CN104150499B - Preparation method of high-purity boric acid and nuclear grade high-purity boric acid - Google Patents
Preparation method of high-purity boric acid and nuclear grade high-purity boric acid Download PDFInfo
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 274
- 239000004327 boric acid Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 39
- 238000002425 crystallisation Methods 0.000 claims abstract description 38
- 239000011575 calcium Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010338 boric acid Nutrition 0.000 claims description 242
- 229960002645 boric acid Drugs 0.000 claims description 241
- 239000000047 product Substances 0.000 claims description 63
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001953 recrystallisation Methods 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- 238000005516 engineering process Methods 0.000 claims description 20
- 230000002000 scavenging effect Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 5
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 17
- 230000008025 crystallization Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 229940028001 boric acid antiseptic and disinfectant Drugs 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 64
- 239000002994 raw material Substances 0.000 description 23
- 239000010413 mother solution Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- IKRMZAOEXULJQX-UHFFFAOYSA-N calcium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Ca+2].O1B([O-])OB2OB([O-])OB1O2 IKRMZAOEXULJQX-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910006130 SO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910021540 colemanite Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of high-purity boric acid and nuclear-grade high-purity boric acid, belonging to the technical field of fine chemical engineering. The method comprises the following process steps: 1) mixing industrial boric acid with water, stirring to remove calcium, magnesium and sodium impurities in the industrial boric acid, and carrying out solid-liquid separation to obtain a high-purity boric acid precursor; 2) dissolving high-purity boric acid precursor in hot pure water to obtain H-containing solution3BO3180 g/L-280 g/L boric acid solution, which is subjected to deep iron and heavy metal removal by using a composite additive, filtering, cooling crystallization, solid-liquid separation, washing and dryingAnd drying to obtain the high-purity boric acid product. And dissolving the high-purity boric acid product in pure water, and recrystallizing, dehydrating and drying for 1-2 times to obtain the nuclear-grade high-purity boric acid product. The method can obtain high-purity boric acid products of different grades, and has the advantages of simple process, easy operation and control, good reproducibility, low production cost and environmental friendliness.
Description
Technical field
The present invention relates to fine chemistry industry production technical field, a kind of high-purity boracic acid and the preparation of core level high-purity boracic acid
Method.
Background technology
Boric acid is of many uses, in addition to being largely used to glassmaking, is additionally operable to the industrial departments such as enamel, pottery, metallurgy.
High-purity boracic acid in addition to the raw material as chemical reagent, fluorescent material and high borosilicate glass, be alternatively arranged as neutron moderator,
Trapping agent and coolant, be largely used in nuclear industry.Along with Nuclear Power Industry is in the whole world, the particularly further development of China, core
The consumption of level boron product will quickly increase.Core level boric acid is to Ca2+、Fe3+、Pb2+、SO4 2-、Cl-Require the highest Deng impurity content, state
Produce SILVER REAGENT boric acid and still can not reach requirement.
Boric acid big producing country in the world, such as the U.S., Turkey, the raw material of employing is tincal, colemanite.Due to former
Material B2O3Content is high (reaching about 45%), and impurity is few, thus the preparation technology of its boric acid and high-purity boracic acid is the simplest.And China uses
Primary raw material in production boric acid is boron magnesium ore and ludwigite, because of its B2O3Content is relatively low, and dopant species is many, content is high so that
The preparation technology of boric acid is complex, produced industrial boric acid Fe, Ca, Mg, SO4 2-Higher Deng impurity content, some industrial boric acids are also
Containing beavy metal impurity (in terms of Pb content about 10 × 10-6).High-purity boracic acid is prepared generally with hydrogen peroxide for raw material with industrial boric acid
Fe in boron oxide acid solution2+For Fe3+, then ferrum precipitation removes.But it is limited in one's ability except ferrum due to this method, it is impossible to by heavy metal
Precipitation removes, and causes the technological process preparing high-purity boracic acid longer.
At present, domestic core level high-purity boracic acid of preparing mainly uses following methods: one is with industrial goods boron trifluoride-10 second
Ether complexes is raw material, and employing calcium chloride is deoxidizer, carries out reaction with methanol for medium and obtains methyl borate., then by boron
Acid trimethyl hydrolysis obtains core level boric acid；Another kind is with industrial boric acid as raw material, prepares core level aoxidizing an esterification crystallization process
High-purity boracic acid.Disclose in Dalian University of Technology's " preparation of photoelectricity/nuclear power-grade high-purity boracic acid and crystallization shape research " literary composition, with
Industrial boric acid is raw material, it is proposed that the method that oxidation-ester crystallization process prepares nuclear power-grade high-purity boracic acid.
It can be seen that the preparation method of above two core level boric acid, all there is use organic compound, not only environment is brought
Impact, and energy consumption is higher, makes product cost the most higher simultaneously.
Although Shi Yigepeng resource-rich country of China, but owing to being limited by boron rock grade and fabricating technology,
High-purity boracic acid used by Chinese Nuclear Industry In The Past is almost complete by external import at present, and not only price is high, and relies on merely import high purity boron
Acid is also unfavorable for the development of domestic Nuclear Power Industry.
Summary of the invention
It is an object of the invention to provide one and prepare high-purity boracic acid and core level high purity boron with domestic industrial boric acid for raw material
The method of acid.The abundant raw material source of the method, economy, technique is simple, it is easy to operation controls, favorable reproducibility, during except ferrum, can be by
Beavy metal impurity removes simultaneously；And without adding organic reagent in preparation process, production cost is relatively low, environmentally friendly.
