CN101811732A - Superfine and high-purity bismuth oxide and preparation method thereof - Google Patents
Superfine and high-purity bismuth oxide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a superfine and high-purity bismuth oxide with the granularity of 10-1000nm and a preparation method thereof. The method takes the solid bismuth with the purity of 4N as a raw material to synthesize the superfine and high-purity bismuth oxide, and is characterized in comprising the following steps of: firstly, soaking the solid bismuth with the purity of 4N into mixed acid solution which is prepared by hydrogen nitrate and muriatic acid; taking out the soaked solid bismuth, and enabling the soaked solid bismuth to react with hydrogen nitrate solution to obtain the bismuth nitrate solution and keep the excessive status of the hydrogen nitrate; mixing the bismuth nitrate solution with the ammonia water solution to perform synthetic reaction; filtrating to obtain white bismuth hydroxide deposition; and washing, drying, calcining and preparing powder according to a conventional method to obtain the superfine and high-purity bismuth oxide with the phase of alpha-Bi2O3, the granularity of 10-100nm and the purity of 5N. The technological condition is easily controlled, has good product homogeneity, and does not need to an add dispersing agent, thereby being capable of obtaining the superfine bismuth oxide powder with even granularity, preventing impurity from being induced, and reducing the preparation cost.
Description
Technical field
The present invention relates to a kind of used in electronic industry bismuth oxide and production method thereof, particularly a kind of granularity is ultra-fine high-purity bismuth oxide and the production method thereof of 10～100nm.
Background technology
Ultra-fine high-purity bismuth oxide is that outward appearance is lurid powder, and thing is α-Bi mutually
2O
3, granularity is 10～100nm, purity is the spherical agglomerates of 5N.Of many uses, be mainly used in the production of electronic ceramics powder body material, ferrite magnetic material, electrolyte, photoelectric material and superconducting material etc., and can be used as additive of organic catalyst compound, special glass, chemical fabrics fire retardant and environment-friendly battery etc.
The method of the ultra-fine high-purity bismuth oxide of preparation mainly contains two big classes at present, and a class is directly to utilize 5N or above high purity bismuth to synthesize through series of process to obtain, because 5N or above high purity bismuth price height, this method does not have economic feasibility.Another kind of is to utilize bismuth-containing material to obtain through leaching, removal of impurities, complex process step such as synthetic, because the bismuth-containing material composition is too complicated, often is difficult to obtain high-purity bismuth oxide.Bismuth with 4N is that the ultra-fine high-purity bismuth oxide of raw material production generally can obtain by following four approach, the one, and mechanical crushing method, can obtain the fine powder that particle diameter is 1 μ m, but in the process of pulverizing, easily sneak into impurity; The 2nd, the molten atomizing method, this method can obtain superfine bismuth oxide in the short period of time in 45～48s, but lack of homogeneity, it is complete to be difficult to oxidation, and production process has dust pollution; The 3rd, preparation α-Bi such as presoma by the hydrolysis oxidation bismuth such as halogenide, acetate, alkoxide
2O
3, the product homogeneity that this method obtains is better, but need synthesize presoma under the anhydrous and oxygen-free condition in organic solvent, to technology, equipment requirements height; The 4th, chemical precipitation method needs to add dispersion agent in preparation process, but mostly selects for use sodium hydroxide to regulate the pH value in reaction process, not only pH is difficult to control, and the sodium salt in the solution is difficult for flush away, and sodium salt also is difficult to decompose and removes during calcining, and then influences the purity of ultra-fine high-purity bismuth oxide.Also have in the prior art earlier solid metal bismuth melt water quenching, nitric acid dissolve, the ammoniacal liquor adjust pH is hydrolyzed into the bismuthyl nitrate precipitation, add carbonate and make the transition into Bismuth carbonate, calcining obtains the method for bismuth oxide, as: the production method of disclosed 200310121804.9 high purity superfine bismuth oxides of Chinese patent, it is to contain Bi
