CN1789373A - Preparation method of fluorescent grade strontium carbonate - Google Patents
Preparation method of fluorescent grade strontium carbonate Download PDFInfo
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- CN1789373A CN1789373A CN 200510022069 CN200510022069A CN1789373A CN 1789373 A CN1789373 A CN 1789373A CN 200510022069 CN200510022069 CN 200510022069 CN 200510022069 A CN200510022069 A CN 200510022069A CN 1789373 A CN1789373 A CN 1789373A
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- strontium
- strontium carbonate
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- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 title claims abstract description 58
- 229910000018 strontium carbonate Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 29
- 229910052788 barium Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 229910052745 lead Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000007796 conventional method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- -1 hydrogen strontium oxide Chemical class 0.000 claims description 4
- SYJBLFMEUQWNFD-UHFFFAOYSA-N magnesium strontium Chemical compound [Mg].[Sr] SYJBLFMEUQWNFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical class [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 159000000011 group IA salts Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000011572 manganese Substances 0.000 description 5
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical class [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of fluorescent grade strontium carbonate, which comprises removing Fe, Pb and other heavy metal impurities and Ba, Ca impurities in raw materials, and adding into strontium salt solution and NH4HCO3Adding beneficial components to the solution, or adding NH as it is synthesized4HCO3Solution or CO2Adding beneficial components into the gas, and performing synthesis reaction, filtering, washing and drying to obtain a product; the SrCO of the fluorescent grade strontium carbonate product3Although the content is only 95-99.5%, the material used as the raw material of the super-long afterglow light-storing luminescent material has excellent service performance, namely the material can be used for producing the light-storing luminescent material with the initial brightness of more than or equal to 25000mcd/m260min afterglow luminance not less than 80mcd/m2The high-quality rare earth super-long afterglow light-storing luminescent material greatly improves the luminescent performance, so that the fluorescent grade strontium carbonate product has high cost performance.
Description
Technical field
The present invention relates to a kind of inorganic chemical product preparing strontium carbonate method, particularly relate to a kind of preparation method who is used to produce the fluorescence grade strontium carbonate of rare earth overlength afterglow light-accumulating luminous material.
Background technology
High-purity strontium carbonate (SrCO
3) be a kind of important inorganic chemical product.Along with the high speed development of industry such as electronics, information, the usage quantity of high-purity strontium carbonate increases year by year, and in general its purity requirement is also more and more higher.The topmost purposes of high-purity strontium carbonate is fluorescent material and electronic component two aspects.The electronic-grade high-purity strontium carbonate requires its median size D usually
50＜1 μ m; Fluorescence level high-purity strontium carbonate is because prescription, the technology of each rare earth overlength afterglow light-accumulating luminous material producer are slightly variant, and its median size has D
50＜1 μ m, D
505 μ m ±, D
50Different stage such as 10 μ m ± wait.
Fluorescence level high-purity strontium carbonate requires its SrCO usually
3Content 〉=99.5% or SrCO
3Content promptly reaches the requirement of analytical pure Strontium carbonate powder at least 〉=99.0%, heavy metal content such as Pb, Ni all≤0.0001%, Ca＜0.03%, Ba＜0.04%, Fe＜0.001%.
But the fluorescence grade strontium carbonate product does not still have unified national standard at present, and each manufacturer carries out company standard.Table 1 is domestic two its fluorescence grade strontium carbonate quality index of tame high-purity strontium carbonate factory.