Realizing foregoing invention purpose, the concrete technical scheme that the present invention uses is:
The preparation method of a kind of high-purity boracic acid, it is characterised in that comprise the following steps that:
1) industrial boric acid sized mixing with water, stir removing calcium, magnesium, sodium impurity, before obtaining high-purity boracic acid after solid-liquid separation
Drive body；
2) high-purity boracic acid presoma is 80 DEG C with temperature～100 DEG C of pure water dissolve, prepare containing H3BO3 180g/L～
The boric acid solution of 280g/L, after compound additive deep iron removal, removing heavy metals, then through filtration, crystallisation by cooling, solid-liquid separation,
Washing, drying, i.e. obtain high-purity boracic acid product.
By step 2) high-purity boracic acid that do not carries out drying and processing is dissolved in pure water, and through 1～2 recrystallization, it is dehydrated, dries, i.e.
Obtain core level high-purity boracic acid product.
Step 2) described in high-purity boracic acid presoma can substitute with industrial boric acid high-class product, this high-class product industrial boric acid
Ca content < 0.032%, Mg content < 0.015%, Fe content < 0.002%, Na content < 0.03%.
Described compound additive is the combination of sulfide and ammonia, and the two uses after sizing mixing.
Described sulfide is any one in ammonium sulfide, barium sulfide, strontium sulfide, Potassium monosulfide., sodium sulfide, or arbitrarily
The combination of two or three；Its consumption is 10～30 times of chemical reaction metering.
The volume by volume concentration of described ammonia is 5%, and its consumption is 30～60 times of sulfide in mass ratio.
The concrete preparation technology of described high-purity boracic acid presoma is: weighed by industrial boric acid, adds 1.5～4 in mass ratio
Water again, stirs 20～60min at a temperature of 10～35 DEG C, i.e. obtains high-purity boracic acid presoma after solid-liquid separation.
Containing H in described mother solution after solid-liquid separation3BO3 35g/L～75g/L, can return to water logging preprocessing process and follows
Ring uses, and when wherein Ca content is accumulate to close to 500mg/L, can be used as preparing the raw material of industrial boric acid or Calcium pyroborate.
The concrete preparation technology of described high-purity boracic acid product is: high-purity boracic acid presoma step 1) prepared adds temperature
Being in the pure water of 80～100 DEG C, after stirring and dissolving obtains boric acid solution, the pH value adding ammonia regulation solution is 4.6～5.3, then
Add compound additive reaction 15～30min, filter, obtain scavenging solution；Then the temperature of scavenging solution is maintained 70～95 DEG C, add
Enter hydrogen peroxide, stir 15～30min, make the S of excess2-It is converted into elementary sulfur or SO4 2-, after filtration, in filtrate, add quality dense
Degree is the nitric acid of 40～45%, and adjusting solution ph is 2.5～4.0, and stirring, crystallisation by cooling to temperature are 10 DEG C～30 DEG C, and solid-liquid divides
From, then with pure water boric acid crystal, after dehydration, in 60 DEG C～70 DEG C of drying high-purity boracic acid products.
Described scavenging solution contains H3BO3 180～280g/L, Ca 18～140mg/L, Mg 14～60mg/L, Fe 0.10～
0.3mg/L, Pb 0.06～0.2mg/L.Before adding composite additive remove impurity, the iron content of solution is 1～13mg/L, lead content
For Pb 0.4～3mg/L.
The addition of described hydrogen peroxide is the 0.2～1.0% of boric acid solution volume.
Described high-purity boracic acid product, its Na content ＜ 40 × 10-6, Fe content ＜ 5 × 10-6, Pb content ＜ 1 × 10-6。
The concrete preparation technology of described core level high-purity boracic acid is: first the high-purity boracic acid not carrying out drying and processing is dissolved in temperature
It is in 80 DEG C～100 DEG C of pure water, prepares containing H3BO3The boric acid solution of 180g/L～280g/L, by 1.5～2.5g/ in solution
L adds ammonium nitrate or ammonium acetate, and insulation is filtered, and under agitation, crystallisation by cooling is to final temperature 10 DEG C～30 DEG C, and then solid-liquid divides
From；So recrystallization 1～2 times, dry, pack and i.e. obtain core level high-purity boracic acid product.
Compared with prior art, it is an advantage of the current invention that:
1, high due to impurity contents such as current many its ferrum of domestic industrial boric acid, calcium, sulfate, thus its purposes is seriously subject to
Limit, market competitive power is the strongest.And the present invention can be directly with domestic industry that the impurity contents such as ferrum, calcium, sulfate, heavy metal are higher
Boric acid is raw material, uses the mode of water logging to remove the impurity such as the part calcium in industrial boric acid, magnesium, sodium and obtains next step and prepare high-purity
The presoma of boric acid, its abundant raw material source, economy；Simultaneously the mother solution after solid-liquid separation also can return to Soaking treatment process and follows
Ring uses one to three time, or is used as to prepare the raw material of industrial boric acid, Calcium pyroborate.Part calcium in removing industrial boric acid, magnesium, sodium are miscellaneous
The technique of matter is simple, it is easy to operation.
2, the present invention removes the part calcium in industrial boric acid by the way of water logging, magnesium, sodium impurity obtain preparing high purity boron
Acid presoma, then with compound additive deep iron removal, removing heavy metals after, cool down, crystallize after obtain high-purity boracic acid, its sodium content
＜ 40 × 10-6, iron content ＜ 5 × 10-6, lead content ＜ 2 × 10-6, reach the requirement to impurity of the analytical pure boric acid.This process is not
But except ferrum, removing heavy metals thoroughly, and when recrystallization without using organic reagent, while reducing environmental pollution, from root
Solve the technical problem preparing core level its complex process of high-purity boracic acid with industrial boric acid for raw material in basis, and achieve preferably
Economic effect.