3+The bismuth nitrate solution of 100～350g/L joins in the ammonium bicarbonate soln that concentration is 10～25wt%, and the ammonium bismuth weight ratio that control adds under normal temperature and stirring state, generates the Bismuth carbonate precipitation in 1.5～3.5 scopes; Filtration washing; Filter cake is heat-treated under 100～700 ℃, obtains the bismuth oxide product.Can further add in the method is the dispersion agent of ammonium bicarbonate soln weight 0.1～5%, and what produced is the high-purity bismuth oxide powder of d50=1～100 μ m.Chinese patent 200810147959.2 discloses a kind of production method of high purity superfine bismuth oxide, its step is as follows: bismuth salt compound, dispersion agent, bicarbonate of ammonia and a small amount of solvent are carried out ball milling together, obtain bismuthyl carbonate with deionized water wash after, calcine after mixing with a certain amount of bicarbonate of ammonia, make target product; Above-mentioned dispersion agent is taken from a kind of of tween, sapn or polyoxyethylene nonylphenol ether; Can obtain granularity is the following fine powder of 1 μ m, and the aforesaid method processing condition are easy to control, the product good uniformity, but technological process is complicated, and production cost is higher.It still will use dispersion agent, adds dispersion agent and easily introduces impurity, also increases cost simultaneously, the separable programming complexity, and the granularity of its product that obtains of what is more important does not all reach the requirement that granularity is 10～100nm.In sum, further research that raw material is easy to get, technology is simple, lower-cost ultra-fine high-purity bismuth oxide preparation method awaits.
Summary of the invention
The object of the present invention is to provide a kind of ultra-fine high-purity bismuth oxide preparation method, but its production granularity is 10～100nm, purity is the ultra-fine high-purity bismuth oxide of 5N, the utilization ratio of bismuth reaches more than 99.5%, and has that raw material is easy to get, technology is simple, lower-cost advantage.
Another object of the present invention is to provide a kind of ultra-fine high-purity bismuth oxide, it is that granularity is 10～100nm, and purity is the spherical agglomerates of 5N.
Technical scheme of the present invention is:
A kind of ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material synthesizing superfine high-purity bismuth oxide with purity, it is characterized in that: it is earlier to be after mixed acid solution that the solid bismuth of 4N places nitric acid and hydrochloric acid to be mixed with soaks with purity, take out with salpeter solution and react, obtain bismuth nitrate solution, and the excessive state of maintenance nitric acid, bismuth nitrate solution mixed with ammonia soln carry out building-up reactions, filtration obtains the bismuth hydroxide precipitation of white, wash according to a conventional method, drying and calcining, powder process, obtaining purity is the ultra-fine high-purity bismuth oxide of 5N.
As to further improvement of the present invention, described mixed acid solution is made up of 2～6g/L nitric acid and 3～8g/L hydrochloric acid, and described solid bismuth soak time in mixed acid solution is 10～50 minutes.
As to further improvement of the present invention, the mass percentage concentration of described salpeter solution is 20～60%, Bi in the described bismuth nitrate solution
3+Volumetric molar concentration is 0.5～2.5mol/L, and the mass percentage concentration of described ammoniacal liquor is 6.4～12.8%.
As to further improvement of the present invention, add sulfuric acid in the described bismuth nitrate solution and carry out deleading and handle, add the vitriolic volume in the described bismuth nitrate solution and be 0.001～0.003 times of bismuth nitrate solution volume, leave standstill clarification, bismuth nitrate solution.
As to further improvement of the present invention, the solvent of described mixed acid solution, salpeter solution, ammonia soln is specific conductivity less than 500us/cm, solubility SiO
2Be lower than the water of 0.02mg/L.
As to further improvement of the present invention, the building-up reactions of described bismuth nitrate solution and ammonia soln be with specific conductivity less than 500us/cm, solubility SiO
2The water that is lower than 0.02mg/L is end liquid, continue to stir, pH is 3.0～6.2, temperature of reaction is that 20～80 ℃, reaction times are to carry out under 30～60 minutes the condition.
