CN101591013B - Organic phase back-extraction method for preparing cerium terbium lanthanum phosphate - Google Patents
Organic phase back-extraction method for preparing cerium terbium lanthanum phosphate Download PDFInfo
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Abstract
The invention relates to an organic phase back-extraction method for preparing cerium terbium lanthanum phosphate, which comprises the following process steps: (1) using hydrochloric acid or nitric acid to dissolve lanthana, cerium oxide and terbia respectively to obtain first solution; (2) preparing organic extractant solution which consists of one or two extractants of 2-ethylhexyl phosphate 2-ethylhexyl ester, trioctyl tertiary amine, dioctylphosphoric acid ester, tributyl phosphate, Cyanex272 and naphthenic acid and sulfonated kerosene to obtain second solution; (3) adding the first solution and the second solution into a reactor to prepare third solution; (4) preparing solution containing phosphate groups to form rare-earth phosphate sediment; and (5) after the precipitation reactionis finished, washing products by water, performing centrifugal dehydration on the product, mixing the product and absolute ethanol into slurry, placing the slurry, carrying out drying treatment on the slurry and calcinating the dried slurry to obtain a cerium terbium lanthanum phosphate powder body. The cerium terbium lanthanum phosphate prepared by the method has low content of impurity, controllability of the granularity of particles, even distribution of the granularity of the particles and good crystal morphology.
Description
(1) technical field
The present invention relates to a kind of process for preparing rare earth phosphate, be specifically related to a kind of preparation method of lanthanum-cerium-terbium phosphate, belong to the rare earth new material technical field in the field of inorganic materials.
(2) background technology
RE phosphate is a kind of application fluorescence luminescent material extremely widely, wherein most representative is lanthanum-cerium-terbium phosphate green emitting phosphor, be a kind of green emitting phosphor that is widely used in purposes such as rare-earth trichromatic luminescent lamp, its molecular formula is (LaCeTb) PO4, is called for short LAP.This kind material is compared with conventional aluminate green powder (CAT), have luminosity height, synthesis temperature is moderate, chromaticity coordinates X value is bigger advantage, be the new generation of green fluorescent material product that replaces CAT, become one of focus of rare earth material chemical field research at present.
In the method for existing preparation lanthanum-cerium-terbium phosphate, can should be mentioned that dry method and wet method.Dry method adopts the high temperature solid-state synthesis technique to make lanthanum-cerium-terbium phosphate usually, it is characterized in that with constitute the lanthanum cerium terbium oxide of fluor matrix and phosphate compounds for example Secondary ammonium phosphate mix with the active compound that contains predetermined amount, under 1000 ℃ of high temperature, make between the solid phase then and react.The defective of this technology is: high temperature easily produces the phosphorus oxide volatilization down, and the ratio of product middle-weight rare earths element and phosphate radical can't accurately be controlled; The calcination temperature height, energy consumption is big; Be mixed with dephasign in the synthetic product; Bigger than normal and the size distribution of the granularity of product compares broad.Therefore, the technical study of synthetic at present lanthanum-cerium-terbium phosphate mainly concentrates on wet method and prepares the aspect.Wet method is normally reacted by two kinds of inorganic solutions and obtained product, and a kind of inorganic solution is chloride soln or the nitrate solution that contains lanthanum cerium terbium element, and is another kind of for containing the inorganic solution such as the ammonium dibasic phosphate solution of phosphate radical.At present the synthetic FAQs that runs into of wet method is that the lanthanum-cerium-terbium phosphate that generates often is gel state, and sedimentation function and strainability are poor, particularly produce sintering through calcining after, the processing that is difficult to sieve of particle formation lump shape.Because product is gel state, the non-rare earth impurity that contains in the raw material just is difficult in the aftertreatment and removes, and the impurity that is present in a large number in the lanthanum-cerium-terbium phosphate precipitation medium will be sneaked in the rare-earth phosphate phosphor.Because product produces sintering at calcination stage, the fine particle unity that forms when making precipitation becomes macrobead, can not control the granularity and the size-grade distribution of product effectively.For the luminescent properties of fluorescent material, the foreign matter content of material, grain graininess and size-grade distribution and microcosmic crystal habit are vital to the influence of luminescent properties.Therefore how to obtain low impurity content, grain graininess is controlled, particle size distribution is even and crystal habit is good lanthanum-cerium-terbium phosphate is the direction that requires further improvement and study.