3, the present invention can prepare high-purity boracic acid and core level high-purity boracic acid with domestic industrial boric acid for raw material simultaneously, and it is molten
Liquid mesoboric acid content reaches 180g/L～280g/L, and high-purity boracic acid can obtain core level high-purity boracic acid product through 1～2 recrystallization,
Subsequent purification process is highly simplified, easily operates.
The present invention can prepare high-purity boracic acid and core level high purity boron while less expensive with domestic industrial boric acid for raw material
Acid, relative to the existing method preparing core level high-purity boracic acid for raw material with industrial boric acid, it is simple that the present invention has technique, operation control
System is relatively easy to, and does not use the advantages such as a large amount of high-purity organic reagent, production cost are low during recrystallization.Owing to first preparing
The high-purity boracic acid that the impurity content such as ferrum, heavy metal is extremely low, thus simplify the subsequent purification process preparing core level high-purity boracic acid, whole
Individual technique is easier to industrializing implementation.
Accompanying drawing explanation
Fig. 1 is the process chart of the inventive method
Fig. 2 is the scanning electron microscope topographic image figure of each rank boric acid
Wherein: a be industrial boric acid microstructure as high-purity boracic acid microstructure that, b is certain import as, c, d are this
Bright core level high-purity boracic acid microstructure as.
Detailed description of the invention
The foregoing of the present invention is described in further detail by detailed description of the invention by the following examples, but not
This should being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example, all is realized based on foregoing of the present invention
High-purity boracic acid technology of preparing belong to the scope of the present invention.
The preparation method of embodiment 1 high-purity boracic acid
Processing step includes: 1) by industrial boric acid with water Leaching Removal part therein calcium, magnesium, sodium impurity, obtain high-purity
Boric acid presoma；2) high-purity boracic acid presoma is 80 DEG C with temperature～90 DEG C of pure water dissolve, prepare containing H3BO3 180g/L～
The boric acid solution of 220g/L, after compound additive deep iron removal, removing heavy metals, then through filtration, crystallisation by cooling, solid-liquid separation,
Washing, drying, i.e. obtain high-purity boracic acid product.
Described compound additive is the combination of sulfide and ammonia, and the two uses after sizing mixing.
Described sulfide is any one in ammonium sulfide, barium sulfide, strontium sulfide, Potassium monosulfide., sodium sulfide, and its consumption is for changing
Learn reaction metering 15～30 times.
The volume by volume concentration of described ammonia is 5%, and its consumption is 40～50 times of sulfide in mass ratio.
The concrete preparation technology of described high-purity boracic acid presoma is: weighed by industrial boric acid, adds 2～4 times in mass ratio
Water, at a temperature of 10～20 DEG C stir 40～60min, after solid-liquid separation, i.e. obtain high-purity boracic acid presoma.
Containing H in described mother solution after solid-liquid separation3BO3 35～49g/L, can return to the circulation of Soaking treatment process and make
With, when wherein Ca content is accumulate to 450～500mg/L, can be used as preparing the raw material of industrial boric acid or Calcium pyroborate.
The concrete preparation technology of described high-purity boracic acid product is: is dissolved in pure water by high-purity boracic acid presoma, in temperature is
After at 80～90 DEG C, stirring and dissolving obtains boric acid solution, the pH value adding ammonia regulation solution is 4.6～5.0, adds compound adding
Add agent reaction 15～30min, filter, be purified liquid；Then the temperature of scavenging solution is maintained 80～95 DEG C, add dioxygen
Water, stirs 25～30min, makes the S of excess2-It is converted into elementary sulfur or SO4 2-, after filtration, in filtrate, add concentration by weight
Being the nitric acid of 40～45%, adjusting solution ph is 3.5～4.0, and stirring, crystallisation by cooling to temperature are 10 DEG C～20 DEG C, and solid-liquid divides
From, then with pure water boric acid crystal, after dehydration, in 65 DEG C of drying high-purity boracic acid products.
Described scavenging solution contains H3BO3 180～223g/L, Fe 0.05～0.1mg/L, Pb 0.05～0.15mg/L.Except ferrum
Front leachate iron content 3～9mg/L, lead content are Pb 1.5～2.5mg/L.
The addition of described hydrogen peroxide is the 0.4～1.0% of boric acid solution volume.
Described high-purity boracic acid product, its Na content ＜ 40 × 10-6, Fe content ＜ 5 × 10-6, Pb content ＜ 1 × 10-6。
The preparation method of embodiment 2 core level high-purity boracic acid
It is in 80 DEG C～90 DEG C of pure water that the high-purity boracic acid without drying and processing that embodiment 1 prepares first is dissolved in temperature, system
H must be contained3BO3The boric acid solution of 180g/L～220g/L, by 2.5～3.5g/L addition ammonium nitrates in solution, insulation is filtered,
Under agitation, crystallisation by cooling is to final temperature 10 DEG C～20 DEG C, then solid-liquid separation；So recrystallization 1～2 times, dry, pack
Obtain product.
The preparation method of embodiment 3 high-purity boracic acid
Processing step includes: 1) by industrial boric acid with water Leaching Removal part therein calcium, magnesium, sodium impurity, obtain high-purity
Boric acid presoma；2) high-purity boracic acid presoma is 80 DEG C with temperature～90 DEG C of pure water dissolve, prepare containing H3BO3 240～280g/
The boric acid solution of L, after compound additive deep iron removal, removing heavy metals, then through filtration, crystallisation by cooling, solid-liquid separation, washing,
Dry, i.e. obtain high-purity boracic acid product.
