WO2013020396A1 - 一种以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶石的循环制备方法 - Google Patents
一种以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶石的循环制备方法 Download PDFInfo
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- WO2013020396A1 WO2013020396A1 PCT/CN2012/074948 CN2012074948W WO2013020396A1 WO 2013020396 A1 WO2013020396 A1 WO 2013020396A1 CN 2012074948 W CN2012074948 W CN 2012074948W WO 2013020396 A1 WO2013020396 A1 WO 2013020396A1
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- sodium
- cryolite
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- acid
- aluminum
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- 239000011734 sodium Substances 0.000 title claims abstract description 49
- 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 title claims abstract description 45
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 45
- 229910001610 cryolite Inorganic materials 0.000 title claims abstract description 36
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 title claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 boron anhydride Chemical class 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 10
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000009969 flowable effect Effects 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C01B35/02—Boron; Borides
- C01B35/023—Boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
- C01B35/06—Boron halogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/76—Double salts, i.e. compounds containing, besides aluminium and sulfate ions, only other cations, e.g. alums
- C01F7/762—Ammonium or alkali metal aluminium sulfates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/18—Electrolytes
Definitions
- the invention relates to a method for preparing elemental boron, in particular to a recyclable preparation method for producing elemental boron with sodium fluoroborate as intermediate material and simultaneously producing low molecular ratio sodium cryolite.
- the raw materials are mainly boric acid and magnesium powder.
- the industrial boric acid is placed on a stainless steel plate and placed in a tube furnace.
- the boronic anhydride is pulverized to 80 mesh, and the magnesium powder is thoroughly mixed with the ratio of 3:1 (mass ratio), and then charged into the reaction tube under vacuum, in the tube In the furnace, the reduction reaction is carried out at 850 ⁇ 900 °C to reduce the boron trioxide to elemental boron.
- the material is soaked in water for two days, and then boiled in hydrochloric acid for four hours to remove impurities such as magnesium oxide, and then washed with water to remove acid.
- impurities such as magnesium oxide
- the above-mentioned boron powder may be added to five times the mass of boron trioxide, and then heated to 800-850 ° C in a reaction furnace under vacuum. And keep it for 3 ⁇ 4 hours, then take out the material and use water to remove excess boronic anhydride. After pickling and washing with water, it is filtered and dried to obtain boron powder with a boron content of more than 90%.
- the main characteristics of the above two methods are low yield, high preparation cost, and the content of the obtained product is generally less than 90%.
- the invention provides a cyclic preparation method for producing elemental boron by using sodium fluoroborate as an intermediate material and synchronizing the production of sodium cryolite, comprising the following steps:
- a method for preparing a low molecular weight low temperature aluminum electrolyte (sodium cryolite) having a molecular weight of 126 and a method for extracting and utilizing fluorine in a sodium cryolite
- the protection method of fluorite resource extension, the by-product sodium cryolite has a good application prospect, and can recycle the by-product sodium cryolite.
- the process flow is simple, short and clean, the overall manufacturing cost is low, the production efficiency is high, and the environmental pollution is reduced.
- the aluminum is liquid aluminum, is added to the reactor in a dropping manner, or the aluminum metal is first placed in the reactor, and after being melted, the reactor is flow-dried.
- Sodium fluoroborate the completion degree of the reaction can be greater than or equal to 95%.
- the inert gas is argon.
- the element boron is produced.
- it has the characteristics of simple preparation process, high production yield and boron content of more than 90%, and can be used as an intermediate material for further production of various boride and boron metal alloys.
- the fluorine element in the sodium cryolite can be recycled and utilized, it is beneficial to realize the extension of the life of the fluorite resource and reduce the pollution to the environment.
- FIG. 1 is a process route diagram for preparing elemental boron and sodium cryolite according to the present invention.
- FIG. 2 is a process flow diagram of the preparation of elemental boron and sodium cryolite according to the present invention.
- 0.62 tons of boric acid or 0.35 tons of boric anhydride is placed in the reaction vessel, and 4 tons of hydrofluoric acid having a mass percentage of 20% is added to react at 10CTC to form fluoroboric acid; and 3 tons of mass percent of fluoroboric acid is added to 20 %
- the sodium carbonate aqueous solution reacts to form sodium fluoroborate, which is concentrated, crystallized and rinsed to obtain 0.95 tons of sodium fluoroborate intermediate material; 0.95 tons of dried sodium fluoroborate is placed in another reactor, and vacuum is applied to argon gas.