The homemade fluorescence level of table 1 high-purity strontium carbonate quality index
| Product index | SrCO 3 | Ba | Ca | Fe | Pb | Ni | Cl | Na | H 2O | D 50 (μm) |
| A factory | 99.9 | 0.0044 | 0.0032 | 0.00066 | 0.00008 | 0.0001 | / | / | / | 0.3 |
| B factory | ＞99.5 | ＜0.04 | ＜0.03 | ＜0.001 | ＜0.0001 | / | ＜0.003 | ＜0.003 | ＜0.5 | ＜0.7 |
Annotate: above-mentioned SrCO
3Its appearance of product is irregularly shaped
The luminous of fluorescent material or phosphor material is material directly is converted to the energy that its inside absorbs in some way nonequilibrium radiation without the overheated stage phenomenon.The overlength afterglow luminescent material is commonly called as " glowing powder ", belongs to a kind of of embedded photoluminescent material, is meant through light source short irradiations such as daylight and long wave ultraviolets, close light source after, still can in a very long time, continue luminous material.To such material, weigh the quality of its luminescent properties usually with original intensity and two indexs of after-glow brightness.
In recent years, the development of rare earth aluminate and rare earth silicate overlength afterglow light-accumulating luminous material and production have obtained further development in China, existing such more than 20 families of manufacturing enterprise.Such luminescent material of producing has been widely used in cove lighting and Emergency Light facility, aviation, navigation and fields such as automobile instrument display panel and industrial art coating.Homemade rare earth overlength afterglow light-accumulating luminous material and corresponding goods are except that many fields (subway, service station, fire-fighting emergent system etc.) are applied at home, also find a good sale in more than 40 countries and regions such as the U.S., Germany, Japan, China has become world rare earth overlength afterglow light-accumulating luminous material big producing country, and its production technology also is in advanced international standard in general.In order further to improve competition capability, domestic main rare earth overlength afterglow light-accumulating luminous material manufacturing enterprise is still constantly carrying out promoting the effort of its product price ratio.
At present, with homemade common fluorescence level high-purity strontium carbonate (SrCO
318000 yuan/ton of content 99.5%, prices) be raw material, its original intensity of overlength afterglow light-accumulating luminous material of production is 15000mcd/m
2About, the 60min after-glow brightness is 50mcd/m
2About.With the good slightly fluorescence level high-purity strontium carbonate (SrCO of quality
3Content＞99.5%) be raw material, can produce original intensity is 20000-22000mcd/m
2, the 60min after-glow brightness is 60mcd/m
2About luminescent material.With the higher fluorescence level high-purity strontium carbonate of purity (as SrCO
3The Strontium carbonate powder that purity 99.9%, price are about 32000 yuan/ton) is raw material, can produces original intensity 〉=25000mcd/m
2, 60min after-glow brightness 〉=70mcd/m
2High-quality rare earth overlength afterglow light-accumulating luminous material, but its production cost is higher, it is applied be restricted.Therefore, produce light-accumulating luminous material, press for exploitation a kind of moderate cost (about 22000 yuan/ton of prices) with excellent luminescent properties, and the fluorescence grade strontium carbonate product of use properties excellence.
Existing fluorescence grade strontium carbonate is a raw material with strontium salt such as strontium nitrate, strontium chloride, strontium hydroxides normally, after repeatedly recrystallization is purified, carry out building-up reactions with bicarbonate of ammonia that passes through purification or carbonic acid gas again and prepare high-purity strontium carbonate, its production cost of products is higher, and is more outstanding away from places of origin of raw materials person.But production cost is low, and the preparation method of the superior fluorescence level high-purity strontium carbonate of use properties does not appear in the newspapers so far.
Summary of the invention:
The present invention is intended to overcome above-mentioned defective, and the preparation method of the low and fluorescence grade strontium carbonate that use properties is superior of a kind of production cost is provided.This fluorescence grade strontium carbonate can be used for producing original intensity 〉=25000mcd/m
2, 60min after-glow brightness 〉=80mcd/m
2High-quality rare earth overlength afterglow light-accumulating luminous material, have the high ratio of performance to price.