Described compound additive is the combination of sulfide and ammonia, and the two uses after sizing mixing.
Described sulfide is the combination of any two in ammonium sulfide, barium sulfide, strontium sulfide, Potassium monosulfide., sodium sulfide, and it is used
Measure 10～15 times for chemical reaction metering.
The volume by volume concentration of described ammonia is 5%, and its consumption is 50～60 times of sulfide in mass ratio.
The concrete preparation technology of described high-purity boracic acid presoma is: weighed by industrial boric acid, adds 1.5～3 in mass ratio
Water again, stirs 30～40min at a temperature of 20～30 DEG C, i.e. obtains high-purity boracic acid presoma after solid-liquid separation.
Containing H in described mother solution after solid-liquid separation3BO346～68g/L, can return to Soaking treatment process and recycle,
When wherein Ca content is accumulate to 500mg/L, can be used as preparing the raw material of industrial boric acid or Calcium pyroborate.
The concrete preparation technology of described high-purity boracic acid product is: is dissolved in pure water by high-purity boracic acid presoma, in temperature is
After at 90～100 DEG C, stirring and dissolving obtains boric acid solution, the pH value adding ammonia regulation solution is 4.8～5.3, adds compound adding
Add agent reaction 20～30min, filter, be purified liquid；Then the temperature of scavenging solution is maintained 85～95 DEG C, add dioxygen
Water, stirs 25～30min, makes the S of excess2-It is converted into elementary sulfur or SO4 2-, after filtration, in filtrate, add concentration by weight
Being the nitric acid of 40～45%, adjusting solution ph is 2.5～3.5, and stirring, crystallisation by cooling to temperature are 20 DEG C～30 DEG C, and solid-liquid divides
From, then with pure water boric acid crystal, after dehydration, in 70 DEG C of drying high-purity boracic acid products.
Described scavenging solution contains H3BO3 240～283g/L, Fe 0.10～0.3mg/L, Pb 0.15～0.22mg/L.Except ferrum
Front leachate iron content 1～6mg/L, lead content is Pb 0.5～1.0 mg/L.
The addition of described hydrogen peroxide is the 0.2～0.5% of boric acid solution volume.
Described high-purity boracic acid product, its Na content ＜ 30 × 10-6, Fe content ＜ 5 × 10-6, Pb content ＜ 2 × 10-6。
The preparation method of embodiment 4 core level high-purity boracic acid
It is in 90 DEG C～100 DEG C of pure water that the high-purity boracic acid without drying and processing that embodiment 3 prepares first is dissolved in temperature, system
H must be contained3BO3The boric acid solution of 220g/L～280g/L, by 3.0～3.5g/L addition ammonium acetates in solution, insulation is filtered,
Under agitation, crystallisation by cooling is to final temperature 20 DEG C～30 DEG C, then solid-liquid separation；So recrystallization 1～2 times, dry, pack
Obtain product.
The preparation method of embodiment 5 high-purity boracic acid
Processing step includes: 1) by industrial boric acid with water Leaching Removal part therein calcium, magnesium, sodium impurity, obtain high-purity
Boric acid presoma；2) high-purity boracic acid presoma is 90 DEG C with temperature～100 DEG C of pure water dissolve, prepare containing H3BO3 240～
The boric acid solution of 280g/L, after compound additive deep iron removal, removing heavy metals, then through filtration, crystallisation by cooling, solid-liquid separation,
Washing, drying, i.e. obtain high-purity boracic acid product.
Described compound additive is the combination of sulfide and ammonia, and the two uses after sizing mixing.
Described sulfide is the combination of any three kinds in ammonium sulfide, barium sulfide, strontium sulfide, Potassium monosulfide., sodium sulfide, and it is used
Measure 15～20 times for chemical reaction metering.
The volume by volume concentration of described ammonia is 5%, and its consumption is 35～45 times of sulfide in mass ratio.
The concrete preparation technology of described high-purity boracic acid presoma is: weighed by industrial boric acid, adds 2～3 times in mass ratio
Water, at a temperature of 25～35 DEG C stir 20～30min, after solid-liquid separation, i.e. obtain high-purity boracic acid presoma.
Containing H in described mother solution after solid-liquid separation3BO355～75g/L, can return to Soaking treatment process and recycle,
When wherein Ca content is accumulate to close to 500mg/L, can be used as preparing the raw material of industrial boric acid or Calcium pyroborate.
The concrete preparation technology of described high-purity boracic acid product is: is dissolved in pure water by high-purity boracic acid presoma, in temperature is
After at 90～100 DEG C, stirring and dissolving obtains boric acid solution, the pH value adding ammonia regulation solution is 5.0～5.3, adds compound adding
Add agent reaction 15～20min, filter, be purified liquid；Then the temperature of scavenging solution is maintained 85～95 DEG C, add dioxygen
Water, stirs 25～30min, makes the S of excess2-It is converted into elementary sulfur or SO4 2-, after filtration, in filtrate add concentration be 40～
The nitric acid of 45wt%, adjusting solution ph is 3.5～4.0, and stirring, crystallisation by cooling to temperature are 25 DEG C～30 DEG C, solid-liquid separation, then
With pure water boric acid crystal, after dehydration, in 65 DEG C of drying high-purity boracic acid products.
Described scavenging solution contains H3BO3 240～280g/L, Fe 0.10～0.2 mg/L.Pb 0.10～0.15 mg/L.Remove
Before ferrum, leachate iron content 4～8mg/L, lead content are Pb 1.0～2.0 mg/L.