- the temperature is raised to 700 ° C, and the aluminum liquid is slowly added dropwise to the reactor according to the reaction ratio, and the mixture is stirred rapidly.
- the reaction is completed to form elemental boron and sodium cryolite; the molten liquid sodium cryolite is extracted, cooled and broken.
- the obtained aqueous solution of hydrofluoric acid can be recycled to the front end for leaching boric acid or boron oxide, thereby achieving the purpose of recycling the intermediate raw material sodium fluoroborate.
- 0.62 tons of boric acid or 0.35 tons of boric anhydride is placed in the reaction vessel, and 4 tons of hydrofluoric acid having a mass percentage of 20% is added to react at 10CTC to form fluoroboric acid; and 3 tons of mass percent of fluoroboric acid is added to 20
- the sodium carbonate aqueous solution is reacted to form sodium fluoroborate. After concentration, crystallization and rinsing, 0.95 tons of sodium fluoroborate intermediate material is obtained.
- the aluminum is placed in another reactor according to the reaction ratio, and argon gas is introduced after vacuuming. The temperature was raised to 700 °C, and the dry flow dynamic sodium fluoroborate 0.95 ton was added to the reactor in a meterable flow manner, and the mixture was stirred rapidly.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
本发明公开了一种以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶石的循环制备方法，包括如下步骤：A）往硼酸或硼酐中加入氢氟酸反应生成氟硼酸；B）往氟硼酸中加入碳酸钠溶液，浓缩结晶得到氟硼酸钠；C）将氟硼酸钠放入反应器中，加入铝反应生成单质硼和钠冰晶石；或者将铝放入反应器中，加入氟硼酸钠反应生成单质硼和钠冰晶石；D）将钠冰晶石抽出，与浓硫酸送入旋转反应釜中，反应生成氟化氢气体以及硫酸铝钠，收集氟化氢气体并溶于水得到氢氟酸；E）所获得的氢氟酸循环至步骤A中用于对硼酸或硼酐实施浸取。本发明可对副产物钠冰晶石循环利用，缩短了单质硼制备的工艺流程，降低了综合生产成本，提高了生产效率，减少了环境污染。
Description
一种以氟硼酸钠为中间原料生产单质硼并同步产出 钠冰晶石的循环制备方法
技术领域
本发明涉及单质硼的制备方法，尤其涉及一种以氟硼酸钠为中间原料生产单 质硼并同步产出低分子比的钠冰晶石的可循环制备方法。
背景技术
工业上生产元素硼一般为下述两种方法：
( 1 ) 镁还原法： 原料主要是硼酸和镁粉， 将工业硼酸置于不锈钢盘上， 装 入管式炉中， 在减压条件下匀速升温至 25CTC ，使硼酸脱水生成硼酐： 2H3B03=B203+3H20; 将硼酐粉碎至 80 目， 与镁粉按 3: 1 (质量比) 的配料比 充分混合后装入反应管中， 在真空条件下， 在管式炉中， 于 850~900°C进行还原 反应，使三氧化二硼还原为元素硼，此反应是热反应，很快就能完成： B203+3Mg =3MgO+2B; 将反应完成的物料用水浸泡两天， 然后在盐酸中煮沸四小时， 以除 去氧化镁等杂质， 再经水洗去酸， 为了除去杂质需要在相同条件下重复一次酸洗 和水洗， 即得硼含量为 85%左右的硼粉， 为了提高硼的质量， 进一步把镁除掉， 可将上述硼粉加入五倍质量的三氧化二硼混匀后，在真空条件下反应炉内加热至 800~850°C， 并保持 3~4小时， 然后取出物料， 用水去过量的硼酐， 再经酸洗和 水洗后， 过滤， 烘干， 即得硼含量大于 90%的硼粉。