The concrete technical scheme that the present invention adopts is as follows:
The preparation method of fluorescence grade strontium carbonate comprises beavy metal impurities such as the Fe, the Pb that remove in the raw material and Ba, Ca impurity, it is characterized in that: by at strontium salt solution and NH
4HCO
3Add useful component in the solution or when synthetic with the NH that adds
4HCO
3Solution or CO
2Gas adds useful component together, makes product through synthetic reaction, filtration, washing, drying, and its concrete processing step is as follows:
The removal of A, Fe, Pb, Ni impurity: industrial strontium salt is dissolved in 40～100 ℃ the pure water, remove contained Fe, Pb, Ni impurity according to a conventional method, Pb in this strontium salt solution, Ni content all＜0.2mg/L, Fe content＜0.8mg/L, Sr content 80～260g/L;
Described industrial strontium salt comprises industrial Sr (NO
3)
2, SrCl
26H
2O, Sr (OH)
28H
2O and industrial magnesium strontium.
When being raw material with the industrial magnesium strontium, with water it is sized mixing earlier, with technical hydrochloric acid or industrial nitric acid its dissolving being obtained Sr content again is the strontium salt solution of 80～260g/L, and then removes beavy metal impurities such as Fe, Pb according to a conventional method.
The removal of B, Ba, Ca impurity:, remove Ba, Ca impurity by recrystallization method or chemical method with the above-mentioned strontium salt solution of removing behind Fe, the Pb.
1) recrystallization method removes Ca, Ba
With the SrCl that removes behind the heavy metals such as Fe, Pb
2Or Sr (NO
3)
2Strontium salt solution is warming up to 100～110 ℃, evaporation concentration to 42～52 ° Be ', and blowing cools off in crystallizer tank and separates out crystal then.By a recrystallization, can remove in the raw material 60～90% Ca and 40～90% Ba.
If is raw material with the industrial hydrogen strontium oxide, then earlier it is dissolved in temperature and is in 95～100 ℃ the pure water, blowing cools off in crystallizer tank and separates out Sr (OH) then
28H
2The O crystal.
2) chemical reaction method removes Ca, Ba
Remove Ba:
Under 30～100 ℃ temperature condition, press chemical equation metering and in strontium salt solution, add sulfuric acid and vitriol for 2～15 times, stirring reaction 20～120min can remove 80～95% Ba in the raw material.
Preferred (the NH of described vitriol
4)
2SO
4
Remove Ca:
Strontium salt solution is warming up to 40～100 ℃, with ammoniacal liquor or Sr (OH)
28H
2O regulator solution pH value is 5～10, extraordinarily goes into NH by chemical equation metering 2～10
4F or NaF, reaction 30～180min, filtration can be removed 60～85% Ca in the raw material.
When the strontium salt intermediate raw material after steps A and step B handle was crystal, its Ca content was 0.005～0.10%, Ba content is 0.005～0.08%, Pb, Ni content all＜0.0001%, Fe content is 0.0001～0.0015%.
If the strontium salt intermediate raw material after steps A and step B processing is a strontium salt solution, then be scaled corresponding SrCl
26H
2O or Sr (NO
3)
2
C, the useful component synthesizing strontium carbonate of interpolation
The strontium salt solution that will obtain after steps A and step B processing is warming up to 40～95 ℃, adds the H that accounts for solid strontium salt weight 0.2～0.5%
2O
2, or add useful component again, fully stir after-filtration.Then filtrate is pumped in the reactor, temperature rises to 40～95 ℃, under agitation condition, adds 1.05～1.35 times of product weights, and the NH after removing the Fe purifying treatment
4HCO
3Solution or CO
2(its consumption is for pressing 1.1～1.8 times that chemical equation measures), slow simultaneously salt and the useful component of alkaline salt that drips rare earth class or facile hydrolysis continues stirring reaction 30～80min, promptly gets the Strontium carbonate powder material.
If the strontium salt intermediate raw material after steps A and step B processing is SrCl
26H
2O or Sr (NO
3)
2Crystal then need be dissolved in earlier in the pure water, and C carries out set by step again.
