CN104310420A - Method for preparing boron-10 acid from boron trifluoride-10 - Google Patents
Method for preparing boron-10 acid from boron trifluoride-10 Download PDFInfo
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- CN104310420A CN104310420A CN201410520396.2A CN201410520396A CN104310420A CN 104310420 A CN104310420 A CN 104310420A CN 201410520396 A CN201410520396 A CN 201410520396A CN 104310420 A CN104310420 A CN 104310420A
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- boron trifluoride
- lithium hydroxide
- acid
- boric
- boron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
Abstract
The invention relates to a method for preparing boron-10 acid from boron trifluoride-10. The method comprises the following steps: by taking a boron trifluoride-10 gas or a boron trifluoride-10 low-carbon alcohol complex as a raw material, reacting with lithium hydroxide to generate boron-10 acid in a water medium, filtering, performing ion exchange and crystallizing a mixed liquid so as to separate boron-10 solid. The method is performed in water, so that the loss of yield caused by the fact that a middle product boric acid ester generated in a conventional esterification hydrolysis method is hydrolyzed as the system contains water is avoided. The treatment process is simple, industrialization is relatively easy to achieve, the boric acid yield and the purity are relatively high, the boric acid yield is greater than 97%, and the purity is greater than 99%.
Description
Technical field
The invention belongs to synthesis and separation technical field, particularly relate to a kind of method by boron trifluoride-10 gas or boron trifluoride-10 low-carbon alcohol complexes preparation boric-10 acid.
Background technology
Boron has two kinds of stable isotropic substances,
10b and
11b, they are approximately 19.8% and about 80.2% in the abundance of occurring in nature.Boron 10 pairs of neutrons have very strong receptivity, and the application in nuclear power, modern industry, military equipment and medicine etc. is increasingly extensive.Compared with the boric acid of natural abundance, adopt in nuclear reactor enrichment boric-10 acid can intensified response heap ability, increase the fuel consumption using mox fuel (mixed oxide), increase fuel combustion and loop cycle, each circulation of minimizing, liquid waste disposal expense, final required fuel cost, centre and last carrying cost all will reduce greatly thus.
The boric acid industrial making method of current maturation has legal in ammonium bicarbonate method, many Sodium Tetraboratees method, sulfuric acid, hydrochloric acid method, electroosmose process etc.Because the raw material producing boric acid is above natural boron rock, thus obtained is the boric acid of natural abundance, cannot meet the application requiring of high abundance boric-10 acid.
In suitability for industrialized production, the chemical isotopes that adopts exchanges rectification method acquisition enrichment more
10bF
3.In order to by enrichment
10bF
3be applied in nuclear industry, need as far as possible by enrichment
10bF
3change into enrichment boric-10 acid.
The Wu Changmei of Liaoning Prov. Chemical Industry Inst., adopts boron trifluoride-10-etherate and calcium chloride to be raw material, uses catalyst reaction to generate trimethyl borate-10 in METHANOL MEDIUM.The boron 10-acid trimethyl hydrolysis obtained is generated boric-10 acid.But because in reaction and still-process, reaction system requires the high loss easily causing trimethyl borate to water-content, reaction yield is the highest only has 70%.
The extra large tinkling of pieces of jade of University Of Tianjin's gold, reacts boron trifluoride 10-etherate and sodium methylate and prepares trimethyl borate-10, centrifugation, and collect the cut of 54-56 DEG C, saltout and obtain trimethyl borate-10 in METHANOL MEDIUM, and then hydrolysis generates boric-10 acid.This technological process is too complicated, and equipment needs to seal completely, and salting-out process consumption lithium chloride is more, and industrialization difficulty is large, and reaction yield is low.
Summary of the invention
The method that the present invention adopts lithium hydroxide and boron trifluoride-10 to react is to synthesize boric-10 acid, and this method is carried out having in aqueous systems, avoids the trimethyl borate hydrolysising loss causing generation because system is moisture.