As to further improvement of the present invention, described washing step is to adopt specific conductivity less than 500us/cm, solubility SiO
2The water slurry that is lower than 0.02mg/L is washed 2～3 times, and drip washing is 2～3 times again.
As to further improvement of the present invention, described drying and calcining step is that bismuth hydroxide is deposited in the loft drier dry 4～8 hours, and drying temperature is 75～90 ℃; Put into calcining furnace then and calcined 2～5 hours, temperature is 350～550 ℃, obtains the particulate state bismuth oxide after the cooling.
As to further improvement of the present invention, described powder process step is the cooled particulate state bismuth oxide of calcining to be obtained thing through powder process be α-Bi mutually
2O
3, granularity is that 10～100nm, purity are the ultra-fine high-purity bismuth oxide of 5N.
A kind of ultra-fine high-purity bismuth oxide, it adopts above-mentioned method preparation, and the thing of described ultra-fine high-purity bismuth oxide is α-Bi mutually
2O
3, granularity is that 10～100nm, purity are 5N.
The principle that the present invention utilized is:
The solid bismuth of 4N is handled through acidity lower hydrochloric acid and nitric acid dousing removal of impurities, dissolve through nitric acid reaction again, obtain bismuth nitrate solution, be precipitation agent then with the ammonia soln, obtain the bismuth hydroxide precipitation by chemical precipitation method, bismuth hydroxide precipitates drying, calcining and powder process step, obtains the ultra-fine high-purity bismuth oxide of 5N at last, and the main chemical reactions formula is as follows:
Fe+2HCl＝FeCl
2+H
2O
Fe+2HNO
3＝Fe(NO
3)
2+H
2O
Bi+6HNO
3＝Bi(NO
3)
3+3NO
2↑+3H
2O
Bi+4HNO
3＝Bi(NO
3)
3+NO↑+2H
2O
Bi(NO
3)
3+3NH
3·H
2O＝Bi(OH)
3+3NH
4NO
3
2Bi(OH)
3＝Bi
2O
3+3H
2O
The present invention has the following advantages:
The present invention adopts chemical precipitation method to prepare ultra-fine high-purity bismuth oxide, compares with chemical precipitation method of the prior art, and the two all has processing condition and is easy to control, the advantage of product good uniformity.
But the present invention still has the following advantages:
1, the present invention is after mixed acid solution that the solid bismuth of 4N places nitric acid and hydrochloric acid to be diluted to by water soaks with purity, can remove the impurity of solid bismuth surface adhesion, the concentration and the soak time of control mixing acid, can realize not only removing solid bismuth surface impurity, but also control the solid bismuth not with the effect of nitric acid in this pretreatment stage generation building-up reactions, improved the purity of reaction raw materials effectively.
2, through soaking solid bismuth and the excessive state of the resulting bismuth nitrate solution maintenance nitric acid of nitric acid reaction after removal of impurities is handled, can suppressing the hydrolysis of bismuth in the bismuth nitrate solution.
3, in bismuth nitrate solution, add sulfuric acid and can further remove lead residual in the solution, make the purity of product higher, the purity of water is limited, can effectively limit by water and be brought into impurity in the solution.
4, pH value, temperature of reaction and the reaction times of the present invention by the control building-up reactions, can transfer bismuth to bismuth hydroxide fully, and effective controls reaction speed.
5, the synthetic bismuth hydroxide that obtains through wash and starch with drip washing, can be with attached to the NH on the bismuth hydroxide
4 +, NO
3 -Flush away, the purity of raising product.
6, the present invention selects for use ammoniacal liquor to make precipitation agent, adopts the reaction of ammoniacal liquor and bismuth nitrate solution to generate the Bismuth trinitrate precipitation, need not to add dispersion agent in the precipitation process, need not to adopt the raw material that contains sodium ion, has avoided bringing in the product Na that is difficult to clean removal
+, fundamentally stopped to contain in the product Na
+, avoided the sodium salt pollution.
