CN104016368B - The xrf analysis preparation method of anhydrous boric acid lithium flux - Google Patents
The xrf analysis preparation method of anhydrous boric acid lithium flux Download PDFInfo
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- CN104016368B CN104016368B CN201410234188.6A CN201410234188A CN104016368B CN 104016368 B CN104016368 B CN 104016368B CN 201410234188 A CN201410234188 A CN 201410234188A CN 104016368 B CN104016368 B CN 104016368B
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- 230000004907 flux Effects 0.000 title claims abstract description 47
- 238000004458 analytical method Methods 0.000 title claims abstract description 44
- RTZKMGZSJBRJFI-UHFFFAOYSA-N boric acid;lithium Chemical compound [Li].OB(O)O RTZKMGZSJBRJFI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000013078 crystal Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004327 boric acid Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 238000009413 insulation Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 5
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 36
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 7
- 239000006210 lotion Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 41
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 18
- 230000007613 environmental effect Effects 0.000 abstract description 3
- -1 Monohydrate lithium hydroxide Chemical class 0.000 abstract 1
- 229960002645 boric acid Drugs 0.000 description 19
- 235000010338 boric acid Nutrition 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 229910013184 LiBO Inorganic materials 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 238000005187 foaming Methods 0.000 description 2
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- 230000000171 quenching effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CBGUOGMQLZIXBE-XGQKBEPLSA-N clobetasol propionate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CCl)(OC(=O)CC)[C@@]1(C)C[C@@H]2O CBGUOGMQLZIXBE-XGQKBEPLSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 210000004940 nucleus Anatomy 0.000 description 1
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- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Analysing Materials By The Use Of Radiation (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The preparation method of xrf analysis anhydrous boric acid lithium flux of the present invention.Monohydrate lithium hydroxide is added in 80 ~ 100 DEG C of pure water or synthesis mother liquid, stir, slowly add boric acid, continue to stir molten clear after, filter, get filtrate under 80 ~ 110 DEG C of conditions, add the lithium tetraborate crystal seed that weight percentage is 1% ~ 3%, insulation reaction 0.5 ~ 5 hour, be cooled to 30 ~ 60 DEG C of insulated and stirred 0 ~ 3 hour, leave standstill 20 ~ 40 minutes, centrifugal solid-liquid is separated, washing obtains lithium tetraborate containing wet crystal, and lithium tetraborate adopts gradient drying technology to carry out drying and dewatering containing wet crystal, obtains anhydrous boric acid lithium flux.The foreign matter content such as present method gained anhydrous boric acid lithium flux Chun Du≤99.99%, K, Na, Ca, Mg, Fe, P, Si, Al is all less than 10ppm, and Song fills Mi Du≤0.65g/cm
-3, size-grade distribution 100 μm ~ 600 μm.The inventive method is simple, and with low cost, product purity is high, and loose density is large, environmental protection.
Description
technical field:
The present invention relates to xrf analysis fusing assistant preparing technical field, be specifically related to the preparation method that a kind of xrf analysis anhydrous boric acid lithium flux comprises anhydrous lithium tetraborate, anhydrous lithium metaborate and both mixed fluxs by a certain percentage.
background technology:
Along with the development of X-ray fluorescence spectra (XRF) analytical technology, the feature that sample technology has quick, high accuracy because of it is prepared in borate melting, finds broad application in industries such as cement, pottery, smeltings.Conventional borate mainly the borate of alkali metal lithium, sodium but the borate of sodium make the easy moisture absorption of fuse piece, can not analyze the sodium in sample, to the specific absorption of X-ray containing shortcomings such as lithium flux are large, at present substantially by the borate of lithium as lithium tetraborate, lithium metaborate and both lithium tetraborate mixed fluxs by a certain percentage thereof replace.In the borate salt system of lithium, lithium atom is little can not be arrived by X-ray detection, thus can not produce interference to the fluorescent line of analytical element.In the borate of lithium, lithium tetraborate is a kind of slightly acidic flux, can melt mutually with basic sample solution; Lithium metaborate is a kind of basic flux, can melt mutually with acidic sample; For in cement, steel industry sample, often comprise acidic oxide and basic oxide, only use lithium tetraborate or lithium metaborate to reach oxide compound in sample is melted completely, and adopt the lithium tetraborate of different ratios and lithium metaborate mixing mixed flux at high temperature can effectively in sample in different acid-base properties of oxides make sample melted reach the uniform state of molecular level, thus stablized, molten sample sheet glass uniformly, reach the object of detection.Lithium tetraborate fusion technology has the advantages such as sample preparation is even, with high accuracy, the cycle is short, analysis cost is low, is more and more subject to each laboratory and adopts.The quality requirements of raising to xrf analysis lithium tetraborate product required analyzing and testing result precision along with client is more and more stricter, domestic and international at present at least 99.99% is greater than to the purity requirement of xrf analysis lithium tetraborate, each foreign matter content requires all to be less than 10ppm, even individual impurities content requirement is less than 5ppm, also has strict regulation to loose density and fine grain content simultaneously: external assay laboratory requires that lithium tetraborate product Song fills Mi Du≤0.9g/cm at present
3, granularity requirements 100 μm ~ 600 μm; Domestic assay laboratory requires that product Song fills Mi Du≤0.55g/cm
3, granularity requirements 200 order screen underflow≤5%, this just has higher requirement to the production technology of lithium tetraborate.
