CN102674428A - High-whiteness spherical nano barium sulfate and preparation method thereof - Google Patents
High-whiteness spherical nano barium sulfate and preparation method thereof Download PDFInfo
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- CN102674428A CN102674428A CN2012101537908A CN201210153790A CN102674428A CN 102674428 A CN102674428 A CN 102674428A CN 2012101537908 A CN2012101537908 A CN 2012101537908A CN 201210153790 A CN201210153790 A CN 201210153790A CN 102674428 A CN102674428 A CN 102674428A
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Abstract
The invention discloses a preparation method of spherical nano barium sulfate, which comprises the following steps: respectively treating a barium hydroxide solution and an ammonium sulfate solution, carrying out parallel flow successive reaction according to the mol ratio of Ba<2+> to SO4<2-> being 1.00/(1.05-1.10), and carrying out solid-liquid separation after the reaction, thereby obtaining a filter cake and a filtrate; dispersing the filter cake obtained in the previous step in water to obtain a slurry, adding sulfuric acid to regulate the pH value of the solution to 2.5-3.0, adding oxydol to react at 70-75 DEG C, and carrying out solid-liquid separation after the reaction finishes, thereby obtaining a filter cake and a filtrate; and dispersing the filter cake obtained in the previous step in water to form a slurry, adding ammonium sulfate until the concentration of the ammonium sulfate solution is 0.04-0.07 mol/L, regulating the pH value to 6.5-7.5, washing at 75-80 DEG C, carrying out solid-liquid separation to obtain a filter cake, evaporating, and drying to obtain the spherical nano barium sulfate product. The barium sulfate content in the barium sulfate product is higher than 99.1%; the manganese content is lower than 1.0ppm; the iron content is lower than 1.0ppm; the whiteness is greater than 98.5%; as for the fineness, the content of 325-mesh screenings is less than 0.10%; and the size of primary particles ranges from 20nm to 40nm.
Description
Technical field
The present invention relates to fine inorganic chemical filler preparing technical field, particularly relate to a kind of high whiteness ball shaped nano permanent white and method of manufacture thereof.
Background technology
Nano barium sulfate is widely used in industries such as paint, printing ink, coating, fiber and plastics; Meanwhile, fields such as high-grade automobile finish, solar cell film backlight and far-infrared reflection film have proposed strict requirement to purity, whiteness and the pattern of nano barium sulfate.
The preparation method of nano barium sulfate is more, and most of preparation method is owing to add promoting agent, surface treatment agent or properties-correcting agent in system, but this kind method bring disadvantageous effect in the production of derived product can for this product.CN101423239A discloses and a kind of moles such as sodium sulfate and bariumchloride has been reacted through full back-mixing liquid film reactor; Through rotor and stator gap width and the rotating speed of regulating this reactor drum; The condition that the control reaction is carried out obtains the controlled permanent white of particle diameter, and wherein used sulfuric acid and bariumchloride are AR, can cause the cost of whole preparation to improve like this; Industrial applications receives bigger restriction, simultaneously the also raising method of not mentioned whiteness of this method.
Summary of the invention
The technical problem that the present invention solves is not add other promoting agent or properties-correcting agent, through microcavity and flow the spherical BaSO that continuous synthesis technique has obtained narrow distribution
4Obtained high whiteness BaSO through the acidic oxidation washing procedure
4And obtained high purity BaSO through control washing
4
The two is carried out and flow the spherical permanent white that successive reaction produces narrow distribution thereby the present invention at first controls hydrated barta and ammonium sulfate mol ratio; Utilize ydrogen peroxide 50 under acidic conditions, to remove the impurity that is mixed with in the permanent white then; Particularly influence the sulfocompound of color; Elements such as ferrimanganic are converted into ionic condition are dissolved into and are removed in the solution, make through this step to obtain the characteristic that spherical permanent white has high whiteness; At last the above-mentioned high whiteness permanent white that obtains is washed, make wherein impurity and the whole washings of ion remove the spherical permanent white of the nanometer that finally obtains high purity, high whiteness.Importantly, the present invention will and flow successive reaction and combines application with the acidic oxidation removal step, further combined with the step of washing, makes preparation method of the present invention finally obtain the nano barium sulfate product of high whiteness simultaneously.