On the other hand, by controlling the ammonia concn and the concentration of Bismuth trinitrate, the speed of response of may command building-up reactions, thereby make resulting bismuth hydroxide granularity refinement and even, drying calcining, pulverizing can obtain the micropowder of bismuth oxide that granularity is 10～100nm, reduce the production cost of micropowder of bismuth oxide.
7, by control bismuth hydroxide time of drying and temperature, can prevent the caking of bismuth hydroxide in drying process; By controlling calcination time and temperature, can preventing bismuth hydroxide burning or sintering, influence quality product.
The present invention directly utilizes the solid bismuth of 4N to produce 5N and above ultra-fine high-purity bismuth oxide, has reduced the purity requirement to raw material, realizes the low-cost raw material production to be easy to get; With the solid bismuth that with purity is 4N is that the prior art of raw material is compared, and the present invention need not pass through steps such as fusion, shrend, bismuth pin, further simplifies technology, has reduced the requirement to equipment; The ultra-fine high-purity bismuth oxide fine size of gained and even, powder active is good, and the bismuth rate of recovery has reduced the consumption of expensive raw material up to more than 99.5%, has low, the advantage of simple technology of cost, has good economic feasibility.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
A kind of ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material with purity, it is with the mixing solutions pre-treatment through nitric acid and the 3g/L hydrochloric acid of 2g/L of the bismuth of 500g4N, be that soak time is to take out and nitric acid reaction after 50 minutes, promptly under continuous stirring condition, slowly add concentration (wt%) and be 60% the about 900mL of nitric acid, and add an amount of specific conductivity less than 500us/cm, solubility SiO
2Be lower than 0.02mg/L distilled water, obtain bismuth nitrate solution, add the sulfuric acid that volume is 0.001 times of a bismuth nitrate solution again to resulting bismuth nitrate solution; The 450mL mass percentage concentration is that 27% ammoniacal liquor and 450mL specific conductivity are less than 500us/cm, solubility SiO
2The distilled water that is lower than 0.02mg/L is that preparation in 1: 1 obtains ammonia soln by volume, and its mass percentage concentration is 12.8%.Adding simultaneously under continuous agitation condition has specific conductivity less than 500us/cm, solubility SiO with above-mentioned bismuth nitrate solution and ammonia soln
2The distilled water that is lower than 0.02mg/L is done in the reactor of end liquid, and the control temperature of reaction system is 30 ℃, and process pH value is controlled to be 3.5, and endpoint pH is controlled to be 4.0, reacts 50min again after reinforced the finishing, and obtains white bismuth hydroxide precipitation.White bismuth hydroxide precipitation slurry is deposited in white bismuth hydroxide oven dry in dry 4 hours under 90 ℃ of temperature in the loft drier again through washing 2 times, drip washing 2 times; Putting into then temperature is set is 350 ℃ of calcining furnaces calcining 5 hours, and cooling back powder process obtains color and is light yellow, thing and is α-Bi mutually
2O
3, granularity is that 95nm, purity are the ultra-fine high-purity bismuth oxide of 5N, wherein major impurity Fe, Pb, Cu quality percentage composition are respectively 0.00029%, 0.00021% and 0.00011%.