The addition of described hydrogen peroxide is the 0.6～0.8% of boric acid solution volume.
Described high-purity boracic acid product, its Na content ＜ 30 × 10-6, Fe content ＜ 5 × 10-6, Pb content ＜ 1 × 10-6。
The preparation method of embodiment 6 core level high-purity boracic acid
It is in 80 DEG C～95 DEG C of pure water that the high-purity boracic acid without drying and processing that embodiment 5 prepares first is dissolved in temperature, system
H must be contained3BO3 The boric acid solution of 180g/L～250g/L, by 2.5～3.5g/L addition ammonium nitrate or ammonium acetates in solution,
Insulation filter, through mechanical agitation, crystallisation by cooling to final temperature 15 DEG C～30 DEG C, recrystallization 1～2 times, be then centrifuged for dehydration, dry,
Packaging into products.
The preparation of embodiment 7 high-purity boracic acid presoma
Primary industry boric acid contains Ca 0.06%, Mg 0.05%, Na 0.035%, Fe0.0052%、Pb0.001%.For with
Lower example 7.1～7.4.
Example 7.1 takes 1000.0g industrial boric acid, is added in the water that 4000mL temperature is 10 DEG C, stirs 60min, mistake
Filter, dries to obtain high-purity boracic acid presoma 867.1g in 65 DEG C；Through to analyze its Ca content be 0.03%, Mg content is 0.009%, Na contains
Amount is 0.021%, and Fe content is 0.0043%.Its Ca removal efficiency is 56.65%, and Mg removal efficiency is 84.39%, and Na removal efficiency is
47.97%, Fe removal efficiency is 28.30%, B2O3The response rate is 86.71%.
Example 7.2 takes 1000.0g industrial boric acid, is added in the water that 2000mL temperature is 20 DEG C, stirs 20min, mistake
Filter, dries to obtain high-purity boracic acid presoma 909.6g in 65 DEG C；Through to analyze its Ca content be 0.028%, Mg content is 0.010%, Na
Content is 0.024 %, and Fe content is 0.0045%.Its Ca removal efficiency is 57.55%, and Mg removal efficiency is 81.81%, and Na removal efficiency is
37.63%, Fe removal efficiency is 18.14%, B2O3The response rate is 90.96%.
Example 7.3 takes 1000.0g industrial boric acid, is added in the water that 1500mL temperature is 35 DEG C, stirs 40min, mistake
Filter, dries to obtain high-purity boracic acid presoma 914.1g in 65 DEG C；Through to analyze its Ca content be 0.031%, Mg content is 0.011%, Na
Content is 0.025%, and Fe content is 0.0046%.Its Ca removal efficiency is 52.77%, and Mg removal efficiency is 79.89%, and Na removal efficiency is
34.71%, Fe removal efficiency is 15.90%, B2O3The response rate is 91.41%.
Example 7.4 takes 1000.0g industrial boric acid, is added in the water that 3000mL temperature is 15 DEG C, stirs 30min, mistake
Filter, dries to obtain high-purity boracic acid presoma 881.2g in 65 DEG C；Through to analyze its Ca content be 0.029%, Mg content be 0.010%,
Na content is 0.023 %, and Fe content is 0.0043%.Its Ca removal efficiency is 55.48%, and Mg removal efficiency is 82.38%, Na removal efficiency
Being 42.09%, Fe removal efficiency is 27.13%, B2O3The response rate is 88.12%.
The preparation of embodiment 8 high-purity boracic acid product
The each 850.0g of high-purity boracic acid presoma that in Example 7, example 7.1-7.4 prepares respectively, fully mixes it.Take
Sample is analyzed, its H3BO3Content is 99.53%, and Ca content is 0.030%, Mg content is 0.010%, Na content is 0.023 %, Fe
Content is 0.0044%, and Pb content is 0.0008%.For example 8 below .1～8.4.
Example 8.1 takes above-mentioned mixed high-purity boracic acid presoma 400.0g, dissolves with the pure water that temperature is 80 DEG C, it is thus achieved that
H3BO3Content be 180.05 g/L, Fe content be 8.0mg/L, Pb content be the solution 2210ml of 1.5mg/L.It it is 80 DEG C in temperature
～at 85 DEG C, the pH value adding proper ammonia regulation solution is 5.3, adds the industrial barium sulfide 0.87g that BaS content is 66%
(10 times of chemical equation metering, size mixing with the ammonia of 26ml 5%), stirring reaction 30min, then it is warming up to 95 DEG C, filter,
Scavenging solution 2185ml.
Scavenging solution contains H3BO3 182.1g/L、Fe 0.22mg/L、Pb 0.21mg/L.At temperature is 80 DEG C～85 DEG C, add
Enter 4.5ml hydrogen peroxide, stir 20min, filter.Adding the dust technology regulation solution ph that concentration is 42% in filtrate is 4.0,
Stirring, crystallisation by cooling to 15 DEG C, filter, with 160ml pure water boric acid, be then dehydrated, and is dried, obtains high-purity boracic acid at 68 DEG C
Product 320.6g, this high-purity boracic acid contains Fe 2.6 × 10-6, containing Pb 1.7 × 10-6, containing Na 15 × 10-6。
This example boric acid crystallization output capacity is 80.16%.