Specifically, the present invention solves the problems of the technologies described above through following technical scheme:
A kind of preparation method of ball shaped nano permanent white comprises the steps:
(1) barium hydroxide solution and ammoniumsulphate soln are handled respectively after, with [Ba
2+]/[SO
4 2-] mol ratio be that 1.00/ (1.05～1.10) are carried out and flowed successive reaction, preferred [Ba
2+]/[SO
4 2-] mol ratio be 1.00/1.08, carry out solid-liquid separation after the reaction, obtain filter cake and filtrating;
(2) filter cake that step (1) is obtained is distributed to and processes slip in the water, adds sulfuric acid adjustment pH value of solution 2.5～3.0, and the back adds ydrogen peroxide 50 70～75 ℃ of reactions, and reaction finishes the back solid-liquid separation and obtains filter cake 2 and filtrating; And
(3) filter cake that step (2) is obtained is distributed to and forms slip in the water; It is 0.04-0.07mol/L that adding ammonium sulfate makes ammoniumsulphate soln concentration, and the concentration of preferably sulfuric acid ammonium is 0.05mol/L, and adjustment pH is 6.5～7.5; The preferred ammonia adjustment pH7.0 that feeds; Wash under 75～80 ℃ of temperature the back, and solid-liquid separation obtains filter cake, and filter cake obtains the ball shaped nano barium sulfate product after evaporation, oven dry.
Wherein, described barium hydroxide solution is handled of step (1) is to be 30～35 ℃ in temperature to filter down that preferred the filtration uses the aperture of filter membrane to be 0.4-0.7 μ m; Preferred aperture is 0.5 μ m; It is to filter that described ammoniumsulphate soln is handled; The preferred filtration uses the aperture of filter membrane to be 0.4-0.7 μ m; Preferred aperture is 0.5 μ m.
Wherein, barium ion concentration is 0.20～0.30mol/L in the described barium hydroxide solution of step (1), and preferred 0.25～0.30mol/L, barium hydroxide solution flow are 2000～6000L/h, preferred 4000～5000L/h, more preferably 4500L/h; The concentration of ammoniumsulphate soln is 0.05～0.50mol/L, preferred 0.25～0.30mol/L, and the ammoniumsulphate soln flow is at 2000～10000L/h scope, preferred 4000～6000L/h, more preferably 5000L/h.
Wherein, step (1) said and stream successive reaction in, stirring velocity is 400～1500rpm, preferred 1000～1200rpm.
Wherein, after the said filtrating of step (1) adds CaO, reclaim NH
3
Wherein, the amount that adds ydrogen peroxide 50 in the step (2) is every cubic metre of slip adding 2-3 liter, preferred 2.5 liters.
Wherein, the reaction times 70～75 ℃ of reactions described in the step (2) is 1-3 hour, preferred 2 hours.
Wherein, step (3) described under 75～80 ℃ of temperature the washing washing time be 0.5-2 hour, be preferably 1 hour.
Wherein, step (2) and the described water of step (3) are deionized water, the 5-8 that the quality that preferred steps (2) and step (3) add entry is respectively the filter cake quality doubly, the quality that preferably adds entry is respectively 6 times of filter cake quality.
A kind of ball shaped nano permanent white is characterized in that, whiteness is all greater than 98.5%, and the particle size range of primary particle is 20-40nm.
Beneficial effect of the present invention is following:
(1) barium sulfate content for preparing of the inventive method all is higher than 99.1%, preferably is higher than 99.3%; Manganese content is lower than 1.0ppm; Iron level is lower than 1.0ppm; Whiteness is preferably greater than 99.0% greater than 98.5%; Fineness in 325 screen residues less than 0.10%; The particle size range of primary particle is 20 ~ 40nm.
(2) processing condition of the present invention are gentle, and ammonia carried out reclaiming can reach through three steps that control permanent white reaches the purity height, ball shaped nano level that whiteness is high must be asked.