The method of current production xrf analysis lithium tetraborate flux has following several:
Quilonum Retard and boric acid are mixed in proportion low temperature and carry out predrainage by solid phase method, and high temperature solid state reaction generates lithium tetraborate flux.This method quality product is limited to material purity, and the impurity in raw material residues in product substantially entirely, and obtain high purity product and pure Lithium Carbonate and high-purity boracic acid must be adopted as raw material, raw materials cost is high; Secondly, lithium tetraborate solubility promoter at high temperature all to be fluxed erosion action to other material except platinum, for ensureing that product purity must carry out Reactive Synthesis in platinum or platinum yellow precious metal vessel; Finally, in this method preparation process, there is carbon dioxide to discharge, cause product to foam fluffy, loose density is low, fine powder is many, be difficult to meet xrf analysis service requirements.
Liquid phase method adopts lithium hydroxide in industrial grade and technical grade boric acid, respectively after purification, carries out the operations such as liquid phase reaction, crystallization, solid-liquid separation, drying and dewatering by a certain percentage and prepares anhydrous boric acid lithium flux.It is large that this method has generation batch, synthesis temperature is low, product purity is high, the advantages such as product granularity pattern is easy to control, but liquid phase synthesis is the lithium tetraborate crystal of band crystal water, crystal water must be carried out remove and could obtain anhydrous product, lithium tetraborate with crystal water adopts conventional drying and dewatering technology easily to foam, and cause loose density low, fine powder is many.Therefore, the product loose density of current most of liquid phase method synthesis is at 0.5g/cm
3below, be difficult to meet xrf analysis service requirements.Japanese Patent Laid-Open No. Sho 62-96315 adopts liquid phase method synthesis Li
2b
4o
7.3H
2o, but the document needs reaction for a long time in long-time 10 ~ 20 hours, could form the Li of crystallization
2b
4o
7.3H
2o crystal, after domestic patent CN102838125.A adopts lithium hydroxide in industrial grade and technical grade boric acid to purify respectively, in proportion by the lithium hydroxide of purification and boric acid neutralization reaction, reaction solution is concentrated into after turning white and pours Stainless Steel Disc evaporate to dryness into, broken, secondary drying obtains lithium tetraborate powder, 930 ~ 950 DEG C of high-temperature fusion 4 ~ 5 hours again, quenching obtains high-density lithium tetraborate crystal, solution evaporate to dryness caking in this technological process, broken other impurity of easily introducing again, document method production energy consumption is high simultaneously, batch is little, the most important thing is that the impurity of this operational path Raw all will residue in product, product purity is difficult to the requirement reaching xrf analysis reagent, patent CN102910638.A discloses a kind of preparation method of anhydrous lithium metaborate, and this method adopts typical liquid phase synthesis route, but product ultimate analysis finds out that K, Na, Ca, Mg content is higher from this method embodiment, and loose density is not discussed yet and controlled, patent CN1818149A describes and produces high pure and high clear Lithium Tetraborate Single Crystals technology with lithium hydroxide in industrial grade and boric acid, this method synthesis lithium tetraborate mainly applies on electronics monocrystal material, though to product purity done some discuss, individual impurities if Mg content is close to 20ppm, according to the checking of dewatered drying condition, adopt and dehydrate condition described in it, lithium tetraborate product foaming and intumescing, loose density is low, and fine powder is many, weightless higher, xrf analysis quality requirements cannot be met.Adopt liquid phase synthesis lithium tetraborate product foreign matter content higher on the whole at present both at home and abroad, product loose density, granularity are discussed or controlled not, to be difficult to satisfied current xrf analysis to lithium tetraborate quality requirements.