Crystalline mother solution 1749ml, containing H3BO3 41.7g/L.Product washing 165ml, containing H3BO3 41.2g/L。
Example 8.2 takes above-mentioned high-purity boracic acid presoma 400.0g, dissolves with the pure water that temperature is 90 DEG C, it is thus achieved that H3BO3Content
Be 240.16 g/L, Fe content be 10.7mg/L, Pb content be the solution 1658ml of 1.9mg/L.It it is 90 DEG C～95 DEG C in temperature
Under, the pH value adding proper ammonia regulation solution is 5.0, adds the industrial barium sulfide 2.61g(chemistry that BaS content is 66% anti-
Answer that formula is measured 30 times, size mixing with the ammonia of 105ml 5%), stirring reaction 15min, filters, obtains scavenging solution 1660ml.
Scavenging solution contains Fe 0.10mg/ L, Pb 0.11mg/l.At temperature is 90 DEG C～95 DEG C, add 16ml hydrogen peroxide,
Stirring 20min, filters.Adding the dust technology regulation solution ph that concentration is 42% in filtrate is 2.5, and stirring, crystallisation by cooling are extremely
20 DEG C, filter, with 160ml pure water boric acid, be then dehydrated, be dried at 65 DEG C, obtain high-purity boracic acid product 328.1g, this height
Pure boric acid contains Fe 1.0 × 10-6, containing Pb 0.7 × 10-6, containing Na 16 × 10-6。
This example boric acid crystallization output capacity is 82.03%.
Crystalline mother solution 1290ml, containing H3BO3 48.22g/ L.Product washing 166ml, containing H3BO3 47.56g/ L。
Example 8.3 takes above-mentioned high-purity boracic acid presoma 400.0g, dissolves with the pure water that temperature is 95 DEG C, it is thus achieved that H3BO3Content
Be 280.0 g/L, Fe content be 12.5mg/L, Pb content be the solution 1421ml of 2.3mg/L.It it is 90 DEG C～95 DEG C in temperature
Under, the pH value adding proper ammonia regulation solution is 5.1, adds Na2S content is the industrial sodium sulfide 0.88gization of 60.0%
Learn reaction equation metering 20 times, size mixing with the ammonia of 53ml 5%), stirring reaction 20min, filters, obtains scavenging solution 1406ml.
Scavenging solution 0.15mg/ L Han Fe0.21mg/L, Pb.At temperature is 90 DEG C～95 DEG C, add 10ml hydrogen peroxide,
Stirring 20min, filters.Adding the dust technology regulation solution ph that concentration is 42% in filtrate is 3.0, and stirring, crystallisation by cooling are extremely
30 DEG C, filter, with 160ml pure water boric acid, be then dehydrated, be dried at 68 DEG C, obtain high-purity boracic acid product 324.1g, this height
Pure boric acid contains Fe1.8 × 10-6, containing Pb 0.9 × 10-6, containing Na 33 × 10-6。
This example boric acid crystallization output capacity is 81.03%.
Crystalline mother solution 1035ml, containing H3BO3 62.85g/l.Product washing 165ml, containing H3BO3 62.60g/l。
Example 8.4 takes high-quality industrial boric acid, and (its major impurity content is respectively Ca 0.019%, Mg 0.010%, Na
0.022 %, Fe 0.0015%, Pb 0.0007%) 400.0g, dissolves with the pure water that temperature is 90 DEG C, it is thus achieved that H3BO3Content is
240.20 g/L, Fe content be 3.6mg/L, Pb content be the solution 1660ml of 1.7mg/L.At temperature is 90 DEG C～95 DEG C,
The pH value adding proper ammonia regulation solution is 5.1, adds the industrial barium sulfide 0.86g(chemical reaction that BaS content is 66%
30 times of formula metering, size mixing with the ammonia of 35ml 5%), stirring reaction 15min, filters, obtains scavenging solution 1660ml.
Scavenging solution contains Fe 0.15mg/ L, Pb 0.12mg/l.At temperature is 90 DEG C～95 DEG C, add 6ml hydrogen peroxide,
Stirring 20min, filters.Adding the dust technology regulation solution ph that concentration is 42% in filtrate is 3.0, and stirring, crystallisation by cooling are extremely
20 DEG C, filter, with 150ml pure water boric acid, be then dehydrated, be dried at 65 DEG C, obtain high-purity boracic acid product 328.7g, this height
Pure boric acid contains Fe 1.4 × 10-6, containing Pb 0.7 × 10-6, containing Na 14 × 10-6。
This example boric acid crystallization output capacity is 82.18%.
Crystalline mother solution 1293ml, containing H3BO3 48.19g/ L.Product washing 155ml, containing H3BO3 47.70g/ L。
The experiment condition of example 8.5 reference example 8.1 and method, with high-purity boracic acid presoma as raw material, take different sulfurations
Thing and combinations thereof prepares high-purity boracic acid product, and its high-purity boracic acid product major impurity index is shown in Table 1.
It can be seen that take high-purity boracic acid product prepared by different composite additive of the present invention, its boric acid product
Na content ＜ 40 × 10-6, Fe content ＜ 3 × 10-6, Pb content ＜ 2 × 10-6。
Embodiment 9 high-purity boracic acid recrystallization prepares core level high-purity boracic acid product
8 high-purity boracic acid products that example 8.1-8.3, example 8.5 in embodiment 8 prepare respectively are taken 300g, and 2400g altogether, by it
Fully mixing.Its H3BO3Content is 99.85%, and major impurity content is Fe 1.9 × 10-6、、Na 19×10-6、Ca 18×10-6、Mg 6×10-6、Pb 1.0×10-6、SO4 2- 22×10-6, for example 9.1-9.3.