Described useful component comprises:
(1) single mineral compound or the organic compound of rare earth element Eu, Dy, Tm, Yb, Ce, Pr, La, Nd, Sm, Tb, Er, Lu, Gd, Ho, Y, Sc, or the mineral compound or the organic compound of arbitrary proportion combination, its content range in Strontium carbonate powder is: 0.0001～0.2%;
(2) single mineral compound or the organic compound of non-rare earth Si, Al, Mn, Sb, Zn, Mg, Sn, Bi, Li, Ga, Ge, In, F and P, or the mineral compound or the organic compound of arbitrary proportion combination, its content range in Strontium carbonate powder is: 0.0008～0.8%.
D, synthetic, filtration, washing, drying
To filter through step C reaction synthetic Strontium carbonate powder material, be 40～90 ℃ pure water then with temperature, press the weight ratio washing leaching cake of wash water/product=15～30, again filter cake is packed after drying under 100～220 ℃ the temperature at last, promptly make fluorescence grade strontium carbonate product of the present invention.
SrCO in the fluorescence grade strontium carbonate product of the present invention
3Content is 95～99.5%, Ca content is 0.01～0.3%, Ba content is 0.01～0.2%.Wherein, SrCO
3The representative value of content is 96.5～98.5%.
The present invention compares with prior art, has the following advantages:
1, prior art is to use pure as far as possible strontium salt solution (as SrCl
2Solution, Sr (NO
3)
2Solution or Sr (OH)
2Solution), reach pure as far as possible NH
4HCO
3Solution or CO through purifying
2Gas avoids various impurity to enter product (Ca＜0.03%, Ba＜0.04%) in the building-up process simultaneously as far as possible, reaches SrCO to guarantee product
3The high purity of content 〉=99.5% satisfies the conventional requirement of overlength afterglow light-accumulating luminous material raw material, and its production cost is higher.
The present invention then only needs appropriateness to remove Ca, Ba, and the product that allows to make has higher Ca (0.05～0.3%), Ba (0.04～0.2%) content, saved the dark expense of removing Ca, Ba, thereby its production cost is relatively low.
2, prior art is under 150～500 ℃ temperature condition the Strontium carbonate powder filter cake to be dried, and the present invention only needs to carry out the oven dry of product 100～220 ℃ lower temperature range, and is energy-conservation more remarkable.
3, prior art wash water consumption is generally wash water/product (weight ratio)=35～50, and wash water consumption of the present invention then is wash water/product (weight ratio)=15～30, has saved water resources more significantly.
4, the present invention is by adding useful component, though the SrCO of product
3Content only is 95～99.5%, but has good use properties as the raw material of overlength afterglow light-accumulating luminous material, promptly can be used for producing original intensity 〉=25000mcd/m
2, 60min after-glow brightness 〉=80mcd/m
2The main raw material(s) of high-quality rare earth overlength afterglow light-accumulating luminous material, help improving greatly the luminescent properties of this luminescent material, have the high ratio of performance to price.
Embodiment
Embodiment 1
With SrCl
26H
2O is a raw material
With industrial strontium salt SrCl
26H
2O is dissolved in 40～80 ℃ the pure water, removes contained Fe, Pb impurity according to a conventional method, and through recrystallization remove Ba, Ca impurity makes SrCl
26H
2O, this SrCl
26H
2O Ca content is 0.027%, Ba content is 0.029%, Pb, Ni content all＜0.0001%, Fe content is 0.0006%.With 48Kg SrCl
26H
2O is dissolved in and obtains the solution that Sr content is 140g/L in the pure water, is warming up to 65 ℃, adds 150mlH
2O
2, add 2.3gMn again
2+(introducing) with the manganese acetate form, 2.2gMg
2+(introducing with the magnesium chloride form), stirring reaction 30min filters, and gets SrCl
2Solution.With this SrCl
2Solution is squeezed in the reactor that volume is 300L, is warming up to 75 ℃, adds under agitation condition and contains NH
4HCO
330.9Kg NH
4HCO
3Scavenging solution slowly drips the lanthanum chloride solution that contains La0.22g simultaneously.Finish NH
4HCO
3Solution and lanthanum chloride solution, continuing stirring reaction 50min, filter, is 750 liters of thorough washing filter cakes of pure water of 40～85 ℃ again with temperature, then with the Strontium carbonate powder filter cake (containing attached water 30%) that obtains in 100～220 ℃ of oven dry, promptly get fluorescence grade strontium carbonate product (26.2Kg).