Lithium tetraborate and the operation such as lithium metaborate or Quilonum Retard and boric acid is mixed in proportion, high temperature melting, quenching, fragmentation are obtained lithium tetraborate flux by high-temperature melting method; patent CN101509847A discloses the method for the vitreous reagent preparing xrf analysis bead, this patent describe by lithium tetraborate, lithium metaborate and boric acid in proportion in platinum crucible high-temperature fusion prepare the vitreous reagent of xrf analysis bead.This method product chemical index relies on the purity of raw material and the utensil of use, and easily obtained high purity, pine fill close degree≤1.0g/cm to adopt high-purity raw material and platinum utensil
3product, the at present external xrf analysis lithium tetraborate fusing assistant major part product that is the production of this method.This method needs high-temperature fusion energy consumption large, and product will reach the requirement of xrf analysis reagent quality and high-purity raw material and platinum crucible must be used as melting utensil, and product comprehensive cost is high, and price is high.
summary of the invention:
The object of the invention is to overcome current lithium tetraborate flux production technique not enough, particularly to product purity, the control of granularity and loose density etc., there is provided a kind of production process simple, with low cost, product purity is high, loose density is large, the xrf analysis anhydrous boric acid lithium production technology of production technique environmental protection.
The object of the present invention is achieved like this:
The preparation method of xrf analysis anhydrous boric acid lithium flux of the present invention, comprises the following steps:
1), in the pure water, by solid-to-liquid ratio 1:3 ~ 5 monohydrate lithium hydroxide being dissolved in 80 ~ 100 DEG C or synthesis mother liquid, stir 10 ~ 30 minutes;
2), in the solution of step 1) slowly add boric acid, boric acid add-on is add 105% ~ 210% of monohydrate lithium hydroxide molar weight in step 1), stirs and makes solution clearly molten;
3), by step 2) in the molten clear liquid of reaction filter, with pump, filtrate got to stainless steel jacket reactor, be heated to 80 ~ 110 DEG C, add the lithium tetraborate crystal seed that weight percentage is 1% ~ 3%, insulation reaction 0.5 ~ 5 hour.
4), logical water coolant makes temperature of reaction system be down to 30 ~ 60 DEG C, and insulated and stirred left standstill 20 ~ 40 minutes after 0 ~ 3 hour.
5), by reaction mass pass into whizzer and carry out solid-liquid separation, solid crystal employing pure water, when wash water pH=7 ~ 8, obtain being with the lithium tetraborate of crystal water containing wet crystal, mother liquor and the recycle of wash water centralized collection;
6), lithium tetraborate is loaded stainless steel drip pan containing wet crystal, control Liao Ceng Hou Du≤3cm, being placed in drying plant adopts gradient drying technology to dry 1 ~ 2 hour, 160 ~ 200 DEG C bakings 2 ~ 4 hours at 100 ~ 120 DEG C, 200 ~ 300 DEG C are dried 2 ~ 4 hours, 500 ~ 600 DEG C are dried 1 ~ 3 hour, are met the anhydrous boric acid lithium flux of xrf analysis.
React clear liquid in above-mentioned method to filter and mainly to remove in supplementary material Fe in insolubles and supplementary material
2+, Fe
3+, Mg
2+, PO
4 -3under alkali system, fine insolubles is formed Deng micro impurity element.Other patented technologies mentioned by this patent are then take to filter lithium hydroxide solution and boric acid solution respectively, and this mode only removes the insolubles in starting material, remove not effect to element impurity.
Above-mentioned lithium tetraborate crystal seed is at least the one in lithium tetraborate, lithium metaborate, preferred lithium tetraborate (Li
2b
4o
73H
2o), lithium metaborate (LiBO
2xH
2the mixture of mixture, 50% lithium tetraborate and the 50% lithium metaborate composition that mixture, 35% lithium tetraborate and 65% lithium metaborate that O), 67% lithium tetraborate and 33% lithium metaborate form form.By lithium tetraborate crystal seed, lithium tetraborate granularity and pattern are regulated and controled, make that the lithium tetraborate of generation is large containing wet crystal grain, crystalline structure is complete, smooth surface, the intergranular impurity brought thus carry secretly and particle surface impurity absorption few, improving product quality.