9.1 recrystallization of example prepare core level high-purity boracic acid
Take 333.0g high-purity boracic acid, 6.5g ammonium nitrate (analytical pure), be dissolved in the pure of 1590ml temperature 90 DEG C～95 DEG C
In water, gained boric acid solution contains H3BO3 180.02g/L、NH4NO3 3.5g/L.Temperature 80 DEG C after filtration, add appropriate nitric acid and adjust
The pH value of joint solution is 4.0, is 10 DEG C by its mechanical agitation, crystallisation by cooling to temperature, and stirring, crystallisation by cooling 10h filter, with
200ml pure water washs in two times.By boric acid crystal in 70 DEG C of drying, obtain boric acid product 271.52 g ((numbered 1#Product), its
Fe content is 1.2 × 10-6, Ca content be 3.5 × 10-6, Mg content be 1.0 × 10-6, Na content be 3.0 × 10-6、SO4 2-Content
It is 2.5 × 10-6、Cl-Content is 1 × 10-6。
This example boric acid recrystallization output capacity is 81.54%.
Above-mentioned several the impurity indexs of this example have reached China nuclear power station user requirement to high-purity boracic acid.
Example 9.2 secondary recrystallization prepares core level high-purity boracic acid
Take 333.0g high-purity boracic acid, 6.5g ammonium acetate (analytical pure), be dissolved in the pure of 1375ml temperature 90 DEG C～95 DEG C
In water, gained boric acid solution contains H3BO3 204.3g/L、NH4NO3 4.0g/L.In temperature 85 DEG C after filtration, add appropriate nitric acid and adjust
The pH value of joint solution is 3.5, is 20 DEG C by its mechanical agitation, crystallisation by cooling to temperature；Stirring, crystallisation by cooling time are 8h, mistake
Filter, washs in two times with 200ml pure water.By boric acid crystal in 65 DEG C of drying, obtaining boric acid product 258.7g, its Fe content is 1.2
×10-6, Ca content be 3 × 10-6, Na content be 4 × 10-6、SO4 2-Content is 2.2 × 10-6。
Taking recrystallization high-purity boracic acid of 235.0g, 2.1g ammonium nitrate (analytical pure), being dissolved in 665ml temperature is 90 DEG C
～in the pure water of 95 DEG C, gained boric acid solution contains H3BO3 280.0g/L、NH4NO3 2.5g/L.By its mechanical agitation, crystallisation by cooling
To 20 DEG C (time 6h), filter, wash in two times with 150ml pure water.By product in 68 DEG C of drying, obtain boric acid product 197.5 g
(numbered 2#Product), its Fe content is 0.7 × 10-6, Ca content is 0.9 × 10-6, Mg content be 0.5 × 10-6, Na content be
0.8×10-6、SO4 2-Content is 1.0 × 10-6、Cl-Content is 0.7 × 10-6.Above-mentioned several impurity indexs all reach China's nuclear power
Stand user's requirement to high-purity boracic acid.
Example 9.3 recrystallization mother liquor and the process of washing liquid
The H of the recrystallization test solution used of example 9.1,9.23BO3Initial content about 180g/L-280g/L, is cooled to 20 DEG C
Time mother solution H3BO3Content about 48g/L.Scrubbed, drying, the single productivity about 77.0% of boric acid, additionally there is the H of about 20%3BO3
It is present in knot mother solution, the H of about 3%3BO3It is present in washing liquid.Should return to improve the response rate of boric acid, crystalline mother solution and washing liquid
Return and utilize.
Each crystalline mother solution and washing liquid major impurity content are shown in Table 2.
Being returned by each mother solution and use once, the most each mother solution is warming up to about 95 DEG C and dissolves corresponding boric acid raw material, so
Afterwards by aforesaid mode crystallisation by cooling, carrying out the washing first of product with corresponding crystallization washing liquid, new wash water consumption is the same, enters
Row secondary recrystallization, the high purity acid product (numbered 3 of output#Product) its Fe content is 0.8 × 10-6, Ca content be 1.3 ×
10-6, Mg content be 0.8 × 10-6, Na content be 1.0 × 10-6, SO4 2-Content is 1.5 × 10-6.Above-mentioned impurity content closes equally
The symbol nuclear power user prescription to high-purity boracic acid.
Recycle after secondary, can be used as primary crystallization mother solution and primary crystallization washing liquid to prepare boric acid presoma Jie
Primary crystallization mother solution (also can be used as to prepare the raw material of low ferrum boric acid) by matter, and one time recrystallization mother liquor is used as subsequent cycle for the first time
The molten material medium of crystallization；Recrystallization washing liquid and secondary recrystallization mother solution are used as the molten material of subsequent cycle recrystallization for the first time and are situated between
Matter；Carry out secondary recrystallization, the high purity acid product (numbered 4 of output#Product) its Fe content is 0.8 × 10-6, Ca content be
1.6×10-6, Mg content be 1.0 × 10-6, Na content be 1.5 × 10-6, SO4 2-Content is 1.7 × 10-6.Circulate and so forth
Operation, the recrystallization operation of boric acid prepares high-purity boracic acid, H3BO3Direct recovery rate up to about 80%.
The core level high-purity boracic acid product quality indicator that embodiment 9 prepares is shown in Table 3.
As can be seen from Table 3:
1, its impurity content of prepared high-purity boracic acid all meets China nuclear industry user prescription to high-purity boracic acid
Index.
2, the known core level high-purity boracic acid obtained by external import, its10B abundance ＞ 19.6%.After testing, prepared by the present invention
The core level high-purity boracic acid obtained its10B abundance is 19.61%～19.65%, product10B content closes symbol requirement.