(2) 铝还原法： 通常是以工业品硼砂为原料， 在常压下置于温度在 750°C 以上的熔炉里脱去 10个结晶水成无水物四硼酸钠， 经冷却、 粗碎、 细碎后， 按一定配比与硫磺、 铝粉充分混合， 投入铸铁反应炉， 在高温下反应： Na2B407+4Al=4B+Na2Al204+Al203; 冷却后将熔块从炉中取出并粉碎， 先用 盐酸浸洗， 再用氢氟酸浸洗， 然后水洗和碱洗 （用 5%的 NaOH溶液)， 最后 再用水洗， 经分离、 干燥即得元素硼。
以上两种方法主要的特点是得率低，制备成本高， 所得产品的含量一般低于 90%。
工业上制备氟铝酸钠（钠冰晶石）的制备方法一般为合成法： 将无水氢氟酸 与氢氧化铝反应，生成氟铝酸，然后在高温下与氢氧化钠反应，再经过滤、烘干、
熔融、破碎，制得氟铝酸钠产品，其反应如下： 6HF+A1(0H)3 =A1F3-3HF+3H20 ， A1F3-3HF+3K0H =Na3AlF6+3H20;用此法合成的钠冰晶石其相对分子量为 209.94， 分子式为： AlF3.mNaF (m=3.0) ， 熔点为 1000°C， 一般地用工业合成法制得的钠 冰晶石其分子比为 m=2.0~3.0之间， 难以获得分子比 m=1.0~1.5之间较为纯净的 低分子量钠冰晶石。
发明内容
为解决现有技术中如何大规模工业化生产获取较为纯净的低分子比钠冰晶 石制备的问题， 以满足低温铝电解工业对电解质的需求， 发明人在中间原料的选 择以及副产物的循环处理方面进行了大量的探索，预料不到地发现， 以氟硼酸钠 为中间原料采取热化学还原的方法生产单质硼的同时可同步产出分子比 m=1.0 的低分子量钠冰晶石， 并且若对该钠冰晶石实施进一步的化学反应， 可实现循环 生产单质硼的目的。本发明工艺简单，与传统的流行制备方法比较，制造成本低， 所获得的产品质量高， 并可实现副产物的循环利用， 提高了生产效率并减少了环 境的污染。
本发明提供一种以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶石的 循环制备方法， 包括如下步骤：
A) 往硼酸或硼酐中加入氢氟酸， 在 100~200°C反应生成氟硼酸； 涉及的化学反 应为：
H3B03+4HF =HBF4+3H20, B203+8HF =2HBF4+3H20 ；
B) 往氟硼酸中加入碳酸钠水溶液反应生成氟硼酸钠溶液， 经浓縮、 结晶、 漂洗 ； 涉 及 的 化 学 反 应 为 ：
C) 将干燥的氟硼酸钠放入反应器中， 抽真空后通入惰性气体， 升温至 700-1000 °C , 往反应器中加入铝， 快速搅拌， 反应 4~6h， 生成单质硼和钠冰 晶石； 或者将金属铝放入反应器中， 抽真空后通入惰性气体， 升温至 700~1000°C，往反应器中加入干燥可流动的氟硼酸钠，快速搅拌，反应 4~6h， 生成单质硼和钠冰晶石； 涉及的化学反应为： NaBF4+Al = B+AlF3.NaF;
D) 将熔融的液态钠冰晶石抽出， 冷却后破碎与浓硫酸一起定量送入旋转反应釜 中， 在 400~500°C环境下反应， 生成氟化氢气体以及硫酸铝钠， 收集氟化氢
气体并溶于水得到氢氟酸水溶液； 硫酸铝钠经破碎后与氢氧化钠的水溶液混 合反应， 分离固体氢氧化铝后得到硫酸钠的水溶液； 涉及的化学反应为：
AlF NaF+2H;S04 = 4HFf +Na.Al(S04):
NaAl(SG4)i十 3N.aOH =2 a2SO (OH¾
E) 所获得的氢氟酸水溶液循环至前端用于对硼酸或硼酐实施浸取， 以达到循环 制备中间原料氟硼酸钠的目的。
采用上述技术方案，达到如下目的： 发明了一种制备分子量为 126 的低分 子比低温铝电解质（钠冰晶石）的制备方法、发明一种将钠冰晶石中的氟元素循 环提取利用的对地下萤石资源延伸的保护方法， 副产物钠冰晶石的应用前景好， 可对副产物钠冰晶石循环利用。与传统的单质硼制备方法相比较，工艺流程简单、 短洁、 综合制造成本低、 生产效率高， 减少了对环境的污染。
作为本发明的进一步改进， 所述步骤 C 中， 铝为液态铝， 以滴加的方式加 入反应器中， 或者先将金属铝放入反应器中， 经融熔后向反应器流加干燥的氟硼 酸钠， 本反应的完成度可达大于或等于 95%。
作为本发明的进一步改进， 所述步骤 C中， 惰性气体为氩气。
本发明的有益效果是：发明了一种可用于大规模工业化生产低分子比 m=1.0 的低分子量（钠冰晶石）的工艺制备方法， 以满足低温铝电解工业对电解质的需 求； 本发明同步产出了元素硼， 与现有技术比较， 其具备制备工艺简单、 生产得 率高、硼含量大于 90%的特点，可作为进一步生产各类硼化物和硼金属合金的中 间原料。 同时， 由于钠冰晶石中的氟元素可循环提取利用， 对实现萤石资源寿命 的延伸有益， 减少了对环境的污染。
附图说明
图 1 为本发明单质硼和钠冰晶石制备的工艺路线图。
图 2为本发明单质硼和钠冰晶石制备的工艺流程图。
具体实施方式
下面通过具体实施例对本发明做进一步详细说明。
实施例一
将 0.62吨硼酸或 0.35吨硼酐置于反应釜中， 加入 4吨质量百分含量为 20% 的氢氟酸， 在 10CTC反应生成氟硼酸； 往氟硼酸中加入 3吨质量百分含量为 20%