Above-mentioned lithium tetraborate is at least the one in lithium tetraborate or lithium metaborate containing wet crystal.
Purity Fen other≤99.9% of above-mentioned monohydrate lithium hydroxide, boric acid, anhydrous boric acid lithium flux Chun Du≤99.99% prepared provides and ensures more reliably.
In above-mentioned method, the mother liquor of solid-liquid separation returns after collecting and carries out recycle.
The drying plant adopted in above-mentioned method is temperature programmed control box-type furnace, rotary type drying oven, the one in infra-red furnace, continuous tunnel furnace, pusher furnace, meshbeltfurnace, chain type resistance furnace, preferred meshbeltfurnace, chain type resistance furnace, infra-red furnace.
Above-mentioned method can be prepared the foreign matter content such as Chun Du≤99.99%, K, Na, Ca, Mg, Fe, P, Si, Al and all be less than 10ppm, and Song fills Mi Du≤0.65g/cm
3, size-grade distribution meets xrf analysis anhydrous boric acid lithium flux at 100 μm ~ 600 μm, greatly can meet xrf analysis and use field to anhydrous boric acid lithium flux quality requirements.
The present invention relates to chemical principle:
Fe
2++2OH
-→Fe(OH)
2↓（1）
Fe
3++3OH
-→Fe(OH)
3↓（2）
Mg
2++2OH
-→Mg(OH)
2↓（3）
3Li
++PO
4 -3→Li
3PO
4↓（4）
4H
3BO
3+2LiOH·H
2O→Li
2B
4O
7·3H
2O+6H
2O（5）
H
3BO
3+LiOH·H
2O→LiBO
2·xH
2O+H
2O（6）
Li
2B
4O
7·3H
2O→Li
2B
4O
7+3H
2O（7）
LiBO
2·xH
2O→LiBO
2+2H
2O（8）
Compared with prior art, the inventive method has the following advantages:
1, adopt the starting material of Chun Du≤99.9% to prepare the foreign matter content such as Chun Du≤99.99%, K, Na, Ca, Mg, Fe, P, Si, Al by preparation method of the present invention and be all less than 10ppm anhydrous boric acid lithium product.
2, add lithium tetraborate crystal seed to be formed to nucleus, synthesize that crystalline structure is complete, grain is large, the lithium tetraborate of size-grade distribution 100 μm ~ 600 μm is containing wet crystal, the employing gradient drying technology of novelty, control moisture and deviate from speed, solve the liquid phase method synthesis lithium tetraborate dehydration technical barrier that easily foaming is fluffy, fine powder is many.The anhydrous boric acid lithium flux product Song adopting the art of this patent to prepare fills Mi Du≤0.65g/cm
3.
3, adopt the inventive method to prepare to have the foreign matter content such as Chun Du≤99.99%, K, Na, Ca, Mg, Fe, P, Si, Al and be all less than 10ppm, Song fills Mi Du≤0.65g/cm
3, size-grade distribution 100 μm ~ 600 μm meet
xfluorometric analysis anhydrous boric acid lithium flux.
4, adopt the inventive method a direct step can generate lithium tetraborate and the lithium metaborate mixing lithium tetraborate flux of different ratios by adjustment proportioning raw materials, solve the direct uniform in quality sex chromosome mosaicism brought with anhydrous lithium tetraborate and anhydrous lithium metaborate mechanical-physical mixture manufacturing anhydrous boric acid lithium flux.Compare solid phase method simultaneously, anhydrous boric acid lithium flux production technique that high-temperature melting method lithium tetraborate mixes with lithium metaborate different ratios, this law, without the need to high temperature, without the need to the platinum utensil of costliness, reduces production cost greatly.
5, mother liquid recycling in the inventive method, non-pollution discharge is the xrf analysis anhydrous boric acid lithium flux production technique of a kind of low cost, environmental protection.
accompanying drawing illustrates:
Fig. 1 is the Lithium Tetraborate Single Crystals XRD diffracting spectrum of the band crystal water of embodiment 1 liquid phase synthesis.
Fig. 2 is the lithium metaborate crystal XRD diffracting spectrum of the band crystal water of embodiment 2 liquid phase synthesis.
Fig. 3 is the lithium metaborate crystal XRD diffracting spectrum of the band crystal water of embodiment 3 liquid phase synthesis.
