-10 gas into the lithium carbonate-water solid-liquid mixture, stirring so as to uniformly disperse the boron trifluoride-10 into the solid-liquid mixture, and stopping gas inflation when the mol ratio of the boron trifluoride-10 to the lithium carbonate reaches (1: 1.5)-1.6; conducting an reaction for 10-25 hours to generate the boron-10 acid; separating, and performing ion exchange and crystallization to separate out the boron-10 acid solid. The preparation method is carried out in an aqueous system, thus avoiding ester hydrolysis in the process of generating trimethyl borate; the preparation method is simple in process and can be industrialized easily; the boric acid is high in yield and purity, the yield is above 95% and the purity is above 98%.

Description

A kind of boric-10 acid preparation method
Technical field
The invention belongs to synthesis and separation technical field, particularly relate to a kind of by enrichment boron trifluoride 10bF 3the method of preparing boric-10 acid.
Background technology
Boron has two kinds of stable isotropic substances, 10b and 11b, they are approximately 19.8% and 80.2% left and right in the abundance of occurring in nature.10 pairs of neutrons of boron have very strong receptivity, increasingly extensive in the application of the aspects such as nuclear power, modern industry, military equipment and medicine.Wherein, enrichment boric-10 acid is good neutron-absorbing material in nuclear industry, compares with the boric acid of natural abundance, adopts enrichment boric-10 acid to have the advantage of two highly significants in nuclear reactor: the one, and in reactor cooling system 10the concentration of B will increase; The 2nd, the whole consumption of boric acid will reduce.According to correlative study, show, 10the benefit that the increase of B concentration brings comprise reactor ability enhancing, can increase use mox fuel (mixed oxide), can increase circulation and combustion period, the fuel consumption of each circulation reduces, liquid waste disposal expense, final required fuel cost, centre and last carrying cost all will dwindle greatly thus.
The chemical isotopic exchange rectification method Separation of boron isotopes of many employings in suitability for industrialized production, after Separation of Boron Isotopes completes, what obtain is enrichment 10bF 3.For by enrichment 10bF 3be applied in nuclear industry, need to be as far as possible by enrichment 10bF 3reaction, changes into enrichment boric-10 acid.
The Wu Changmei of Liaoning Prov. Chemical Industry Inst. is in the manufacture method of the high-purity boric-10 acid of article, and adopting boron trifluoride-ether complex and calcium chloride is raw material, and in METHANOL MEDIUM, reaction generates trimethyl borate-10, and simple distillation, collects the cut of 58～60 ℃.In cut, add deionized water, the boron 10-acid trimethyl hydrolysis obtaining is generated to boric-10 acid, separation obtains boric-10 acid product.But this method easily causes the hydrolysis of trimethyl borate in reaction and still-process, reaction yield is low.This reaction equation can be expressed as follows:
Figure BDA0000416462330000011
B(CH 3O) 3+H 2O→H 3BO 3+CH 3OH （2）
The gold Hai Ling of University Of Tianjin etc. synthesizes in trimethyl borate with boron trifluoride ethyl ether complex at article, boron trifluoride 10-etherate is reacted and prepares trimethyl borate-10 with sodium methylate in METHANOL MEDIUM, centrifugal to remove Sodium Fluoride to the mixed solution after having reacted, to centrifugal supernatant liquor simple distillation, collect the cut of 54-56 ℃, to adding chlorination lithium salts in cut, analyse, the upper strata stillness of night obtaining is trimethyl borate-10, after adding water, trimethyl borate-10 hydrolysis generates boric-10 acid, through concentrated, the dry boric-10 acid product that obtains.This method easily causes the hydrolysis of trimethyl borate in reaction and still-process, and salting-out process consumption lithium chloride is more, is unfavorable for industrial applications, and reaction yield is low.The chemical equation of reaction can be expressed as follows:
Na+CH 3OH→CH 3ONa+H 2 （3）
(C 2H 5) 2O·BF 3+3NaOCH 3+CH 3OH→
[B(OCH 3) 3+CH 3OH]+3NaF+(C 2H 5) 2O （4）
[B(OCH 3) 3+CH 3OH]+LiCl→B(OCH 3) 3+[CH 3OH+LiCl] （5）
In order to improve enrichment boron trifluoride 10bF 3reaction generates yield and the purity of enrichment boric-10 acid, is more conducive to enrichment boric-10 acid suitability for industrialized production, at present all in research and development.
Summary of the invention
The present invention adopts Quilonum Retard and enrichment boron trifluoride 10bF 3the method of reaction is synthesized boric-10 acid, and this method is carried out in having aqueous systems, has avoided generating the hydrolysis of ester in trimethyl borate process.Quilonum Retard and enrichment boron trifluoride 10bF 3reaction directly generates boric-10 acid, and adopts filtration or suction filtration mode to remove the lithium fluoride of generation, filtrate is removed to a small amount of remaining lithium ion through cationic exchange, and Crystallization Separation goes out high purity boric-10 acid.
Technical solution of the present invention is as follows:
A preparation method, step is as follows:
(1) solidliquid mixture of configuration Quilonum Retard and water;
(2) above-mentioned solidliquid mixture is heated to after 40～80 ℃, in the solidliquid mixture of Quilonum Retard and water, pass into boron trifluoride-10 gas, stirring is dispersed in above-mentioned solidliquid mixture boron trifluoride-10, stops ventilation when the mol ratio of boron trifluoride-10 and Quilonum Retard reaches 1:1.5～1.6; React 10～25 hours, reaction generates boric-10 acid;
(3) lithium fluoride solid is removed in the solidliquid mixture separation after reaction is completed, till obtaining filtrate clarification;
(4) by clear filtrate through strong acid cation exchange resin column generation ion-exchange, remove lithium ion;
(5) the solution evaporation moisture through ion-exchange is concentrated, Crystallization Separation goes out boric-10 acid solid, through 60～80 ℃ of freeze-day with constant temperature, within 20～30 hours, obtains boric-10 acid product.
Enrichment boron trifluoride 10bF 3according to reacting in the aqueous solution, reaction generates lithium fluoride, carbonic acid gas and boric-10 acid with Quilonum Retard, and total reaction equation can be expressed as following form:
2BF 3+3Li 2CO 3+3H 2O→6LiF+2H 3BO 3+3CO 2 (6)
In described Quilonum Retard and the solidliquid mixture of water, the mass ratio of Quilonum Retard and water is 1:5～6.
The described speed that passes into boron trifluoride-10 gas is 10～40mL/min.
Described strong acid cation exchange resin column is 732 strong acid cation exchange resin columns; Linear velocity exchange with 1～4cm/min.
Treating processes of the present invention is simpler, is easier to realize industrialization, and boric acid yield and purity higher, boric acid yield is more than 95%, purity is more than 98%.
Embodiment
Embodiment 1
Take Powdered carbonic acid lithium (Li 2cO 3) 55.4g(0.75mol, boron trifluoride and Quilonum Retard ratio are 1:1.5), add 277.0g water dissolution, form the solidliquid mixture of Quilonum Retard and water.Solidliquid mixture is heated to after 40 ℃, with the speed of 10ml/min, slowly passes into enrichment boron trifluoride 10bF 333.9g(0.5mol), constantly stir boron trifluoride simultaneously 10bF 3the time of passing into is about 2h.Boron triflouride gas has passed into rear continuation water-bath and has maintained 40 ℃ of reactions 25 hours, promotes the generation of reaction (6).
Reacted rear pH value of solution in 7 left and right, the lithium fluoride of generation is that the solid state that is very easy to filter precipitates.Under room temperature, filter, lithium fluoride and mother liquor are separated, and with about 100g deionized water wash solid filter cake, gained washing lotion is mixed with mother liquor.
All filtrate is carried out ion-exchange with the linear velocity of 1cm/min by 732 storng-acid cation exchange resins, and a small amount of lithium ion exchanged remaining in solution is become to hydrogen ion.All filtrate, by after ion exchange resin, uses 200g deionized water wash resin to reclaim by the mother liquor of resin absorption.
Add hot filtrate, transpiring moisture, until there is boric-10 acid crystal to separate out.Afterwards the suspension containing separating out solid is cooled to about 0 ℃, continues to separate out boric-10 acid crystal.Filtration obtains boric acid solid, and with deionized water rinsing boric-10 acid solid, the filtrate obtaining is mixed and proceeded evaporative crystallization with mother liquor.Repetitive operation, until can not get boric-10 acid solid after evaporative crystallization.Through 60 ℃ of freeze-day with constant temperature, within 30 hours, obtain boric-10 acid product.This method obtains boric-10 acid yield more than 95%, and purity is more than 98%.
Embodiment 2
Take Powdered carbonic acid lithium (Li 2cO 3) 57.3g(0.775mol, boron trifluoride and Quilonum Retard ratio are 1:1.55), add 315.2g water dissolution, form the solidliquid mixture of Quilonum Retard and water.Solidliquid mixture is heated to the speed with 25ml/min after 60 ℃ and slowly adds enrichment boron trifluoride 10bF 333.9g(0.5mol), constantly stir boron trifluoride simultaneously 10bF 3the time of passing into is about 0.8h.Boron triflouride gas has passed into rear continuation water-bath and has maintained 60 ℃ of reactions 15 hours, promotes the generation of reaction (6).
Reacted rear pH value of solution in 7 left and right, the lithium fluoride of generation is that the solid state that is very easy to filter precipitates.Under room temperature, filter, lithium fluoride and mother liquor are separated, and with about 100g deionized water wash solid filter cake, gained washing lotion is mixed with mother liquor.
All filtrate is carried out ion-exchange with the linear velocity of 2cm/min by 732 storng-acid cation exchange resins, and a small amount of lithium ion exchanged remaining in solution is become to hydrogen ion.All filtrate, by after ion exchange resin, uses 200g water washing resin to reclaim by the mother liquor of resin absorption.
Add hot filtrate, transpiring moisture, until there is boric-10 acid crystal to separate out.Afterwards the suspension containing separating out solid is cooled to about 0 ℃, continues to separate out boric-10 acid crystal.Filtration obtains boric acid solid, and with deionized water rinsing boric-10 acid solid, the filtrate obtaining is mixed and proceeded evaporative crystallization with mother liquor.Repetitive operation, until can not get boric-10 acid solid after evaporative crystallization.Through 70 ℃ of freeze-day with constant temperature, within 25 hours, obtain boric-10 acid product.This method obtains boric-10 acid yield more than 95%, and purity is more than 98%.
Embodiment 3
Take Powdered carbonic acid lithium (Li 2cO 3) 59.1g(0.8mol, boron trifluoride and Quilonum Retard ratio are 1:1.6), add 354.6g water dissolution, form the solidliquid mixture of Quilonum Retard and water.Solidliquid mixture is heated to after 80 ℃, with the speed of 40ml/min, slowly adds enrichment boron trifluoride 10bF 333.9g(0.5mol), constantly stir boron trifluoride simultaneously 10bF 3the time of passing into is about 0.5h.Boron triflouride gas has passed into rear continuation water-bath and has maintained 80 ℃ of reactions 10 hours, promotes the generation of reaction (6).
Reacted rear pH value of solution in 7 left and right, the lithium fluoride of generation is that the solid state that is very easy to filter precipitates.Under room temperature, filter, lithium fluoride and mother liquor are separated, and with about 100g deionized water wash solid filter cake, gained washing lotion is mixed with mother liquor.
All filtrate is carried out ion-exchange with the linear velocity of 4cm/min by 732 storng-acid cation exchange resins, and a small amount of lithium ion exchanged remaining in solution is become to hydrogen ion.All filtrate, by after ion exchange resin, uses 200g water washing resin to reclaim by the mother liquor of resin absorption.
Add hot filtrate, transpiring moisture, until there is boric-10 acid crystal to separate out.Afterwards the suspension containing separating out solid is cooled to about 0 ℃, continues to separate out boric-10 acid crystal.Filtration obtains boric acid solid, and with deionized water rinsing boric-10 acid solid, the filtrate obtaining is mixed and proceeded evaporative crystallization with mother liquor.Repetitive operation, until can not get boric-10 acid solid after evaporative crystallization.Through 80 ℃ of freeze-day with constant temperature, within 20 hours, obtain boric-10 acid product.This method obtains boric-10 acid yield more than 95%, and purity is more than 98%.