(3) summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, the preparation method of a kind of low impurity content, grain graininess is controlled, particle size distribution is even and crystal habit is good lanthanum-cerium-terbium phosphate is provided.
The object of the present invention is achieved like this: a kind of organic phase back-extraction method for preparing cerium terbium lanthanum phosphate is characterized in that this method comprises following processing step:
(1) a kind of complex chlorides or compound nitrate solution that contains lanthanum, cerium, three kinds of rare earth elements of terbium simultaneously, chemical formula is (La
xCe
yTb
z) Cl
3Or (La
xCe
yTb
z) (NO
3)
3, wherein x, y, z satisfy: 0＜x＜1; 0＜y＜1; The numerical value of 0＜z＜1 and x+y+z=1.Its compound method is with hydrochloric acid or nitric acid difference dissolved oxygen lanthanum, cerium oxide and terbium sesquioxide, mixing back formation concentration according to stoichiometric ratio is rare-earth chloride solution or the rare earth nitrate solution of 0.1～2mol/L, preferred concentration is at 0.5～1.0mol/L, and this method is prepared into first solution.
(2) a kind of organic extraction agent solution, form by the own ester of 2-ethylhexyl phosphoric acid single 2-ethyl, three octyl tertiary amines, di (isooctyl) phosphate, tributyl phosphate, Cyanex272, naphthenic acid one or both extraction agents (A) and sulfonated kerosene (B) wherein, wherein the former extraction agent A volume ratio is between 0.1～0.3, latter B volume ratio is between 0.7～0.9, and sulfonated kerosene mainly plays the dilution extractant concentration.With this extraction agent solution and stoichiometric sodium hydroxide or ammonium hydroxide reaction, make the saponification value of extraction agent solution reach 0.1～0.5M.This method is prepared into second solution.
(3) add first solution and second solution in reactor, the volume of first solution and second solution adds than being controlled between 1: 5～1: 10.It is 60HZ that two kinds of solution mix back controlling reactor oscillation frequency, and duration of oscillation is 3～10 minutes.After vibration finishes mixing solutions was left standstill 3～5 minutes, organic phase is fully separated with water, remove water and keep upper organic phase, contain lanthanum, cerium, terbium three kind rare earth elements in the organic phase this moment.This method is prepared into the 3rd solution.
(4) a kind of solution that contains phosphate radical of preparation, adopt hydrogen ion concentration to prepare phosphoric acid solution by stoichiometry at 10～15 normal phosphoric acid and deionized water, the hydrogen ion concentration of solution is controlled at 0.5～1.5mol/L, the requirement of phosphoric acid by 1.5～2.0 times of dissolving rare earth oxide amount of substance (mole number).In reactor, add a certain amount of deionized water solution, in reactor, add the 3rd solution and phosphoric acid solution simultaneously, the adding speed of controlling the two is 50～100ml/ minute, guarantee that the two adds simultaneously, pH value in the controlling reactor is between 1.5～2.0, formation RE phosphate precipitation keeps temperature of reaction at 20～70 ℃ in the precipitation process.
(5) after precipitin reaction finishes, with product with deionized water wash to pH value to 5.0～6.5; Through centrifuge dehydration, the product after the dehydration with dehydrated alcohol furnishing pulpous state, is placed baking oven again, carry out drying treatment under 80～100 ℃ of temperature, be more than 5 hours time of drying; Dried product is moved in the high-purity ceramic crucible, under clean air atmosphere, calcine, obtain the lanthanum-cerium-terbium phosphate powder.
The present inventor finds, can preferentially select rare earth element to come together in the organic phase non-rare earth impurity Fe in while first solution when adopting among the A single extraction agent or two kinds of mixed extractants to carry out extractive reaction with first solution
2O
3The overwhelming majority also is extracted in the organic phase, and in the organic phase, this step is very ineffective to the removal of the CaO in the non-rare earth impurity and the CaO overwhelming majority is come together, and clearance can reach 70%～80%.And in (4) processing step, the reaction of the organic phase of phosphoric acid solution and supported rare earth the time can preferentially be selected the phosphate radical that rare earth element back extraction from organic phase is got off with aqueous phase is formed the RE phosphate precipitation, and most non-rare earth impurity Fe
2O
3Do not obtain back extraction, this step is to Fe
2O
3Clearance can reach 70%～80%.Therefore, by above-mentioned extraction and two steps of back extraction, the non-rare earth impurity in the raw material has only 10%～20% to enter into final lanthanum-cerium-terbium phosphate product.