Embodiment 2
A kind of ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material synthesizing superfine high-purity bismuth oxide with purity, it is with nitric acid and the pre-treatment of 5g/L hydrochloric acid soln through 3g/L of the solid bismuth of 500g4N, be that soak time is to take out and nitric acid reaction after 40 minutes, promptly under continuous stirring condition, slowly add concentration (wt%) and be 50% the about 1050mL of nitric acid, and add an amount of specific conductivity less than 500us/cm, solubility SiO
2Be lower than the deionized water of 0.02mg/L, the bismuth nitrate solution that obtains adds the vitriolization that volume is 0.002 times of a bismuth nitrate solution again; The 450mL mass percentage concentration is that 27% ammoniacal liquor and 900mL specific conductivity are less than 500us/cm, solubility SiO
2The deionized water that is lower than 0.02mg/L is that to obtain mass percentage concentration be 8.3% ammonia soln in preparation in 1: 2 by volume.Adding simultaneously under constantly stirring has specific conductivity less than 500us/cm, solubility SiO with above-mentioned bismuth nitrate solution and ammonia soln
2The deionized water that is lower than 0.02mg/L is done in the reactor of end liquid, 50 ℃ of control temperature of reaction system, and process pH is 4.5, terminal point pH is 4.8, reacts 60min again after reinforced the finishing, and obtains white bismuth hydroxide precipitation.White bismuth hydroxide precipitation is through washing and starching drip washing 3 times, oven dry in dry 5 hours under 85 ℃ of temperature in loft drier again 2 times; Putting into then temperature is set is 420 ℃ of calcining furnaces calcining 4 hours, and cooling back powder process obtains color and is light yellow, thing and is α-Bi mutually
2O
3, granularity is that 85nm, purity are the ultra-fine high-purity bismuth oxide of 5N, wherein major impurity Fe, Pb, Cu quality percentage composition are respectively 0.00025%, 0.00018% and 0.0001%.
Embodiment 3
A kind of ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material synthesizing superfine high-purity bismuth oxide with purity, it is with nitric acid and the pre-treatment of 5g/L hydrochloric acid soln through 4g/L of the solid bismuth of 500g4N, be that soak time is to take out and nitric acid reaction after 30 minutes, promptly under continuous stirring condition, slowly add concentration (wt%) and be 40% the about 1300mL of nitric acid, and add an amount of specific conductivity less than 500us/cm, solubility SiO
2Be lower than the distilled water of 0.02mg/L, the bismuth nitrate solution that obtains adds the vitriolization that volume is 0.002 times of a bismuth nitrate solution again; The 450mL mass percentage concentration is that 27% ammoniacal liquor and 900mL specific conductivity are less than 500us/cm, solubility SiO
2The distilled water that is lower than 0.02mg/L is that to obtain mass percentage concentration be 8.3% ammonia soln in preparation in 1: 2 by volume.Adding simultaneously under constantly stirring has specific conductivity less than 500us/cm, solubility SiO with above-mentioned bismuth nitrate solution and ammonia soln
2The distilled water that is lower than 0.02mg/L is done in the reactor of end liquid, 60 ℃ of control temperature of reaction system, and process pH is 4.5, terminal point pH is 6.0, reacts 40min again after reinforced the finishing, and obtains white bismuth hydroxide precipitation.White bismuth hydroxide precipitation is through washing and starching drip washing 2 times, oven dry in dry 6.5 hours under 80 ℃ of temperature in loft drier again 3 times; Putting into then temperature is set is 500 ℃ of calcining furnaces calcining 3.5 hours, and cooling back powder process obtains color and is light yellow, thing and is α-Bi mutually
2O
3, granularity is that 75nm, purity are the ultra-fine high-purity bismuth oxide of 5N, wherein major impurity Fe, Pb, Cu quality percentage composition are respectively 0.0002%, 0.00015% and less than 0.0001%.
