CN114275794A - Preparation method of high-purity boric acid - Google Patents
Preparation method of high-purity boric acid Download PDFInfo
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- CN114275794A CN114275794A CN202210121587.6A CN202210121587A CN114275794A CN 114275794 A CN114275794 A CN 114275794A CN 202210121587 A CN202210121587 A CN 202210121587A CN 114275794 A CN114275794 A CN 114275794A
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- boron
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of high-purity boric acid, which comprises the steps of taking boron halide as a raw material, generating boric acid and hydrogen halide through hydrolysis reaction, and concentrating, crystallizing, filtering and drying the boric acid to obtain the high-purity boric acid; wherein the halogen in the boron halide is chlorine element or bromine element. In the invention, the whole reaction avoids the introduction of metal cations and anions except chloride ions or bromide ions, the reaction process is easy to control, the purification process is simple, the industrial production is easy to realize, and the yield and the purity of the boric acid are high, the yield of the boric acid is over 95 percent, and the purity of the boric acid is over 99.9 percent.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of high-purity boric acid.
Background
The natural boron element has two stable isotopes, i.e.10B and11and B, the relative abundance is 19.78% and 80.22% respectively.10B has the characteristic of extremely high absorption of neutrons, the absorption cross section of the B for thermal neutrons is 3837 targets, and the B is a high-efficiency thermal neutron absorbent which is indispensable in a safety and control system in a nuclear power plant.11B is just opposite to B, almost does not absorb neutrons, so the conductive material is used as a doping agent in the manufacturing process of a semiconductor device, and the conductive performance and the radiation and interference resistance of the semiconductor device can be effectively improved. The boron-10 acid has wide application in the fields of nuclear industry, medicine and science and technology. In protective articles, boron-10 acid is enriched and mainly used for protecting middle bullets, such as nuclear protective clothing, neutron gun protective clothing and the like; in the nuclear industry, boron-10 acid is an ideal material for shielding radiation and controlling the intensity of nuclear reactions in nuclear reactions; in modern medical field, boron neutron capture therapy for cancer (NCT) is a new radiotherapy method, and neutrons are mainly associated with target Nuclide (NCT) in NCT medicine10B isotope) to generate secondary radiation and recoil particles which have the function of killing cancer cells. The high-abundance boron-11 acid can be used as a preparation raw material of a boron compound related to the concentrated boron-11 isotope, the high-abundance boron-11 acid can also be used as a raw material for preparing a series of boron-11 acid ester, the boron-11 acid ester can be used as a boron-11 isotope doping source in the ultra-large scale integrated circuit semiconductor device manufacturing process, and the manufactured semiconductor device has excellent anti-interference and anti-radiation performance. The high-purity boric acid can be used as a high-purity reagent and a raw material of a high-purity borate crystal material, and can also be used in a nuclear power station.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity boric acid, which has the characteristics of simple purification process, easy control of reaction process, high yield and high purity of the boric acid.
The preparation method of the high-purity boric acid takes boron halide as a raw material, boric acid and hydrogen halide are generated through hydrolysis reaction, and the boric acid is concentrated, crystallized, filtered and dried to obtain the high-purity boric acid; wherein the halogen in the boron halide is chlorine element or bromine element.
In the invention, the halogen in the boron halide is chlorine element or bromine element, metal cations are easy to remove by rectification and purification, and the reaction solvent and the reactant are deionized water or ultrapure water to avoid ion introduction, so that the conversion rate relative to boron atoms is high. If boron trifluoride is used for hydrolysis, fluoroborate is generated, other chemical agents are added for removing impurities, and other negative and positive impurity ions are introduced.
The reaction formula of the boron halide hydrolysis reaction is as follows:
BX3+3H2O→H3BO3+3HX，(X＝Cl、Br)
preferably, the boron halide is boron halide of natural boron, boron halide enriched with boron-10 or boron-11 isotopes, wherein the abundance of boron-10 isotopes is not less than 20%, and the abundance of boron-11 isotopes is not less than 80%. Further, the boron halide of the natural boron is prepared from boron trifluoride of the natural boron and aluminum trichloride or aluminum tribromide. Further, the boron halide enriched with boron-10 or boron-11 isotopes is prepared from boron trifluoride enriched with boron-10 or boron-11 isotopes and aluminum trichloride or aluminum tribromide. Further, the high-purity boric acid is natural boric acid, enriched boron-10 acid or enriched boron-11 acid.
Preferably, the reaction solvent for hydrolysis is deionized water or ultrapure water.