Fig. 4 be embodiment 4 synthesize consist of 67% lithium tetraborate and 33% lithium metaborate mixed flux XRD diffracting spectrum.
Fig. 5 be commercially available Solid phase synthesis consist of 67% lithium tetraborate and 33% lithium metaborate mixed flux XRD diffracting spectrum.
embodiment:
The raw material related in following embodiment is Chun Du≤99.9% of the applicant's manufacture order water lithium hydroxide and boric acid.Chun Du≤99.9% boric acid and monohydrate lithium hydroxide all can be buied from market, also obtain by adopting technical grade product recrystallization.
Embodiment 1:
9.25kg monohydrate lithium hydroxide is dropped in the pure water of 40kg temperature 80 DEG C, stir 15 minutes, then boric acid 28kg is slowly added, stir molten clear rear filtration, with pump filtrate got in 100L stainless steel jacket reactor and continue to be heated to 100 DEG C, add 0.2kg lithium tetraborate crystal seed, insulation reaction 4 hours; System temperature is down to 60 DEG C by logical water coolant, and material passes into whizzer and carries out solid-liquid separation, pure water, detects washing lotion pH=7 ~ 8, stops washing, and continuation centrifuge dehydration obtains the lithium tetraborate (Li containing crystal water
2b
4o
73H
2o) containing wet crystal, after filtrate collection, utilization is returned to.Dry containing wet crystal sabot, bed thickness 3cm, be placed in infra-red furnace and adopt gradient drying technology to dry 2 hours, 180 DEG C bakings 3 hours at 120 DEG C, 300 DEG C are dried 4 hours, and 500 DEG C are dried 2 hours, obtain anhydrous lithium tetraborate 16.4kg.By XRD diffraction analysis, the intensity of the lithium tetraborate diffraction peak of the band crystal water of this embodiment synthesis and go out peak position with Li
2b
4o
73H
2o standard card is consistent, as shown in Figure 1.Product is through analysis of chemical elements, and purity is greater than more than 99.99%, foreign matter content analysis in table 2.
Embodiment 2:
7kg monohydrate lithium hydroxide drops in the pure water of 30kg temperature 90 DEG C, stirs 20 minutes, then slowly adds boric acid 10.5kg, stir molten clear rear filtration, filter pump is got to 100L stainless steel jacket reactor and is heated to 90 DEG C, adds 0.15kg lithium metaborate crystal seed, insulation reaction 0.5 hour; Logical water coolant makes system temperature be down to 50 DEG C, insulated and stirred 1.5 hours, standing sedimentation 20 minutes; Material passes into whizzer and carries out solid-liquid separation, pure water, detects washing lotion pH=7 ~ 8, stops washing, continues centrifuge dehydration and obtains containing crystal water lithium metaborate (LiBO
2xH
2o) containing wet crystal; Mother liquor Collection utilization.Dry containing wet crystal sabot, bed thickness 2cm, be placed in infra-red furnace and adopt gradient oven dry to dry 4 hours 120 DEG C of bakings 1 hour, 160 DEG C, 260 DEG C are dried 3 hours, and 500 DEG C of bakings obtain anhydrous lithium metaborate flux 7.5kg for 2 hours.Synthesis wet feed by XRD diffraction analysis, the intensity of diffraction peak and go out peak position with standard card 27-1223Li
2b
2o
44H
2o is consistent, as shown in Figure 2.Product is through chemical analysis, and purity is greater than more than 99.99%, foreign matter content analysis in table 2.
Embodiment 3:
7kg monohydrate lithium hydroxide drops in the mother liquor of 28kg temperature 90 DEG C, stirs 30 minutes, then slowly adds boric acid 10.6kg, stir molten clear rear filtration, filter pump is got to stainless steel cauldron and is heated to 90 DEG C, adds 0.2kg lithium metaborate crystal seed, insulation reaction 1 hour; Logical water coolant makes system temperature be down to 30 DEG C, insulated and stirred 1.5 hours, standing sedimentation 30 minutes; Material passes into whizzer and carries out solid-liquid separation, pure water, detects washing lotion pH=7 ~ 8, stops washing, continues centrifuge dehydration and obtains containing crystal water lithium metaborate (LiBO
2xH
2o) containing wet crystal; Mother liquor Collection utilization.Wet feed sabot is dried, bed thickness 2cm, and be placed in infra-red furnace and adopt gradient to dry 120 DEG C of bakings, 2 hours, 160 DEG C bakings 4 hours, 280 DEG C are dried 4 hours, and 600 DEG C are dried 3 hours, obtain anhydrous lithium metaborate flux 7.62kg.Should containing wet crystal by XRD diffraction analysis, the intensity of diffraction peak and go out peak position with standard card 51-0514LiBO28H
2o is consistent, as shown in Figure 3.Product is greater than 99.99% through chemical analysis purity, foreign matter content analysis in table 2.