Wherein boron trifluoride-10 can be boron trifluoride-10 gas or boron trifluoride-10 low-carbon alcohol complex compound;
Lithium hydroxide and boron trifluoride-10 gas or boron trifluoride-10 low-carbon alcohol complex compound react and directly generate boric-10 acid, and the lithium fluoride that the removing of adopter's filter type generates, by filtrate through a small amount of remaining lithium ion of cationic exchange removing, and Crystallization Separation goes out high purity boric-10 acid.
Technical solution of the present invention is as follows:
By the method for boron trifluoride-10 gas generation boric-10 acid, step is as follows:
(1) configure the aqueous solution of lithium hydroxide, wherein the mass ratio of lithium hydroxide crystal and water is 1:7 ~ 1:9;
(2) under normal temperature water-bath, boron trifluoride-10 and lithium hydroxide react, and wherein boron trifluoride-10 is 1:3 ~ 1:5 with the mol ratio of lithium hydroxide; Fed in raw material rear water-bath or oil bath is heated to mixture boiling, react 15 ~ 25 hours, generation boric-10 acid;
(3) by the solidliquid mixture suction filtration removing lithium fluoride solid after having reacted, filtrate is obtained;
(4) by filtrate through 732 type strong acid cation exchange resin columns, with the linear velocity generation ion-exchange of 3 ~ 5cm/min, removing lithium ion and some other positively charged ion, wherein resin particle diameter is 0.3-1.2mm;
(5) the solution evaporation moisture through ion-exchange is concentrated, when there being fine crystals to separate out in solution, crystallization is carried out with the stirring velocity of the speed of cooling of 0.5 ~ 2 DEG C/min, 50 ~ 150r/min, Tc is 5 ~ 15 DEG C, crystallization time is 8 ~ 15h, and the boric-10 acid solid filtered to isolate obtains boric-10 acid product in 20 ~ 24 hours through 60 ~ 70 DEG C of freeze-day with constant temperature.
Wherein: when boron trifluoride-10 and lithium hydroxide react, be that the selection of different material is as follows according to boron trifluoride-10:
When boron trifluoride-10 is boron trifluoride-10 gas, step (2) is:
In lithium hydroxide aqueous solution, pass into boron trifluoride-10 gas, gas speed control is made as without white cigarette in reactor, stirs simultaneously and makes to mix;
During for boron trifluoride-10 low-carbon alcohol complex compound, step 2 is:
Boron trifluoride-10 low-carbon alcohol complex compound (as methyl alcohol, ethanol etc.) is added in lithium hydroxide aqueous solution, wherein in complex compound, the massfraction of boron trifluoride-10 is 0.2 ~ 0.6, and it is that 10 ~ 20mL/min, temperature in the kettle are below 40 DEG C that complex compound rate of addition controls.
Treating processes of the present invention is more simple, is easier to realize industrialization, and boric acid yield and purity higher, boric acid yield is more than 97%, and purity is more than 99%.
Embodiment
When boron trifluoride-10 is boron trifluoride-10 gas:
Embodiment 1
(1) Powdered lithium hydroxide crystal (LiOHH is taken
2o, analytical pure 90%) 34.95g (0.75mol, boron trifluoride and lithium hydroxide molar ratio are 1:3), add 244.65g water (mass ratio of lithium hydroxide crystal and water is 1:7) and dissolve, form the mixture of lithium hydroxide and water.
(2) slowly pass into boron trifluoride-10 gas 16.95g (0.25mol), gas speed about 5mL/min, constantly stir simultaneously, rear oil bath of having fed in raw material is heated to mixture boiling, reacts 15 hours.
(3) reacted mixture is filtered, and with about 100g deionized water wash solid filter cake, filtrate is boric acid solution.
(4) all filtrate carries out ion-exchange with the linear velocity of 3cm/min by 732 type storng-acid cation exchange resins, after whole filtrate passes through ion exchange resin, with 150g deionized water wash resin to reclaim by the mother liquor of resin absorption.