Introduce organic solution among the present invention and participate in precipitin reaction, rare earth element is present in the organic solution with the form of organic complex, when acidic substance are added dropwise in the organic solution, control suitable pH value and adding speed and can control the required ion of generation precipitating action effectively, phosphate anion and rare earth ion Be Controlled are emitted and combination lentamente in the present invention, avoided the local overrich phenomenon of conventional intermediate processing ion, prevent that effectively the too high rapid reaction of ionic concn from causing aggregation phenomenon between particle, the product grain graininess that obtains is between 4～6 μ m, and particle size distribution is more sharp-pointed normal distribution, and particulate microcosmic crystal habit is spherical.
Manufacturing process of the present invention is novel unique, is different from conventional wet method and prepares lanthanum-cerium-terbium phosphate technology, and technological process and equipment are simple, is easy to realize reaction conditions gentleness, sedimentation and filtration good dispersion property.The product foreign matter content is low, and controllable granularity is between 4～6 μ m, and particle size distribution is narrow, has good fluorescence property.
In sum, the present invention adopts the organic solution and the another kind of manufacturing technology that contains the inorganic solution interreaction of phosphate radical of a kind of supported rare earth element (lanthanum cerium terbium).By this method, the foreign matter content of lanthanum-cerium-terbium phosphate product can be reduced effectively, the granularity and the size-grade distribution of product can be simply controlled, can obtain the microcosmic crystal habit is the spheric powder product, and the good dispersity of product can directly use, and need not milled processed.
(4) embodiment
Embodiment 1:
With hydrochloric acid difference dissolved oxygen lanthanum 20g, cerium oxide 10g, terbium sesquioxide 5g, it is 250ml that three's chloride soln mixed population is amassed, and concentration is 0.8mol/L; Get the own ester of 2-ethylhexyl phosphoric acid single 2-ethyl (P507) 50ml and mix, add the NaOH saponification to 0.35M with sulfonated kerosene 350ml; Earth solution and mixed extractant are moved in the reactor, and the adjusting oscillation frequency is 60HZ, and duration of oscillation is the organic phase solution 400ml that after 3 minutes the mixing solutions standing separation is gone out supported rare earth; Measure high concentration phosphorus acid solution (14N) 25ml, add deionized water 325ml and be deployed into the phosphoric acid solution that hydrogen ion concentration is 1.0mol/L; In reactor, add the 200ml deionized water, under 200 rev/mins stirring velocity, in reactor, add load organic phases and phosphoric acid solution simultaneously by the automatic flow control device, keeping adding speed is the 60ml/ branch, the two adds simultaneously, formation RE phosphate precipitation keeps 40 ℃～50 ℃ of temperature of reaction in the precipitation process, ph value of reaction is 2.0; With deionized water the RE phosphate precipitation being washed till PH after precipitation finishes is 6.5 back centrifuge dehydrations; Product is placed baking oven with dehydrated alcohol furnishing pulpous state, under 80 ℃～100 ℃, carry out 8 hours drying treatment; Dried product is placed the inherent 900 ℃ of calcinations of retort furnace 2 hours, obtain Powdered lanthanum-cerium-terbium phosphate.Fe in the product
2O
3Content is 2ppm, and CaO content is 5ppm, and granularity is 4.8 μ m, and size-grade distribution is narrow, and particulate microcosmic crystal habit is spherical in shape.