Description of drawings:
Fig. 1: reaction process schema of the present invention;
Fig. 2: and flow successive reaction equipment synoptic diagram;
Each numbering is represented as follows respectively among the figure: the 1-reactor body; 2-first material inlet; The 3-material outlet; 4-also flows reaction chamber; The 5-stir chamber; The 6-current limiting plate; 7-first spray hole; The 8-agitating vane; The 9-baffle plate; The 10-reservoir; 11-second material inlet; 12-second spray hole; 13-taper fairing cap; The 14-motor; The 15-metering hole; 16-reactor body bottom; 17-also flows the reaction chamber bottom.
Embodiment
The present invention prepares the method for high whiteness ball shaped nano permanent white, realizes through following chemical reaction:
Ba
2++SO
4 2-→BaSO
4↓
S
2- X+1+H
2O
2+H
+→SO
4 2-+H
2O
Wherein the present invention carries out the high whiteness sphere of the prepared in reaction method of permanent white so with hydrated barta and ammonium sulfate, realizes through following chemical reaction:
Ba(OH)
2+(NH
4)
2SO
4→BaSO
4↓+2NH
4OH
S
2- X+1+H
2O
2+H
+→SO
4 2-+H
2O
Specifically, the present invention realizes through following technical scheme:
The preparation method of ball shaped nano permanent white of the present invention comprises the steps:
(1) barium hydroxide solution and ammoniumsulphate soln are handled respectively after, with [Ba
2+]/[SO
4 2-] mol ratio is that 1.00/ (1.05～1.10) are carried out and flowed successive reaction, carries out solid-liquid separation after the reaction, obtains filter cake and filtrating; It is to be 30～35 ℃ in temperature to filter down that wherein said ammoniumsulphate soln is handled, and preferably filters with 0.5 μ m aperture accurate filter; It is with 0.5 μ m aperture secondary filter that described ammoniumsulphate soln is handled; Barium ion concentration is 0.20～0.30mol/L in the wherein said barium hydroxide solution, preferred 0.25～0.30mol/L; The concentration of ammoniumsulphate soln is 0.05～0.50mol/L, preferred 0.25～0.30mol/L; Wherein said and stream successive reaction in the barium hydroxide solution flow be 2000～6000L/h, preferred 4000～5000L/h; The ammoniumsulphate soln flow is in 2000～10000L/h scope, preferred 4000～6000L/h; Stirring velocity is 400～1500rpm, preferred 1000～1200rpm; After wherein said mother liquor adds CaO, reclaim NH
3
Equation so that barium hydroxide solution and ammoniumsulphate soln react is following:
Ba(OH)
2+(NH
4)
2SO
4→BaSO
4↓+2NH
4OH
The purpose of this step is with after containing hydrated barta and ammoniumsulphate soln and carrying out proper process earlier; Again with certain concentration and flow make the two and flow in the flow reactor and react; After carry out solid-liquid separation and obtain filter cake and mother liquor, mother liquor is reclaimed ammonia after treatment.
(2) filter cake that step (1) is obtained is distributed to and processes slip in the water, adds sulfuric acid adjustment pH value of solution 2.5～3.0, and the back adds ydrogen peroxide 50 70～75 ℃ of reactions, and reaction finishes the back solid-liquid separation and obtains filter cake and filtrating; The amount of wherein said adding ydrogen peroxide 50 is that every cubic metre of slip adds 2-3 liter, preferred 2.5 liters; The time of wherein said reaction is 1-3 hour, preferred 2 hours.And
Concrete reaction equation is following in this step:
S
2- X+1+H
2O
2+H
+→SO
4 2-+H
2O
The purpose of this step is the sulfur compound impurities reaction that under acidic conditions and in the permanent white, is mixed with ydrogen peroxide 50; Negatively charged ion wherein is converted into sulfate radical; The metals ion that simultaneously metallic impurity elements such as ferrimanganic is converted into solubility makes it to get in the solution and separates through solid-liquid separation; Remove the impurity that is mixed with in the permanent white; Particularly influence the sulfocompound of color, will be converted into ionic condition and be dissolved in the solution and be removed, make through this step to obtain the characteristic that spherical permanent white has high whiteness.