的碳酸钠水溶液反应生成氟硼酸钠， 经浓縮、 结晶、漂洗后得到氟硼酸钠中间原 料 0.95吨； 将 0.95吨干燥的氟硼酸钠放入另一反应器中， 抽真空后通入氩气， 升温至 700°C， 按反应比例往反应器中缓慢滴加铝液， 快速搅拌， 反应 5h后反 应完全， 生成单质硼和钠冰晶石； 将熔融的液态钠冰晶石抽出， 冷却后破碎， 称 重， 与按反应比例加入的浓硫酸一起定量送入旋转反应釜中， 在 400~500°C环境 下反应， 生成氟化氢气体以及硫酸铝钠， 收集氟化氢气体并溶于水得到氢氟酸； 所获得的氢氟酸水溶液可循环至前端用于对硼酸或氧化硼实施浸取，从而实现循 环制备中间原料氟硼酸钠的目的。
实施例二
将 0.62吨硼酸或 0.35吨硼酐置于反应釜中， 加入 4吨质量百分含量为 20% 的氢氟酸， 在 10CTC反应生成氟硼酸； 往氟硼酸中加入 3吨质量百分含量为 20% 的碳酸钠水溶液反应生成氟硼酸钠， 经浓縮、 结晶、漂洗后得到氟硼酸钠中间原 料 0.95 吨； 按反应比例称取铝置于另一反应器中， 抽真空后通入氩气， 升温至 700 °C , 将干燥流动态的氟硼酸钠 0.95吨以可计量流动的方式加入反应器中， 快 速搅拌， 反应 5h后反应完全， 生成单质硼和钠冰晶石； 将熔融的液态钠冰晶石 抽出， 冷却后破碎， 称重， 与按反应比例加入的浓硫酸一起定量送入旋转反应釜 中， 在 400~500°C环境下反应， 生成氟化氢气体以及硫酸铝钠， 收集氟化氢气体 并溶于水得到氢氟酸；所获得的氢氟酸水溶液可循环至前端用于对硼酸或氧化硼 实施浸取， 从而实现循环制备中间原料氟硼酸钠的目的。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能 认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术 人员来说， 在不脱离本发明构思的前提下， 还可以做出若干简单推演或替换， 都 应当视为属于本发明的保护范围。
Claims
1. 一种以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶石的循环制备方 法， 其特征在于， 包括如下步骤：
A) 往硼酸或硼酐中加入氢氟酸， 在 100~200°C反应生成氟硼酸；
B) 往氟硼酸中加入碳酸钠水溶液反应生成氟硼酸钠溶液， 经浓縮、 结晶、 漂洗 后得到氟硼酸钠中间原料；
C) 将干燥的氟硼酸钠放入反应器中， 抽真空后通入惰性气体， 升温至 700-1000 °C , 往反应器中加入铝， 快速搅拌， 反应 4~6h， 生成单质硼和钠冰晶 石；或者将金属铝放入反应器中，抽真空后通入惰性气体，升温至 700~1000°C， 往反应器中加入干燥可流动的氟硼酸钠， 快速搅拌， 反应 4~6h， 生成单质硼和 钠冰晶石；
D) 将熔融的液态钠冰晶石抽出， 冷却后破碎与浓硫酸一起定量送入旋转反应釜 中， 在 400~500°C环境下反应， 生成氟化氢气体以及硫酸铝钠， 收集氟化氢气体 并溶于水得到氢氟酸水溶液； 硫酸铝钠经破碎后与氢氧化钠的水溶液混合反应， 分离固体氢氧化铝后得到硫酸钠的水溶液；
E) 所获得的氢氟酸水溶液循环至前端用于对硼酸或氧化硼实施浸取， 以达到循 环制备中间原料氟硼酸钠的目的。
2. 根据权利要求 1所述的以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶 石的循环制备方法， 其特征在于： 所述步骤 C中， 铝为液态铝， 以滴加的方 式加入反应器中或者将干燥流动态的氟硼酸钠以可计量流动的方式加入反应 器中。
3. 根据权利要求 1所述的以氟硼酸钠为中间原料生产单质硼并同步产出钠冰晶 石的循环制备方法， 其特征在于： 所述步骤 C中， 惰性气体为氩气。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2666889A1 (en) * | 2012-05-23 | 2013-11-27 | Shenzhen Sunxing Light Alloys Materials Co., Ltd | Sodium cryolite for aluminum electrolysis industry and preparation method thereof |
| CN114933321A (zh) * | 2022-05-24 | 2022-08-23 | 淄博馨泽新材料科技有限公司 | 一种氟铝钾钠的配方及其制备方法 |
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| WO2012159590A1 (zh) * | 2012-05-23 | 2012-11-29 | 深圳市新星轻合金材料股份有限公司 | 铝电解过程中的电解质补充体系及其制备方法 |
| CN109179444B (zh) * | 2018-10-11 | 2020-08-25 | 武汉科技大学 | 一种无定形硼粉的制备方法 |
| CN113955765B (zh) * | 2021-12-22 | 2022-03-01 | 苏州欣诺科生物科技有限公司 | 四氟硼酸银的制备方法 |
| CN115650248B (zh) * | 2022-11-15 | 2024-05-31 | 山东重山光电材料股份有限公司 | 一种硼-10酸生产废液中硼-10的回收方法 |