Embodiment 2:
With nitric acid difference dissolved oxygen lanthanum 20g, cerium oxide 10g, terbium sesquioxide 5g, it is 250ml that three's nitrate solution mixed population is amassed, and concentration is 0.8mol/L; Get naphthenic acid 50ml and mix, add the NaOH saponification to 0.35M with sulfonated kerosene 350ml; Earth solution and mixed extractant are moved in the reactor, and the adjusting oscillation frequency is 60HZ, and duration of oscillation is the organic phase solution 400ml that after 3 minutes the mixing solutions standing separation is gone out supported rare earth; Measure high concentration phosphorus acid solution (14N) 25ml, add deionized water 325ml and be deployed into the phosphoric acid solution that hydrogen ion concentration is 1.0mol/L; In reactor, add the 200ml deionized water, under 200 rev/mins stirring velocity, in reactor, add load organic phases and phosphoric acid solution simultaneously by the automatic flow control device, keeping adding speed is the 60ml/ branch, the two adds simultaneously, formation RE phosphate precipitation keeps 40 ℃～50 ℃ of temperature of reaction in the precipitation process, ph value of reaction is 2.0; With deionized water the RE phosphate precipitation being washed till PH after precipitation finishes is 6.5 back centrifuge dehydrations; Product is placed baking oven with dehydrated alcohol furnishing pulpous state, under 80 ℃～100 ℃, carry out 8 hours drying treatment; Dried product is placed the inherent 900 ℃ of calcinations of retort furnace 2 hours, obtain Powdered lanthanum-cerium-terbium phosphate.Fe in the product
2O
3Content is 2ppm, and CaO content is 5ppm, and granularity is 5.1 μ m, and size-grade distribution is narrow, and particulate microcosmic crystal habit is spherical in shape.
Embodiment 3:
With hydrochloric acid difference dissolved oxygen lanthanum 25g, cerium oxide 10g, terbium sesquioxide 5g, it is 250ml that three's chloride soln mixed population is amassed, and concentration is 0.8mol/L; Get the own ester of 2-ethylhexyl phosphoric acid single 2-ethyl (P507) 40ml, Cyanex272 10ml, sulfonated kerosene 350ml mixes, and adds the NaOH saponification to 0.4M; Earth solution and mixed extractant are moved in the reactor, and the adjusting oscillation frequency is 60HZ, and duration of oscillation is the organic phase solution 400ml that after 3 minutes the mixing solutions standing separation is gone out supported rare earth; Measure high concentration phosphorus acid solution (14N) 30ml, add deionized water 320ml and be deployed into the phosphoric acid solution that hydrogen ion concentration is 1.0mol/L; In reactor, add the 200ml deionized water, under 200 rev/mins stirring velocity, in reactor, add load organic phases and phosphoric acid solution simultaneously by the automatic flow control device, keeping adding speed is the 60ml/ branch, the two adds simultaneously, formation RE phosphate precipitation keeps 40 ℃～50 ℃ of temperature of reaction in the precipitation process, ph value of reaction is 2.0; With deionized water the RE phosphate precipitation being washed till PH after precipitation finishes is 6.5 back centrifuge dehydrations; Product is placed baking oven with dehydrated alcohol furnishing pulpous state, under 80 ℃～100 ℃, carry out 8 hours drying treatment; Dried product is placed the inherent 900 ℃ of calcinations of retort furnace 2 hours, obtain Powdered lanthanum-cerium-terbium phosphate.Fe in the product
2O
3Content is 2ppm, and CaO content is 5ppm, and granularity is 5.03 μ m, and size-grade distribution is narrow, and particulate microcosmic crystal habit is spherical in shape.
Embodiment 4:
With hydrochloric acid difference dissolved oxygen lanthanum 25g, cerium oxide 10g, terbium sesquioxide 5g, it is 250ml that three's chloride soln mixed population is amassed, and concentration is 0.8mol/L; Get three octyl tertiary amine 25ml, naphthenic acid 25ml, sulfonated kerosene 350ml mixes, and adds the NaOH saponification to 0.4M; Earth solution and mixed extractant are moved in the reactor, and the adjusting oscillation frequency is 60HZ, and duration of oscillation is the organic phase solution 400ml that after 3 minutes the mixing solutions standing separation is gone out supported rare earth; Measure high concentration phosphorus acid solution (14N) 30ml, add deionized water 320ml and be deployed into the phosphoric acid solution that hydrogen ion concentration is 1.0mol/L; In reactor, add the 200ml deionized water, under 200 rev/mins stirring velocity, in reactor, add load organic phases and phosphoric acid solution simultaneously by the automatic flow control device, keeping adding speed is the 60ml/ branch, the two adds simultaneously, formation RE phosphate precipitation keeps 40 ℃～50 ℃ of temperature of reaction in the precipitation process, ph value of reaction is 2.0; With deionized water the RE phosphate precipitation being washed till PH after precipitation finishes is 6.5 back centrifuge dehydrations; Product is placed baking oven with dehydrated alcohol furnishing pulpous state, under 80 ℃～100 ℃, carry out 8 hours drying treatment; Dried product is placed the inherent 900 ℃ of calcinations of retort furnace 2 hours, obtain Powdered lanthanum-cerium-terbium phosphate.Fe in the product
2O
3Content is 2ppm, and CaO content is 5ppm, and granularity is 4.92 μ m, and size-grade distribution is narrow, and particulate microcosmic crystal habit is spherical in shape.