Claims (4)

1. a boric-10 acid preparation method, is characterized in that step is as follows:
(1) solidliquid mixture of configuration Quilonum Retard and water;
(2) above-mentioned solidliquid mixture is heated to after 40～80 ℃, in the solidliquid mixture of Quilonum Retard and water, pass into boron trifluoride-10 gas, stirring is dispersed in above-mentioned solidliquid mixture boron trifluoride-10, stops ventilation when the mol ratio of boron trifluoride-10 and Quilonum Retard reaches 1:1.5～1.6; React 10～25 hours, reaction generates boric-10 acid;
(3) lithium fluoride solid is removed in the solidliquid mixture separation after reaction is completed, till obtaining filtrate clarification;
(4) by clear filtrate through strong acid cation exchange resin column generation ion-exchange, remove lithium ion;
(5) the solution evaporation moisture through ion-exchange is concentrated, Crystallization Separation goes out boric-10 acid solid, through 60～80 ℃ of freeze-day with constant temperature, within 20～30 hours, obtains boric-10 acid product.
2. the method for claim 1, is characterized in that in the solidliquid mixture of described Quilonum Retard and water, the mass ratio of Quilonum Retard and water is 1:5～6.
3. the method for claim 1, is characterized in that the described speed that passes into boron trifluoride-10 gas is 10～40mL/min.
4. the method for claim 1, is characterized in that described strong acid cation exchange resin column is 732 strong acid cation exchange resin columns; Linear velocity exchange with 1～4cm/min.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103950950A (en) * 2014-05-20 2014-07-30 方治文 Preparation method of boron-11 acid with high abundance
CN104310420A (en) * 2014-09-30 2015-01-28 天津大学 Method for preparing boron-10 acid from boron trifluoride-10

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102774846A (en) * 2012-07-16 2012-11-14 天津大学 Method for producing enriched boric-10 acid from trifluoride-anisole complex and application thereof
CN103130235A (en) * 2013-03-22 2013-06-05 天津大学 Method for preparing boron-10 acid through boron trifluoride-10 one-step method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102774846A (en) * 2012-07-16 2012-11-14 天津大学 Method for producing enriched boric-10 acid from trifluoride-anisole complex and application thereof
CN103130235A (en) * 2013-03-22 2013-06-05 天津大学 Method for preparing boron-10 acid through boron trifluoride-10 one-step method

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103950950A (en) * 2014-05-20 2014-07-30 方治文 Preparation method of boron-11 acid with high abundance
CN103950950B (en) * 2014-05-20 2015-11-11 方治文 The preparation method of high abundance boron-11 acid
CN104310420A (en) * 2014-09-30 2015-01-28 天津大学 Method for preparing boron-10 acid from boron trifluoride-10
CN104310420B (en) * 2014-09-30 2016-06-01 天津大学 The method of boric-10 acid is prepared by boron trifluoride-10

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