Preferably, the preparation method of the high-purity boric acid provided by the invention can be specifically carried out according to the following steps:
(1) synthesizing:
introducing boron halide into a hydrolysis kettle containing a reaction solvent heated to 20-90 ℃, generating boric acid and hydrogen halide through hydrolysis reaction, stopping introducing the boron halide when the reaction reaches the end point, and heating the mixture in the hydrolysis kettle to 95 ℃ for heat preservation;
(2) concentration:
pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution;
(3) and (3) crystallization:
transferring the concentrated solution into a crystallization tank for crystallization;
(4) and (3) filtering:
filtering and separating the crystallized mixture through a filter, and collecting the mother liquor into a waste liquor tank for centralized treatment;
(5) and (3) drying:
and (3) placing the filtered crystal in a dryer, drying at the temperature of 30-100 ℃ to obtain high-purity boric acid, and collecting the product in a product collecting container for storage.
Preferably, the drying method in the step (5) may specifically adopt one or a combination of several of tunnel continuous drying, air flow drying, fluidized bed drying, freeze drying and vacuum drying.
The invention has the advantages that: the method takes boron halide (bromine and chlorine) as raw materials, takes deionized water or ultrapure water as a reaction solvent, and generates boric acid and hydrogen halide through hydrolysis reaction, so that the whole reaction avoids the introduction of metal cations and anions except chloride ions or bromide ions, the reaction process is easy to control, the purification process is simple, the industrial production is easy to realize, the yield and the purity of the boric acid are high, the yield of the boric acid is over 95 percent, and the purity of the boric acid is over 99.9 percent.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
a preparation method of high-purity boric acid comprises the following steps:
(1) synthesis of
Introducing high-purity boron trichloride gas in a storage tank into a hydrolysis kettle, heating the gas to a deionized water solution at 70 ℃, and carrying out hydrolysis reaction on the high-purity boron trichloride in water to generate boric acid and hydrogen chloride, wherein the reaction formula is as follows:
BCl3+3H2O→H3BO3+3HCl
when the reaction reaches the end point, stopping introducing the high-purity boron trichloride gas, heating the mixture in the hydrolysis kettle to 95 ℃, and preserving heat.
(2) Concentrating
And pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution.
(3) Crystallization of
And transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture.
(4) Filtering to remove mother liquor
And filtering and separating the crystallization mixture through a filter to remove mother liquor, and collecting the mother liquor into a waste liquor tank for centralized treatment.
(5) Drying
And (3) placing the filtered crystal in a dryer, drying at a constant temperature of 75 ℃ to obtain high-purity boric acid, and collecting the product in a product collecting container for storage.
The actual consumption of 1000 g of high-purity boron trichloride can obtain 506 g of high-purity boric acid with the purity of 99.9%. The yield is 96 percent calculated according to the actual consumption of high-purity boron trichloride.
Example 2:
a preparation method of high-purity boric acid comprises the following steps:
(1) synthesis of
Introducing high-purity boron trichloride-10 gas in a storage tank into a hydrolysis kettle, heating the gas to a deionized water solution at 80 ℃, and carrying out hydrolysis reaction on the high-purity boron trichloride-10 gas in water to generate boron-10 acid and hydrogen chloride, wherein the reaction formula is as follows:
10BCl3+3H2O→H3 10BO3+3HCl
when the reaction reaches the end point, stopping introducing the abundant boron trichloride-10 gas, heating the mixture in the hydrolysis kettle to 95 ℃ and preserving heat.
(2) Concentrating
And pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution.
(3) Crystallization of
And transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture.
(4) Filtering to remove mother liquor
And filtering and separating the crystallization mixture through a filter to remove mother liquor, and collecting the mother liquor into a waste liquor tank for centralized treatment.
(5) Drying
And (3) placing the filtered filter cake into a dryer, drying at a constant temperature of 60 ℃ to obtain the high-abundance boron-10 acid, and collecting the product into a product collecting container for storage.
Actually consuming 1000 g of boron trichloride-10 with 96% abundance of boron-10 to obtain 512 g of boron-10 acid with high abundance and 99.9% purity. The yield is 97 percent according to the calculation of actually consumed high-abundance boron trichloride-10.
Example 3:
a preparation method of high-purity boric acid comprises the following steps:
(1) synthesis of
Introducing high-purity boron trichloride-11 gas in a storage tank into a hydrolysis kettle, heating the gas to a deionized water solution at 70 ℃, and carrying out hydrolysis reaction on the high-purity boron trichloride-11 gas in water to generate boron-11 acid and hydrogen chloride, wherein the reaction formula is as follows:
11BCl3+3H2O→H3 11BO3+3HCl
when the reaction reaches the end point, stopping introducing high-purity boron trichloride-11 gas, heating the mixture in the hydrolysis kettle to 95 ℃, and preserving heat.
(2) Concentrating
And pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution.
(3) Crystallization of
And transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture.
(4) Filtering to remove mother liquor
And filtering and separating the crystallization mixture through a filter to remove mother liquor, and collecting the mother liquor into a waste liquor tank for centralized treatment.