(5) concentrated filtrate is heated, until there is fine crystals to separate out, carry out crystallization with the stirring velocity of the speed of cooling of 0.5 DEG C/min, 50r/min, Tc is 5 DEG C, crystallization time is 8h, and the boric-10 acid crystal filtered to isolate obtains boric-10 acid product in 20 hours through 60 DEG C of freeze-day with constant temperature.This method obtains boric-10 acid yield more than 97%, and purity is more than 99%.
Embodiment 2
(1) Powdered lithium hydroxide crystal (LiOHH is taken
2o, analytical pure 90%) 46.60g (1mol, boron trifluoride and lithium hydroxide molar ratio are 1:4), add 372.80g water (mass ratio of lithium hydroxide crystal and water is 1:8) and dissolve, form the mixture of lithium hydroxide and water.
(2) slowly pass into boron trifluoride-10 gas 16.95g (0.25mol), gas speed about 15mL/min, constantly stir simultaneously, rear oil bath of having fed in raw material is heated to mixture boiling, reacts 20 hours.
(3) reacted mixture is filtered, and with about 100g deionized water wash solid filter cake, filtrate is boric acid solution.
(4) all filtrate carries out ion-exchange with the linear velocity of 4cm/min by 732 type storng-acid cation exchange resins, after whole filtrate passes through ion exchange resin, with 150g deionized water wash resin to reclaim by the mother liquor of resin absorption.
(5) concentrated filtrate is heated, until there is fine crystals to separate out, carry out crystallization with the stirring velocity of the speed of cooling of 1.0 DEG C/min, 100r/min, Tc is 9 DEG C, crystallization time is 11h, and the boric-10 acid crystal filtered to isolate obtains boric-10 acid product in 22 hours through 65 DEG C of freeze-day with constant temperature.This method obtains boric-10 acid yield more than 97%, and purity is more than 99%.
Embodiment 3
(1) Powdered lithium hydroxide crystal (LiOHH is taken
2o, analytical pure 90%) 58.25g (1.25mol, boron trifluoride and lithium hydroxide molar ratio are 1:5), add 524.25g water (mass ratio of lithium hydroxide crystal and water is 1:9) and dissolve, form the mixture of lithium hydroxide and water.
(2) slowly pass into boron trifluoride-10 gas 16.95g (0.25mol), gas speed about 25mL/min, constantly stir simultaneously, rear oil bath of having fed in raw material is heated to mixture boiling, reacts 25 hours.
(3) reacted mixture is filtered, and with about 100g deionized water wash solid filter cake, filtrate is boric acid solution.
(4) all filtrate carries out ion-exchange with the linear velocity of 5cm/min by 732 type storng-acid cation exchange resins, after whole filtrate passes through ion exchange resin, with 150g deionized water wash resin to reclaim by the mother liquor of resin absorption.
(5) concentrated filtrate is heated, until there is fine crystals to separate out, carry out crystallization with the stirring velocity of the speed of cooling of 2 DEG C/min, 150r/min, Tc is 15 DEG C, crystallization time is 15h, and the boric-10 acid crystal filtered to isolate obtains boric-10 acid product in 24 hours through 70 DEG C of freeze-day with constant temperature.This method obtains boric-10 acid yield more than 97%, and purity is more than 99%.
During for boron trifluoride-10 low-carbon alcohol complex compound:
Embodiment 1
(1) Powdered lithium hydroxide crystal (LiOHH is taken
2o, analytical pure 90%) 34.95g (0.75mol, boron trifluoride and lithium hydroxide molar ratio are 1:3), add 244.65g water (mass ratio of lithium hydroxide crystal and water is 1:7) and dissolve, form the mixture of lithium hydroxide and water.
(2) add boron trifluoride-10-methanol complex 84.75g (0.25mol, massfraction is 0.2), rate of addition is 20mL/min, constantly stirs simultaneously, and rear oil bath of having fed in raw material is heated to mixture boiling, reacts 15 hours.