Its SrCO of this product
3Content is 97.1%, and Ca content is 0.052%, Ba content is 0.051%, Mn, Mg, La content are respectively 0.0077%, 0.0055%, 0.0008%, Pb content＜0.0001%, Ni content 0.00009%.
Synthetic finishing contains NH in the synthesis mother liquid of filtration gained
4Cl (NH
4 +27g/L), can be used for producing industrial ammonium chloride.
Embodiment 2
With Sr (NO
3)
2Be raw material
Strontium nitrate after a recrystallization is removed impurity such as Ba, Ca, Ca content are 0.025%, Ba content is 0.031%, Pb, Ni content all＜0.0001%, Fe content is 0.0003%.120 kilograms of strontium nitrates are dissolved in the solution that obtains containing Sr 147g/L in the pure water, it is warming up to 70 ℃, add 300mlH
2O
2, add 11gMn again
2+(introducing) with the manganous nitrate form, 8gMg
2+(introducing with the magnesium chloride form) after fully stirring, filters, and gets Sr (NO
3)
2Solution.Then it is squeezed in the reactor that volume is 1000L with pump, is warming up to 65 ℃, under agitation condition, add through purification and NH
4HCO
3Solution (contains NH
4HCO
3100Kg).Adding NH
4HCO
3In the time of solution, slowly drip the sodium silicate solution that contains Si 10.5g, finish NH
4HCO
3And water glass, continuing stirring reaction 40min, blowing filters.Be 1850 liters of thorough washing filter cakes of pure water of 40～85 ℃ then with temperature, will under 110～200 ℃ of temperature, dry through the Strontium carbonate powder filter cake that washing obtains again, promptly get fluorescence grade strontium carbonate product (84.2Kg).
Its SrCO of this product
3Content is 98.5%, and Ca content is 0.036%, Ba content is 0.045%, Mn, Mg, Si content are respectively 0.011%, 0.0076%, 0.012%, and Pb content is 0.00009%.Synthesis mother liquid can be used for producing industrial ammonium nitrate.
Embodiment 3
With Sr (OH)
28H
2O is a raw material
Will be through the conventional 100kg Sr (OH) that removes Fe, Pb and a recrystallization acquisition
28H
2It is in 90～100 ℃ the pure water that O is dissolved in 650 intensification degree, adds 280 liters of NH down in 80～90 ℃ temperature, agitation condition
4HCO
3Scavenging solution (contains NH
4HCO
364Kg), drip MnCl simultaneously
2(Mn
2+10.2g), NdCl
3(Nd
3+0.58g), SbCl
3(Sb
3+0.9g) solution.Reinforced finishing continues stirring reaction 50min again, and blowing filters, and is 1070 liters of washing leaching cakes of pure water of 40～70 ℃ then with temperature, will wash the Strontium carbonate powder filter cake that obtains again and dry under 100～220 ℃ temperature, promptly gets fluorescence grade strontium carbonate product 53.4Kg.
This product contains SrCO
399.0%, contain Ca 0.019%, contain Ba 0.028%, contain Pb0.0001%, contain Mn 0.017%, contain Nd 0.001%, contain Sb 0.0015%.