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| US2810683A (en) * | 1954-09-16 | 1957-10-22 | Callery Chemical Co | Production of elemental boron by fused salt electrolysis |
| WO2003051773A1 (en) * | 2001-12-19 | 2003-06-26 | Groupe Minutia Inc. | Process for the production of elemental boron by solid state reaction |
| JP2006104055A (ja) * | 2004-10-08 | 2006-04-20 | Rohm & Haas Co | 水素化ホウ素ナトリウムの直接元素合成 |
| CN101863662A (zh) * | 2010-07-15 | 2010-10-20 | 武汉工程大学 | 纳米硼粉的制备方法 |
| CN102180474A (zh) * | 2010-11-23 | 2011-09-14 | 王嘉兴 | 一种用硼泥洗液制备单质硼和三氯化铝的方法 |
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| US2692186A (en) * | 1953-06-25 | 1954-10-19 | Kamlet Jonas | Manufacture of sodium fluoride low in silica content |
| JPS4537133B1 (zh) * | 1967-07-26 | 1970-11-25 | ||
| CN102211777A (zh) * | 2011-03-05 | 2011-10-12 | 兰州理工大学 | 一种纯硼的制备方法 |
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- 2012-04-29 WO PCT/CN2012/074948 patent/WO2013020396A1/zh active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2810683A (en) * | 1954-09-16 | 1957-10-22 | Callery Chemical Co | Production of elemental boron by fused salt electrolysis |
| WO2003051773A1 (en) * | 2001-12-19 | 2003-06-26 | Groupe Minutia Inc. | Process for the production of elemental boron by solid state reaction |
| JP2006104055A (ja) * | 2004-10-08 | 2006-04-20 | Rohm & Haas Co | 水素化ホウ素ナトリウムの直接元素合成 |
| CN101863662A (zh) * | 2010-07-15 | 2010-10-20 | 武汉工程大学 | 纳米硼粉的制备方法 |
| CN102180474A (zh) * | 2010-11-23 | 2011-09-14 | 王嘉兴 | 一种用硼泥洗液制备单质硼和三氯化铝的方法 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2666889A1 (en) * | 2012-05-23 | 2013-11-27 | Shenzhen Sunxing Light Alloys Materials Co., Ltd | Sodium cryolite for aluminum electrolysis industry and preparation method thereof |
| CN114933321A (zh) * | 2022-05-24 | 2022-08-23 | 淄博馨泽新材料科技有限公司 | 一种氟铝钾钠的配方及其制备方法 |
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| GB2502496A (en) | 2013-11-27 |
| EP2631217A1 (en) | 2013-08-28 |
| EP2631217B1 (en) | 2017-10-25 |
| CN102583420B (zh) | 2013-03-13 |
| ES2655490T3 (es) | 2018-02-20 |
| CN102583420A (zh) | 2012-07-18 |
| GB201316355D0 (en) | 2013-10-30 |
| US8557209B2 (en) | 2013-10-15 |
| GB2502496B (en) | 2014-04-23 |
| US20130095024A1 (en) | 2013-04-18 |
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