(5) Drying
And (3) placing the filtered filter cake into a dryer, drying at a constant temperature of 75 ℃ to obtain high-purity boric-11 acid, and collecting the product into a product collecting container for storage.
The weight of boron trichloride-11 which actually consumes 99.7 percent of abundance of boron-11 is 1000 g, and the product high-purity boron-11 acid is obtained with 506 g and the purity is 99.9 percent. The yield is 96 percent according to the actual consumption of the high-purity boron trichloride-11.
Example 4:
a preparation method of high-purity boric acid comprises the following steps:
(1) synthesis of
Dropwise adding the high-purity boron tribromide liquid in the storage tank into a deionized water solution heated to 70 ℃ in a hydrolysis kettle, and carrying out hydrolysis reaction on the high-purity boron tribromide in water to generate boric acid and hydrogen bromide, wherein the reaction formula is as follows:
BBr3+3H2O→H3BO3+3HBr
when the reaction reaches the end point, stopping dropwise adding the high-purity boron tribromide liquid, and heating the mixture in the hydrolysis kettle to 95 ℃ for heat preservation.
(2) Concentrating
And pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution.
(3) Crystallization of
And transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture.
(4) Filtering to remove mother liquor
And filtering and separating the crystallization mixture through a filter to remove mother liquor, and collecting the mother liquor into a waste liquor tank for centralized treatment.
(5) Drying
And (3) placing the filtered crystal in a dryer, drying at a constant temperature of 70 ℃ to obtain high-purity boric acid, and collecting the product in a product collecting container for storage.
The actual consumption of 1000 g of high-purity boron tribromide results in 242 g of high-purity boric acid with a purity of 99.9%. The yield was 98% calculated on actual consumption of high purity boron tribromide.
Example 5:
a preparation method of high-purity boric acid comprises the following steps:
(1) hydrolysis of boron tribromide-10 to prepare boron-10 acid
Dropwise adding the high-purity boron tribromide-10 liquid in the storage tank into an ultrapure water solution heated to 70 ℃ in a hydrolysis kettle, wherein the high-purity boron tribromide-10 is subjected to hydrolysis reaction in water to generate boron-10 acid and hydrogen bromide, and the reaction formula is as follows:
10BBr3+3H2O→H3 10BO3+3HBr
when the reaction reaches the end point, stopping dripping the high-abundance boron tribromide-10 liquid, and heating the mixture in the hydrolysis kettle to 95 ℃ for heat preservation.
(2) Concentrating
And pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution.
(3) Crystallization of
And transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture.
(4) Filtering to remove mother liquor
And filtering and separating the crystallization mixture through a filter to remove mother liquor, and collecting the mother liquor into a waste liquor tank for centralized treatment.
(5) Drying
And (3) placing the filtered filter cake into a dryer, drying at a constant temperature of 60 ℃ to obtain the high-abundance boron-10 acid, and collecting the product into a product collecting container for storage.
The actual consumption of 1000 g of boron tribromide with 96% abundance of boron-10 results in 236 g of high-abundance boron-10 acid with a purity of 99.9%. The yield is 96 percent calculated according to the actual consumption of the abundant boron tribromide-10.
Example 6:
the preparation method of the high-purity boric acid comprises the following steps.
(1) Hydrolysis of boron tribromide-11
Dropwise adding the high-purity boron tribromide-11 liquid in the storage tank into an ultrapure water solution heated to 65 ℃ in a hydrolysis kettle, wherein the high-purity boron tribromide-11 generates hydrolysis reaction in water to generate boron-11 acid and hydrogen bromide, and the reaction formula is as follows:
11BBr3+3H2O→H3 11BO3+3HBr
when the reaction reaches the end point, stopping dropwise adding the high-purity boron tribromide-11 liquid, and heating the mixture in the hydrolysis kettle to 95 ℃ for heat preservation.
(2) Concentrating
And pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution.
(3) Crystallization of
And transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture.
(4) Filtering to remove mother liquor
And filtering and separating the crystallization mixture through a filter to remove mother liquor, and collecting the mother liquor into a waste liquor tank for centralized treatment.
(5) Drying
And (3) placing the filtered crystal in a dryer, drying at a constant temperature of 65 ℃ to obtain high-purity boric acid, and collecting the product in a product collecting container for storage.
The actual consumption of 1000 g of boron tribromide-11 with 99.7% abundance of boron-11 results in 239 g of high-purity boron-11 acid with a purity of 99.9%. The yield was 97% calculated on actual consumption of high purity boron tribromide-11.