Embodiment 4 fluorescence grade strontium carbonates are used contrast experiment's data
Being produced fluorescence level carbonic acid with A factory, B factory and the present invention respectively is main raw material, adds high-purity Al by certain prescription
2O
3, high-purity H
3BO
3, high-purity Eu
2O
3, high-purity Dy
2O
3Deng, thorough mixing.Press high temperature solid phase synthesis and produce rare earth overlength afterglow light-accumulating luminous material.Its luminous index of the overlength afterglow light-accumulating luminous material of output sees Table 2.
Table 2 is its luminescent properties contrast of overlength afterglow light-accumulating luminous material of feedstock production with different fluorescence grade strontium carbonates
| The fluorescence level SrCO that uses 3 | The luminous index of overlength afterglow light-accumulating luminous material of output | |
| Original intensity | The 60min after-glow brightness | |
| (mcd/m 2) | ||
| A SrCO that factory produces 3(purity 99.9%) | 25000～26000 | 70～100 |
| B SrCO that factory produces 3(content＞99.5%) | 20000～21000 | 55 |
| SrCO that the present invention produces 3(content 97%) | ＞25000 | 80～140 |
Claims (8)
1, the preparation method of fluorescence grade strontium carbonate comprises beavy metal impurities such as the Fe, the Pb that remove in the raw material and Ba, Ca impurity, it is characterized in that: by at strontium salt solution and NH
4HCO
3Add useful component in the solution or when synthetic with the NH that adds
4HCO
3Solution or CO
2Gas adds useful component together, makes product through synthetic reaction, filtration, washing, drying, and its concrete processing step is as follows:
The removal of A, Fe, Pb, Ni impurity: industrial strontium salt is dissolved in 40～100 ℃ the pure water, removes contained Fe, Pb, Ni impurity according to a conventional method;
The removal of B, Ba, Ca impurity:, remove Ba, Ca impurity by recrystallization method or chemical method with the above-mentioned strontium salt solution of removing behind Fe, the Pb;
1) recrystallization method removes Ca, Ba
With the SrCl that removes behind Fe, the Pb heavy metal
2Or Sr (NO
3)
2Strontium salt solution is warming up to 100～110 ℃, evaporation concentration to 42～52
0Be ', blowing cools off in crystallizer tank and separates out crystal then;
If is raw material with the industrial hydrogen strontium oxide, then earlier it is dissolved in temperature and is in 95～100 ℃ the pure water, blowing cools off in crystallizer tank and separates out Sr (OH) then
28H
2The O crystal;
2) chemical reaction method removes Ca, Ba
Remove Ba: under 30～100 ℃ temperature condition, in strontium salt solution, add sulfuric acid and vitriol for 2～15 times by stoichiometry, stirring reaction 20～120min, 80～95% Ba is removed in the raw material;
Remove Ca: strontium salt solution is warming up to 40～100 ℃, with ammoniacal liquor or Sr (OH)
28H
2O regulator solution pH value is 5～10, extraordinarily goes into NH by chemical equation metering 2～10
4F or NaF, reaction 30～180min filters, and 50～85% Ca is removed in the raw material;
C, the useful component synthesizing strontium carbonate of interpolation
The strontium salt solution that will obtain after steps A and step B processing is warming up to 40～95 ℃, adds the H that accounts for solid strontium salt weight 0.2～0.5%
2O
2, or add useful component again, fully stir after-filtration.Then filtrate is pumped in the reactor, temperature rises to 40～95 ℃, under agitation condition, adds 1.05～1.35 times of product weights, and the NH after removing the Fe purifying treatment
4HCO
3Solution or CO
2, 1.1～1.8 times meterings of its consumption for pressing chemical equation, slow simultaneously salt and the useful component of alkaline salt that drips rare earth class or facile hydrolysis continues stirring reaction 30～80min, promptly gets the Strontium carbonate powder material;
If the strontium salt intermediate raw material after steps A and step B processing is SrCl
26H
2O or Sr (NO
3)
2Crystal then need be dissolved in earlier in the pure water, and C carries out set by step again;
D, synthetic, filtration, washing, drying
To filter through step C reaction synthetic Strontium carbonate powder material, be 40～90 ℃ pure water then with temperature, press the weight ratio washing leaching cake of wash water/product=15～30, again filter cake is packed after drying under 100～220 ℃ the temperature at last, promptly make fluorescence grade strontium carbonate product of the present invention.