Embodiment 4
A kind of ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material synthesizing superfine high-purity bismuth oxide with purity, it is with nitric acid and the pre-treatment of 7g/L hydrochloric acid soln through 5g/L of the solid bismuth of 500g4N, be that soak time is to take out and nitric acid reaction after 20 minutes, promptly under continuous stirring condition, slowly add concentration (wt%) and be 30% the about 2200mL of nitric acid, and add an amount of specific conductivity less than 500us/cm, solubility SiO
2Be lower than the distilled water of 0.02mg/L, the bismuth nitrate solution that obtains adds the vitriolization that volume is 0.003 times of a bismuth nitrate solution again; The 450mL mass percentage concentration is that 27% ammoniacal liquor and 1350mL specific conductivity are less than 500us/cm, solubility SiO
2The distilled water that is lower than 0.02mg/L is that to obtain mass percentage concentration be 6.2% ammonia soln in preparation in 1: 3 by volume.Adding simultaneously under constantly stirring has specific conductivity less than 500us/cm, solubility SiO with above-mentioned bismuth nitrate solution and ammonia soln
2The distilled water that is lower than 0.02mg/L is done in the reactor of end liquid, 70 ℃ of control temperature of reaction system, and process pH is 4.8, terminal point pH is 6.0, reacts 40min again after reinforced the finishing, and obtains white bismuth hydroxide precipitation.White bismuth hydroxide precipitation is through washing and starching drip washing 3 times, oven dry in dry 6.5 hours under 80 ℃ of temperature in loft drier again 3 times; Putting into then temperature is set is 500 ℃ of calcining furnaces calcining 3.5 hours, and cooling back powder process obtains color and is light yellow, thing and is α-Bi mutually
2O
3, granularity is that 68nm, purity are the ultra-fine high-purity bismuth oxide of 5N, wherein major impurity Fe, Pb, Cu quality percentage composition are respectively 0.00018%, 0.00014% and less than 0.0001%.
Embodiment 5
A kind of ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material synthesizing superfine high-purity bismuth oxide with purity, it is with nitric acid and the pre-treatment of 8g/L hydrochloric acid soln through 6g/L of the solid bismuth of 500g4N, be that soak time is to take out and nitric acid reaction after 10 minutes, promptly under continuous stirring condition, slowly add concentration (wt%) and be 20% the about 2650mL of nitric acid, and add an amount of specific conductivity less than 500us/cm, solubility SiO
2Be lower than the water of 0.02mg/L, the bismuth nitrate solution that obtains adds the vitriolization that volume is 0.003 times of a bismuth nitrate solution again; The 450mL mass percentage concentration is that 27% ammoniacal liquor and 1350mL specific conductivity are less than 500us/cm, solubility SiO
2The distilled water that is lower than 0.02mg/L is that to obtain mass percentage concentration be 6.2% ammonia soln in preparation in 1: 3 by volume.Adding simultaneously under constantly stirring has specific conductivity less than 500us/cm, solubility SiO with above-mentioned bismuth nitrate solution and ammonia soln
2The distilled water that is lower than 0.02mg/L is done in the reactor of end liquid, 70 ℃ of control temperature of reaction system, and process pH is 5.0, terminal point pH is 7.0, reacts 30min again after reinforced the finishing, and obtains white bismuth hydroxide precipitation.White bismuth hydroxide precipitation is through washing and starching drip washing 3 times, oven dry in dry 8 hours under 75 ℃ of temperature in loft drier again 3 times; Putting into then temperature is set is 550 ℃ of calcining furnaces calcining 2 hours, and cooling back powder process obtains color and is light yellow, thing and is α-Bi mutually
2O
3, granularity is that 68nm, purity are the ultra-fine high-purity bismuth oxide of 5N, wherein major impurity Fe, Pb, Cu quality percentage composition are respectively 0.00015%, 0.00012% and less than 0.0001%.
Claims (10)
1. ultra-fine high-purity bismuth oxide preparation method, it is that the solid bismuth of 4N is a raw material synthesizing superfine high-purity bismuth oxide with purity, it is characterized in that: it is earlier to be after mixed acid solution that the solid bismuth of 4N places nitric acid and hydrochloric acid to be mixed with soaks with purity, take out with salpeter solution and react, obtain bismuth nitrate solution, and the excessive state of maintenance nitric acid, bismuth nitrate solution mixed with ammonia soln carry out building-up reactions, filtration obtains the bismuth hydroxide precipitation of white, wash according to a conventional method, drying and calcining, powder process, obtaining purity is the ultra-fine high-purity bismuth oxide of 5N.
2. ultra-fine high-purity bismuth oxide preparation method according to claim 1 is characterized in that: described mixed acid solution is made up of 2～6g/L nitric acid and 3～8g/L hydrochloric acid, and described solid bismuth soak time in mixed acid solution is 10～50 minutes.