Embodiment 4:
9.25kg monohydrate lithium hydroxide is dropped in the synthesis mother liquid of 40L temperature 110 DEG C, stir 20 minutes, then boric acid 22.1kg is slowly added, stir molten clear rear filtration, filter pump is got to stainless steel cauldron and is heated to 100 DEG C, add 0.3kg67% lithium tetraborate and 33% lithium metaborate mixture as crystal seed, insulation reaction 4 hours; System temperature is down to 50 DEG C by logical water coolant, material is passed into whizzer and carries out solid-liquid separation by insulated and stirred after 1.5 hours, pure water, detect washing lotion pH=7 ~ 8, stop washing, continue centrifuge dehydration to obtain mixing with lithium metaborate containing wet crystal containing the lithium tetraborate of crystal water, after filtrate collection, return to utilization.Dry containing wet crystal sabot, bed thickness 3cm, being placed in infra-red furnace adopts gradient drying technology to dry 2 hours, 180 DEG C bakings, 3 hours, 250 DEG C bakings 3 hours at 120 DEG C, and 550 DEG C are dried 2 hours, obtain anhydrous lithium tetraborate and anhydrous lithium metaborate mixed flux product 13.5kg.Product is by XRD diffraction analysis, and this lithium tetraborate mixed flux is made up of lithium tetraborate and lithium metaborate, and XRD diffracting spectrum and analysis of chemical elements all with 67%Li commercially available at present
2b
4o
7with 33%LiBO
2the lithium tetraborate mixed flux of composition is consistent, as shown in Figure 4,5.Product purity is greater than more than 99.99%, and other impurity analysis are in table 2.Table 1 is for the present embodiment is with current commercially available 67%Li
2b
4o
7with 33%LiBO
2the analysis of lithium tetraborate mixed flux contrasts.
Table 1
| Lithium tetraborate mixed flux | Purity (%) | Li 2O(%) | B 2O 3(%) |
| Commercially available 6733 products | 99.9 | 21.5 | 78.5 |
| The present embodiment product | >99.99 | 21.6 | 78.4 |
Embodiment 5:
The high-purity monohydrate lithium hydroxide of 8.0kg is dropped in the synthesis mother liquid of 40L temperature 90 DEG C, stir 20 minutes, then boric acid 16.5kg is slowly added, stir molten clear rear filtration, filter pump is got to 100L stainless steel jacket reactor and is heated to 100 DEG C, add 0.2kg35% lithium tetraborate and 65% lithium metaborate mixture as crystal seed, insulation reaction 3 hours; System temperature is down to 40 DEG C by logical water coolant, material is passed into whizzer and carries out solid-liquid separation by insulated and stirred after 2 hours, pure water, detect washing lotion pH=7 ~ 8, stop washing, continue centrifuge dehydration to obtain mixing with lithium metaborate containing wet crystal containing the lithium tetraborate of crystal water, after filtrate collection, return to utilization.Wet feed sabot is dried, bed thickness 2cm, and be placed in infra-red furnace and adopt gradient drying technology to dry 2 hours, 160 DEG C bakings, 4 hours, 260 DEG C bakings 3 hours at 120 DEG C, 550 DEG C are dried 3 hours, obtain anhydrous lithium tetraborate and anhydrous lithium metaborate mixed flux product 10.7kg.Commercialization Epidemiological Analysis Li
2o accounts for 44.6%, B
2o
3account for 55.1%, with commercially available 35%Li
2b
4o
7with 65%LiBO
2the mixed flux Li of mixing composition
2o, B
2o
3content is consistent.
Table 2: the lithium tetraborate product ultimate analysis that the embodiment of the present invention is obtained:
The various embodiments described above are further described foregoing of the present invention, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to above-described embodiment.All technology realized based on foregoing all belong to scope of the present invention.