2, the preparation method of fluorescence grade strontium carbonate according to claim 1 is characterized in that: described industrial strontium salt comprises industrial Sr (NO
3)
2, SrCl
26H
2O, Sr (OH)
28H
2O and industrial magnesium strontium.
3, the preparation method of fluorescence grade strontium carbonate according to claim 1 and 2, it is characterized in that: when described steps A is raw material with the industrial magnesium strontium, with water it is sized mixing earlier, with technical hydrochloric acid or industrial nitric acid its dissolving being obtained Sr content again is the strontium salt solution of 80～260g/L, and then removes beavy metal impurities such as Fe, Pb according to a conventional method.
4, the preparation method of fluorescence grade strontium carbonate according to claim 1 is characterized in that: the preferred (NH of described vitriol
4)
2SO
4
5, the preparation method of fluorescence grade strontium carbonate according to claim 1, it is characterized in that: when the strontium salt intermediate raw material after steps A and step B handle was crystal, its Ca content was 0.005～0.10%, Ba content is 0.005～0.08%, Pb, Ni content all＜0.0001%, Fe content is 0.0001～0.0015%.
6, the preparation method of fluorescence grade strontium carbonate according to claim 1 is characterized in that: described useful component comprises:
Single mineral compound or the organic compound of A, rare earth element Eu, Dy, Tm, Yb, Ce, Pr, La, Nd, Sm, Tb, Er, Lu, Gd, Ho, Y, Sc, or the mineral compound or the organic compound of arbitrary proportion combination, its content range in strontium carbonate product is: 0.0001～0.2%;
Single mineral compound or the organic compound of B, non-rare earth Si, Al, Mn, Sb, Zn, Mg, Sn, Bi, Li, Ga, Ge, In, F and P, or the mineral compound or the organic compound of arbitrary proportion combination, its content range in strontium carbonate product is: 0.0008～0.8%.
7, the preparation method of fluorescence grade strontium carbonate according to claim 1 is characterized in that: SrCO in the described fluorescence grade strontium carbonate product
3Content is 95～99.5%, Ca content is 0.01～0.3%, Ba content is 0.01～0.2%.
8, according to the preparation method of claim 1 or 7 described fluorescence grade strontium carbonates, it is characterized in that: SrCO in the described fluorescence grade strontium carbonate product
3Content is 96.5～98.5%.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277005A (en) * | 2018-01-26 | 2018-07-13 | 温州大学 | A kind of multiduty fluorescent crystal material and preparation method thereof |
| CN108818834A (en) * | 2018-07-12 | 2018-11-16 | 东北林业大学 | A kind of preparation method of the laminated transparent timber of long-afterglow fluorescent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104559A (en) * | 1987-06-26 | 1988-01-20 | 自贡市轻工业设计研究院 | The method of production of strontium salt using strontianite |
| CN1050531A (en) * | 1989-09-26 | 1991-04-10 | 福州市工业科学技术研究所 | The production method of Strontium carbonate powder |
| CN1057507C (en) * | 1996-12-27 | 2000-10-18 | 熊海宁 | Preparation high purity strontium carbonate |
-
2005
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277005A (en) * | 2018-01-26 | 2018-07-13 | 温州大学 | A kind of multiduty fluorescent crystal material and preparation method thereof |
| CN108818834A (en) * | 2018-07-12 | 2018-11-16 | 东北林业大学 | A kind of preparation method of the laminated transparent timber of long-afterglow fluorescent |
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