(3) reacted mixture is filtered, and with about 100g deionized water wash solid filter cake, filtrate is boric acid solution.
(4) all filtrate carries out ion-exchange with the linear velocity of 3cm/min by 732 type storng-acid cation exchange resins, after whole filtrate passes through ion exchange resin, with 150g deionized water wash resin to reclaim by the mother liquor of resin absorption.
(5) concentrated filtrate is heated, until there is fine crystals to separate out, carry out crystallization with the stirring velocity of the speed of cooling of 2 DEG C/min, 50r/min, Tc is 5 DEG C, crystallization time is 8h, and the boric-10 acid crystal filtered to isolate obtains boric-10 acid product in 20 hours through 60 DEG C of freeze-day with constant temperature.This method obtains boric-10 acid yield more than 97%, and purity is more than 99%.
Embodiment 2
(1) Powdered lithium hydroxide crystal (LiOHH is taken
2o, analytical pure 90%) 46.60g (1mol, boron trifluoride and lithium hydroxide molar ratio are 1:4), add 372.80g water (mass ratio of lithium hydroxide crystal and water is 1:8) and dissolve, form the mixture of lithium hydroxide and water.
(2) add boron trifluoride-10-ethanol complex 42.38g (0.25mol, massfraction is 0.4), rate of addition is 15mL/min, constantly stirs simultaneously, and rear oil bath of having fed in raw material is heated to mixture boiling, reacts 20 hours.
(3) reacted mixture is filtered, and with about 100g deionized water wash solid filter cake, filtrate is boric acid solution.
(4) all filtrate carries out ion-exchange with the linear velocity of 4cm/min by 732 type storng-acid cation exchange resins, after whole filtrate passes through ion exchange resin, with 150g deionized water wash resin to reclaim by the mother liquor of resin absorption.
(5) concentrated filtrate is heated, until there is fine crystals to separate out, carry out crystallization with the stirring velocity of the speed of cooling of 1.0 DEG C/min, 100r/min, Tc is 9 DEG C, crystallization time is 11h, and the boric-10 acid crystal filtered to isolate obtains boric-10 acid product in 22 hours through 65 DEG C of freeze-day with constant temperature.This method obtains boric-10 acid yield more than 97%, and purity is more than 99%.
Embodiment 3
(1) Powdered lithium hydroxide crystal (LiOHH is taken
2o, analytical pure 90%) 58.25g (1.25mol, boron trifluoride and lithium hydroxide molar ratio are 1:5), add 524.25g water (mass ratio of lithium hydroxide crystal and water is 1:9) and dissolve, form the mixture of lithium hydroxide and water.
(2) add boron trifluoride-10-methanol complex 28.25g (0.25mol, massfraction is 0.6), rate of addition is 10mL/min, constantly stirs simultaneously, and rear oil bath of having fed in raw material is heated to mixture boiling, reacts 25 hours.
(3) reacted mixture is filtered, and with about 100g deionized water wash solid filter cake, filtrate is boric acid solution.
(4) all filtrate carries out ion-exchange with the linear velocity of 5cm/min by 732 type storng-acid cation exchange resins, after whole filtrate passes through ion exchange resin, with 150g deionized water wash resin to reclaim by the mother liquor of resin absorption.
(5) concentrated filtrate is heated, until there is fine crystals to separate out, crystallization is carried out with the stirring velocity of the speed of cooling of 0.5 DEG C/min, 150r/min, Tc is 15 DEG C, crystallization time is 15h, and the boric-10 acid crystal filtered to isolate obtains boric-10 acid product in 24 hours through 70 DEG C of freeze-day with constant temperature.This method obtains boric-10 acid yield more than 97%, and purity is more than 99%.