Claims (7)
1. the preparation method of a high-purity boracic acid, it is characterised in that: comprise the following steps that:
1) industrial boric acid sized mixing with water, stir removing calcium, magnesium, sodium impurity, after solid-liquid separation, obtain high-purity boracic acid presoma；
2) high-purity boracic acid presoma is 80 DEG C with temperature～100 DEG C of pure water dissolve, prepare containing H3BO3 180g/L's～280g/L
Boric acid solution, after compound additive deep iron removal, removing heavy metals, then through filtration, crystallisation by cooling, solid-liquid separation, wash, dry
Dry, i.e. obtain high-purity boracic acid product；
Described compound additive is the combination of sulfide and ammonia, and the two uses after sizing mixing；
Described sulfide is any one in ammonium sulfide, barium sulfide, strontium sulfide, Potassium monosulfide., sodium sulfide, or any two kinds
Or the combination of three kinds, and 10～30 times that the consumption of sulfide is chemical reaction metering；
The volume by volume concentration of described ammonia is 5%, and its consumption is 30～60 times of sulfide in mass ratio.
The preparation method of high-purity boracic acid the most according to claim 1, it is characterised in that: by step 2) do not carry out drying and processing
High-purity boracic acid is dissolved in pure water, through 1～2 recrystallization, is dehydrated, dries, i.e. obtains core level high-purity boracic acid product.
The preparation method of high-purity boracic acid the most according to claim 1, it is characterised in that: described high-purity boracic acid presoma concrete
Preparation technology is: weighed by industrial boric acid, adds the pure water of 1.5～4 times in mass ratio, stirs 20 at a temperature of 10～35 DEG C
～60min, after solid-liquid separation, i.e. obtain high-purity boracic acid presoma.
The preparation method of high-purity boracic acid the most according to claim 1, it is characterised in that: step 2) described in high-purity boracic acid before
Drive body to substitute with industrial boric acid high-class product, the Ca content of this high-class product industrial boric acid < 0.032%, Mg content < 0.015%, Fe content
< 0.002%, Na content < 0.03%.
The preparation method of high-purity boracic acid the most according to claim 1, it is characterised in that: the concrete system of described high-purity boracic acid product
Standby technique is: high-purity boracic acid presoma step 1) prepared adds in the pure water that temperature is 80 DEG C～100 DEG C, and stirring and dissolving obtains
After boric acid solution, the pH value adding ammonia regulation solution is 4.6～5.3, adds compound additive reaction 15～30min, mistake
Filter, obtains scavenging solution；Then the temperature of scavenging solution is maintained 70～95 DEG C, add hydrogen peroxide, stir 15～30min, make excess
S2-It is converted into elementary sulfur or SO4 2-, after filtration, in filtrate, add the nitric acid that mass concentration is 40～45%, adjust solution ph
Being 2.5～4.0, stirring, crystallisation by cooling to temperature are 10 DEG C～30 DEG C, solid-liquid separation, then with pure water boric acid crystal, through de-
After water, in 60 DEG C～70 DEG C of drying high-purity boracic acid products；Described high-purity boracic acid product, its Na content ＜ 40 × 10-6, Fe contains
Amount ＜ 5 × 10-6, Pb content ＜ 2 × 10-6。
The preparation method of high-purity boracic acid the most according to claim 5, it is characterised in that: the addition of described hydrogen peroxide is boric acid
The 0.2～1.0% of liquor capacity.
The preparation method of high-purity boracic acid the most according to claim 2, it is characterised in that: the tool of described core level high-purity boracic acid product
Preparation process is: it is in 80 DEG C～100 DEG C of pure water that high-purity boracic acid product is first dissolved in temperature, prepares containing H3BO3 180g/L～
The boric acid solution of 280g/L, by 1.5～2.5g/L addition ammonium nitrate or ammonium acetates in solution, insulation is filtered, at stirring bar
Under part, crystallisation by cooling is to final temperature 10 DEG C～30 DEG C, then solid-liquid separation；So recrystallization 1～2 times, dry, pack and i.e. obtain core level
High-purity boracic acid product.
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| CN114249332B (en) * | 2020-09-23 | 2023-06-13 | 南通新宙邦电子材料有限公司 | Anti-caking boric acid treatment method and system |
| CN113816393B (en) * | 2021-10-19 | 2023-03-17 | 青海利亚达化工有限公司 | Iron removal method for preparing high-purity boric acid |
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| CN114349016B (en) * | 2021-12-23 | 2023-03-03 | 大连理工大学 | Method for removing trace calcium in high-purity boric acid |
| CN115196647B (en) * | 2022-06-29 | 2023-06-23 | 中国石油大学(北京) | Sheet boric acid and preparation method thereof |
| CN115636420A (en) * | 2022-10-18 | 2023-01-24 | 广东先导微电子科技有限公司 | High-purity boron oxide preparation system and preparation process thereof |
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| CN102001675A (en) * | 2010-12-10 | 2011-04-06 | 大连理工大学 | Method for preparing nuclear power-grade high-purity boracic acid |
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|---|---|---|---|---|
| US4756894A (en) * | 1986-01-29 | 1988-07-12 | Materias Primas Magdalena S.A.DE C.V. | Process for the obtainment of boric acid from colemanite and/or howlite minerals |
| CN101209844A (en) * | 2006-12-31 | 2008-07-02 | 肖莹 | Technique for preparing high quality boric acid from salt lake type boron ore by one-step method |
| CN101585543A (en) * | 2009-07-08 | 2009-11-25 | 成都市蜀阳硼业化工有限公司 | Method for preparing special boric acid of special glass through oxidization and precipitation |
| CN102001675A (en) * | 2010-12-10 | 2011-04-06 | 大连理工大学 | Method for preparing nuclear power-grade high-purity boracic acid |
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