The purity of the high-purity boric acid, the boron-10 acid and the boron-11 acid prepared by the invention is high, can reach more than 99.9 percent, and can meet the requirements of the scientific and technical fields of nuclear industry, medicine, semiconductors and the like, the high-abundance boron-10 acid prepared by the invention can be used in nuclear power stations as thermal neutron absorption, nuclear protection clothes, neutron gun protection clothes and the like, the high-abundance boron-11 acid can be used as a raw material for preparing related boron compounds in the fields of semiconductors for concentrating boron-11 isotopes and the like, and the high-purity boric acid can be used as a raw material of boric acid, a high-purity reagent and a high-purity borate crystal material in the general industrial field, and can also be used in the nuclear power stations.
The invention provides a preparation method of high-purity boric acid, which can be realized by changing process parameters, equipment structure design and the like by the technical personnel in the field through the content of the invention. The above 6 examples are only preferred embodiments of the present invention, and similar substitutions and modifications can be made without departing from the technical scope of the present invention.
Claims (8)
1. The preparation method of the high-purity boric acid is characterized in that boron halide is used as a raw material, the boric acid and hydrogen halide are generated through hydrolysis reaction, and the boric acid is concentrated, crystallized, filtered and dried to obtain the high-purity boric acid; wherein the halogen in the boron halide is chlorine element or bromine element.
2. The method for preparing high-purity boric acid according to claim 1, wherein the boron halide is a boron halide of natural boron, a boron halide enriched with boron-10 or boron-11 isotopes, wherein the abundance of boron-10 isotopes is not less than 20% and the abundance of boron-11 is not less than 80%.
3. The method for preparing high-purity boric acid according to claim 2, wherein the boron halide of natural boron is prepared from boron trifluoride of natural boron and aluminum trichloride or aluminum tribromide.
4. The method for preparing high-purity boric acid according to claim 2, wherein the boron halide enriched with boron-10 or boron-11 isotope is prepared from boron trifluoride enriched with boron-10 or boron-11 isotope and aluminum trichloride or aluminum tribromide.
5. The method according to claim 2, wherein the high purity boric acid is natural boric acid, enriched boric-10 acid or enriched boric-11 acid.
6. The method according to claim 1, wherein the solvent for hydrolysis is deionized water or ultrapure water.
7. The method for preparing high purity boric acid according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) synthesizing:
introducing boron halide into a hydrolysis kettle containing a reaction solvent heated to 20-90 ℃, generating boric acid and hydrogen halide through hydrolysis reaction, stopping introducing the boron halide when the reaction reaches the end point, and heating the mixture in the hydrolysis kettle to 95 ℃ for heat preservation;
(2) concentration:
pumping the reacted mixture into a concentration tank for concentration to obtain a concentrated solution;
(3) and (3) crystallization:
transferring the concentrated solution into a crystallization tank for crystallization to obtain a crystallization mixture;
(4) and (3) filtering:
filtering and separating the crystallized mixture through a filter, and collecting the mother liquor into a waste liquor tank for centralized treatment;
(5) and (3) drying:
and (3) placing the filtered crystal in a dryer, drying at the temperature of 30-100 ℃ to obtain high-purity boric acid, and collecting the product in a product collecting container for storage.
8. The method for preparing high-purity boric acid according to claim 7, wherein the drying in the step (5) is one or a combination of tunnel continuous drying, pneumatic drying, fluidized bed drying, freeze drying and vacuum drying.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1236730A2 (en) * | 2001-03-02 | 2002-09-04 | Clariant GmbH | Process for preparing boronic and borinic acids |
| CN103950948A (en) * | 2014-05-20 | 2014-07-30 | 方治文 | Preparation method of high-purity boron trifluoride-11 |
| JP2015182936A (en) * | 2014-03-25 | 2015-10-22 | Jx日鉱日石金属株式会社 | High-purity boron and production method thereof |
| CN109305981A (en) * | 2018-11-20 | 2019-02-05 | 白银棓诺新材料有限公司 | The synthetic method of 2 hydroxy naphthalene -1- boric acid |
| CN113307281A (en) * | 2021-05-28 | 2021-08-27 | 天津大学 | Method for synthesizing nuclear grade boric acid by hydrolyzing boron trifluoride |
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- 2022-02-09 CN CN202210121587.6A patent/CN114275794B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1236730A2 (en) * | 2001-03-02 | 2002-09-04 | Clariant GmbH | Process for preparing boronic and borinic acids |
| JP2015182936A (en) * | 2014-03-25 | 2015-10-22 | Jx日鉱日石金属株式会社 | High-purity boron and production method thereof |
| CN103950948A (en) * | 2014-05-20 | 2014-07-30 | 方治文 | Preparation method of high-purity boron trifluoride-11 |
| CN109305981A (en) * | 2018-11-20 | 2019-02-05 | 白银棓诺新材料有限公司 | The synthetic method of 2 hydroxy naphthalene -1- boric acid |
| CN113307281A (en) * | 2021-05-28 | 2021-08-27 | 天津大学 | Method for synthesizing nuclear grade boric acid by hydrolyzing boron trifluoride |
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