Claims (8)
1. prepare a boric-10 acid method by boron trifluoride-10, it is characterized in that step is as follows:
(1) configure the aqueous solution of lithium hydroxide, wherein the mass ratio of lithium hydroxide crystal and water is 1:7 ~ 1:9;
(2) under normal temperature water-bath, boron trifluoride-10 and lithium hydroxide react, and wherein boron trifluoride-10 is 1:3 ~ 1:5 with the mol ratio of lithium hydroxide; Fed in raw material rear water-bath or oil bath is heated to mixture boiling, react 15 ~ 25 hours, generation boric-10 acid;
(3) by the solidliquid mixture suction filtration removing lithium fluoride solid after having reacted, filtrate is obtained;
(4) by filtrate through 732 type strong acid cation exchange resin columns, with the linear velocity generation ion-exchange of 3 ~ 5cm/min, removing lithium ion and some other positively charged ion, wherein resin particle diameter is 0.3-1.2mm;
(5) the solution evaporation moisture through ion-exchange is concentrated, when there being fine crystals to separate out in solution, crystallization is carried out with the stirring velocity of the speed of cooling of 0.5 ~ 2 DEG C/min, 50 ~ 150r/min, Tc is 5 ~ 15 DEG C, crystallization time is 8 ~ 15h, and the boric-10 acid solid filtered to isolate obtains boric-10 acid product in 20 ~ 24 hours through 60 ~ 70 DEG C of freeze-day with constant temperature.
2. the method for claim 1, is characterized in that boron trifluoride-10 is boron trifluoride-10 gas or boron trifluoride-10 low-carbon alcohol complex compound.
3. the method for claim 1, when it is characterized in that boron trifluoride-10 for boron trifluoride-10 gas, described step 2) be: in lithium hydroxide aqueous solution, pass into boron trifluoride-10 gas, gas speed control is made as without white cigarette in reactor, stirs simultaneously and makes to mix.
4. the method for claim 1, when it is characterized in that boron trifluoride-10 for boron trifluoride-10 low-carbon alcohol complex compound, step 2) be: in lithium hydroxide aqueous solution, add boron trifluoride-10 low-carbon alcohol complex compound, wherein in complex compound, the massfraction of boron trifluoride-10 is 0.2 ~ 0.6, and it is that 10 ~ 20mL/min, temperature in the kettle are below 40 DEG C that complex compound rate of addition controls.
5. the method for claim 1, is characterized in that the mass ratio of lithium hydroxide and water in the mixture of described lithium hydroxide and water is 1:7 ~ 1:9.
6. the method for claim 1, described boron trifluoride-10 is 1:3 ~ 1:5 with the mol ratio of lithium hydroxide.
7. the method for claim 1, reaction system is reacted 15 ~ 25 hours under boiling state.
8. the method for claim 1, is characterized in that described strong acid cation exchange resin column is 732 type strong acid cation exchange resin columns.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436475A (en) * | 2019-09-11 | 2019-11-12 | 北京镭硼科技有限责任公司 | A kind of preparation method of high-purity fluorine boric-10 acid potassium |
| CN113307281A (en) * | 2021-05-28 | 2021-08-27 | 天津大学 | Method for synthesizing nuclear grade boric acid by hydrolyzing boron trifluoride |
| CN115159539A (en) * | 2022-08-02 | 2022-10-11 | 山东合益气体股份有限公司 | Preparation method of boric acid |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US2789884A (en) * | 1954-06-30 | 1957-04-23 | Clement J Rodden | Method of preparing pure boric oxide |
| US3682590A (en) * | 1969-06-06 | 1972-08-08 | Eagle Picher Ind Inc | Method of forming boric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110436475A (en) * | 2019-09-11 | 2019-11-12 | 北京镭硼科技有限责任公司 | A kind of preparation method of high-purity fluorine boric-10 acid potassium |
| CN113307281A (en) * | 2021-05-28 | 2021-08-27 | 天津大学 | Method for synthesizing nuclear grade boric acid by hydrolyzing boron trifluoride |
| CN115159539A (en) * | 2022-08-02 | 2022-10-11 | 山东合益气体股份有限公司 | Preparation method of boric acid |
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