All organic extractants of mentioning among the present invention comprise the own ester of 2-ethylhexyl phosphoric acid single 2-ethyl, three octyl tertiary amines, di (isooctyl) phosphate, tributyl phosphate, Cyanex272, all applicable present method of naphthenic acid one or both extraction agents wherein, and specific embodiment is enumerated no longer one by one.
Claims (2)
1. the method for an organic phase back-extraction method for preparing cerium terbium lanthanum phosphate is characterized in that this method comprises following processing step:
(1) a kind of complex chlorides or compound nitrate solution that contains lanthanum, cerium, three kinds of rare earth elements of terbium simultaneously, chemical formula is (La
xCe
yTb
z) Cl
3Or (La
xCe
yTb
z) (NO
3)
3, wherein x, y, z satisfy: 0＜x＜1; 0＜y＜1; The numerical value of 0＜z＜1 and x+y+z=1, its preparation method is with hydrochloric acid or nitric acid difference dissolved oxygen lanthanum, cerium oxide and terbium sesquioxide, mixing back formation concentration according to stoichiometric ratio is rare-earth chloride solution or the rare earth nitrate solution of 0.1～2mol/L, and this method is prepared into first solution;
(2) a kind of organic extraction agent solution, this solution is made up of the own ester of 2-ethylhexyl phosphoric acid single 2-ethyl, three octyl tertiary amines, di (isooctyl) phosphate, tributyl phosphate, Cyanex272, naphthenic acid one or both extraction agents and sulfonated kerosene wherein, wherein the former extraction agent volume ratio is between 0.1～0.3, latter's sulfonated kerosene volume ratio is between 0.7～0.9, with this extraction agent solution and stoichiometric sodium hydroxide or ammonium hydroxide reaction, make the saponification value of extraction agent solution reach 0.1～0.5M, this method is prepared into second solution;
(3) in reactor, add first solution and second solution, the volume of first solution and second solution adds than being controlled between 1: 5～1: 10, it is 60Hz that two kinds of solution mix back controlling reactor oscillation frequency, duration of oscillation is 3～10 minutes, after vibration finishes mixing solutions was left standstill 3～5 minutes, make organic phase and aqueous phase separation, remove water and keep upper organic phase, contain lanthanum, cerium, terbium three kind rare earth elements in the organic phase this moment, and this method is prepared into the 3rd solution;
(4) a kind of solution that contains phosphate radical of preparation, adopt hydrogen ion concentration to prepare phosphoric acid solution by stoichiometry at 10～15 normal phosphoric acid and deionized water, the hydrogen ion concentration of solution is controlled at 0.5～1.5mol/L, the requirement of phosphoric acid be step (3) 1.5～2.0 times of mole number of the 3rd solution middle-weight rare earths oxide material, in reactor, add deionized water, in reactor, add the 3rd solution and phosphoric acid solution simultaneously, the adding speed of controlling the two is 50～100ml/ minute, controlling the two adds simultaneously, pH value in the controlling reactor is between 1.5～2.0, formation RE phosphate precipitation keeps temperature of reaction at 20～70 ℃ in the precipitation process;
(5) after precipitin reaction finishes, with product with deionized water wash to pH value to 5.0～6.5, again through centrifuge dehydration, product after the dehydration with dehydrated alcohol furnishing pulpous state, is placed baking oven, under 80～100 ℃ of temperature, carry out drying treatment, be more than 5 hours time of drying, dried product is moved in the high-purity ceramic crucible, under clean air atmosphere, calcine, obtain the lanthanum-cerium-terbium phosphate powder.
2. the method for a kind of organic phase back-extraction method for preparing cerium terbium lanthanum phosphate according to claim 1 is characterized in that described step (1) middle-weight rare earths chloride soln or rare earth nitrate solution concentration are at 0.5～1.0mol/L.
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| CN106244804B (en) * | 2016-07-29 | 2017-12-29 | 江西理工大学 | Villaumite acid system is preferentially complexed the ferrochrome separation method of the heavy iron of selectivity |
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