3. ultra-fine high-purity bismuth oxide preparation method according to claim 1 and 2, it is characterized in that: the mass percentage concentration of described salpeter solution is 20～60%, the Bi3+ volumetric molar concentration is 0.5～2.5mol/L in the described bismuth nitrate solution, and the mass percentage concentration of described ammoniacal liquor is 6.4～12.8%.
4. ultra-fine high-purity bismuth oxide preparation method according to claim 3 is characterized in that: 0.001～0.003 times the sulfuric acid that adds volume in the described bismuth nitrate solution and be the bismuth nitrate solution volume carries out deleading to be handled, and leaves standstill clarification, bismuth nitrate solution.
5. ultra-fine high-purity bismuth oxide preparation method according to claim 4 is characterized in that: the solvent of described mixed acid solution, salpeter solution, ammonia soln is specific conductivity less than 500us/cm, solubility SiO
2Be lower than the water of 0.02mg/L.
6. ultra-fine high-purity bismuth oxide preparation method according to claim 4 is characterized in that: the building-up reactions of described bismuth nitrate solution and ammonia soln be with specific conductivity less than 500us/cm, solubility SiO
2The water that is lower than 0.02mg/L is end liquid, continue to stir, pH is 3.0～6.2, temperature of reaction is that 20～80 ℃, reaction times are to carry out under 30～60 minutes the condition.
7. ultra-fine high-purity bismuth oxide preparation method according to claim 6 is characterized in that: described washing step is to adopt specific conductivity less than 500us/cm, solubility SiO
2The water slurry that is lower than 0.02mg/L is washed 2～3 times, and drip washing is 2～3 times again.
8. ultra-fine high-purity bismuth oxide preparation method according to claim 7 is characterized in that: described drying and calcining step is that bismuth hydroxide is deposited in the loft drier dry 4～8 hours, and drying temperature is 75～90 ℃; Put into calcining furnace then and calcined 2～5 hours, temperature is 350～550 ℃, obtains the particulate state bismuth oxide after the cooling.
9. ultra-fine high-purity bismuth oxide preparation method according to claim 7 is characterized in that: described powder process step is the cooled particulate state bismuth oxide of calcining to be obtained thing through powder process be α-Bi mutually
2O
3, granularity is that 10～100nm, purity are the ultra-fine high-purity bismuth oxide of 5N.
10. ultra-fine high-purity bismuth oxide is characterized in that: its adopts each described method preparation of claim 1-9, and the thing of described ultra-fine high-purity bismuth oxide is α-Bi mutually
2O
3, granularity is that 10～100nm, purity are 5N.
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| CN103112893A (en) * | 2013-01-29 | 2013-05-22 | 广东先导稀材股份有限公司 | Preparation method of bismuth hydroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103112893A (en) * | 2013-01-29 | 2013-05-22 | 广东先导稀材股份有限公司 | Preparation method of bismuth hydroxide |
| CN103112893B (en) * | 2013-01-29 | 2015-02-04 | 广东先导稀材股份有限公司 | Preparation method of bismuth hydroxide |
| CN104030351A (en) * | 2014-06-20 | 2014-09-10 | 湖南金旺铋业股份有限公司 | Production method of alpha-bismuth oxide |
| CN104835648A (en) * | 2015-04-08 | 2015-08-12 | 苏州大学 | Preparation method for bismuth oxide nano-particle/titania nano-tube array |
| CN107398265A (en) * | 2017-08-09 | 2017-11-28 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method based on graphene oxide catalysis material |
| CN108557881A (en) * | 2018-01-15 | 2018-09-21 | 俞淼 | A kind of method of bismuth-containing material production high-purity bismuth oxide |
| CN108557881B (en) * | 2018-01-15 | 2020-07-28 | 俞淼 | Method for producing high-purity bismuth oxide from bismuth-containing material |
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