Claims (6)
- The 1.X fluorometric analysis preparation method of anhydrous boric acid lithium flux, this preparation method comprises the following steps:1), by solid-liquid weight ratio 1: 3 ~ 5 monohydrate lithium hydroxide is dropped in the pure water of 80 ~ 100 DEG C or mother liquor, stirs 10 ~ 30 minutes, the purity Fen of monohydrate lithium hydroxide, boric acid Bie≤99.9%;2), in the solution in step 1) slowly add boric acid, boric acid add-on is 105% ~ 210% of monohydrate lithium hydroxide molar weight, stirs and makes solution clearly molten;3), by step 2) in solution filter, with pump, filtrate is got in stainless steel jacket reactor, is heated to 80 ~ 110 DEG C, add weight percentage be the lithium tetraborate of 1% ~ 3% as crystal seed, insulation reaction 0.5 ~ 5 hour;4), logical water coolant makes system temperature be down to 30 ~ 60 DEG C, and insulated and stirred 0 ~ 3 hour, leaves standstill 20 ~ 40 minutes;5), by reaction mass pass into whizzer and carry out solid-liquid separation, solid crystal adopts pure water, controls washing lotion pH=7 ~ 8, obtains being with the lithium tetraborate of crystal water containing wet crystal, mother liquor and the recycle of wash water centralized collection;6), the lithium tetraborate of band crystal water is loaded stainless steel drip pan containing wet crystal, bed thickness Kong Zhi≤3cm, being placed in drying plant adopts gradient drying technology to dry 1 ~ 2 hour, 160 ~ 200 DEG C bakings 2 ~ 4 hours at 100 ~ 120 DEG C, 200 ~ 300 DEG C are dried 2 ~ 4 hours, and 500 ~ 600 DEG C of bakings obtain anhydrous boric acid lithium flux for 1 ~ 3 hour.
- 2. the preparation method of xrf analysis anhydrous boric acid lithium flux according to claim 1, is characterized in that lithium tetraborate crystal seed is at least the one in lithium tetraborate, lithium metaborate.
- 3. according to claim 1 and 2 xthe fluorometric analysis preparation method of anhydrous boric acid lithium flux, is characterized in that the lithium tetraborate synthesized is at least the one in lithium tetraborate, lithium metaborate containing wet crystal.
- 4. according to claim 1 and 2 xthe fluorometric analysis preparation method of anhydrous boric acid lithium flux, is characterized in that the drying plant adopted is the one in temperature programmed control box-type furnace, rotary type drying oven, infra-red furnace, continuous tunnel furnace, pusher furnace, meshbeltfurnace, chain type resistance furnace.
- 5. according to claim 1 and 2 xthe fluorometric analysis preparation method of anhydrous boric acid lithium flux, is characterized in that returning after the mother liquor of solid-liquid separation is collected carrying out recycle.
- 6. according to claim 1 and 2 xthe fluorometric analysis preparation method of anhydrous boric acid lithium flux, it is characterized in that preparing according to the method to have Chun Du≤99.99%, K, Na, Ca, Mg, Fe, P, Si, Al foreign matter content is all less than 10ppm, and Song fills Mi Du≤0.65g/cm 3, size-grade distribution 100 μm ~ 600 μm meet xfluorometric analysis anhydrous boric acid lithium flux.
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| CN102838125A (en) * | 2012-09-19 | 2012-12-26 | 湖北百杰瑞新材料有限公司 | Preparation method of high-purity and high-density lithium tetraborate |
| CN102910638A (en) * | 2012-11-15 | 2013-02-06 | 湖北百杰瑞新材料有限公司 | Preparation method of anhydrous lithium metaborate |
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| CN1818149A (en) * | 2005-06-22 | 2006-08-16 | 广州锐鑫锂能新材料科技有限公司 | Production of high-purity lithium tetraborate crystal by industrial lithium hydroxide and boric acid |
| AU2011218725A1 (en) * | 2011-09-02 | 2013-03-21 | Xrf Chemicals Pty Ltd | Lithium X-Ray Flux Composition by Dissolution |
| CN102838125A (en) * | 2012-09-19 | 2012-12-26 | 湖北百杰瑞新材料有限公司 | Preparation method of high-purity and high-density lithium tetraborate |
| CN102910638A (en) * | 2012-11-15 | 2013-02-06 | 湖北百杰瑞新材料有限公司 | Preparation method of anhydrous lithium metaborate |
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