(3) filter cake that step (2) is obtained is distributed to and forms slip in the water, and behind the adding ammonium sulfate, adjustment pH is 6.5～7.5; The preferred ammonia adjustment pH that feeds; Wash under 75～80 ℃ of temperature the back, and solid-liquid separation obtains filter cake, and filter cake obtains the ball shaped nano barium sulfate product after evaporation, oven dry; Wherein said washing time is 0.5-2 hour, is preferably 1 hour.
The purpose of this step is to wash obtaining the permanent white solid in the step (2); The purpose that wherein in solution, adds ammonium sulfate is that sulfate ion concentration is increased; Utilize the common-ion effcet of permanent white, thereby the concentration of the barium ion when reducing balance in the solution suppresses crystal growth, but general just through increasing the crystalline growth that wherein a kind of ionic concentration suppresses permanent white; And can not add two kinds of ions simultaneously, prevented that newly-generated vitriol from coating the permanent white of original generation; Also acid ion is neutralized in this step; And under neutral or nearly neutral condition, wash; Not only make the permanent white that obtains for neutral, and removed the adherent foreign ion of the permanent white metallic element ionic content such as ferrimanganic that further improved purity drop.
More particularly, to prepare the method for high whiteness ball shaped nano permanent white following in the present invention:
With Ba (OH)
2Solution temperature is adjusted to 30～35 ℃ of scopes, [Ba
2+] 0.20～0.30mol/L, preferred 0.25～0.30mol/L filters for use with 0.5 μ m aperture accurate filter.
With (NH
4)
2SO
4Solution is adjusted into 0.05～0.50mol/L scope, preferred 0.25～0.30mol/L, and 0.5 μ m aperture secondary filter is for use under the normal temperature.
Control the synthesizer stirring velocity in 400～1500rpm scope, preferred 1000～1200rpm.
Control the barium hydroxide solution flow in 2000～6000L/h scope with constant flow pump, preferred 4000～5000L/h.
With constant flow pump control (NH
4)
2SO
4Solution flow is in 2000～10000L/h scope, preferred 4000～6000L/h.
Control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/ (1.05～1.10) scope.
The building-up reactions slurry carries out solid-liquid separation, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation:
Filter cake is placed in the acid-resistant container, press material-water ratio 1:6 and add deionized water, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution 2.5～3.0, rise preferred 2.5 liters ratio in every cubic metre of slip 2-3 and add technical grade ydrogen peroxide 50, chuck heat temperature raising; Hierarchy of control temperature is 70～75 ℃ of scopes; Stirring oxidation rinsing solid-liquid separation after 2 hours, filtrating is handled discharging, and filter cake gets into next-step operation.
Filter cake is placed in the washing pot, press material-water ratio and add deionized water at 1: 6, dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4, make [SO in the solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, feeds NH
3Adjustment slip pH6.5～7.5 scopes, chuck is warming up to 75～80 ℃ of scopes, and agitator treating is solid-liquid separation after 1 hour, and filtrating is handled discharging, and filter cake flash distillation oven dry obtains spherical nano barium sulfate product.
Embodiment
Used determinator and measuring method describes as follows when at first, high whiteness ball shaped nano permanent white among the following embodiment being prepared process and product and analyzes:
About the use of the part measuring method in the barium sulfate product analysis is the measuring method among the standard SN/T 0480-1995 (outlet tiff analytical procedure);
Specifically, barium sulfate content is measured the method that adopts among the SN/T 0480.5-1995;
The model that measuring brightness adopts Jinan MICHAEL DRAKE Instr Ltd. to produce is that the measuring brightness appearance (adopt 200 mesh sieves, measure after 105 ℃ of oven dry) of DRK103A is measured according to disclosed method among the SN/T 0480.12-1995;
200 mesh sieves: ASTM standard sieve;
Fineness (325 screen residue) adopts the method for SN/T 0480.2-1995 to measure;
325 mesh sieves: ASTM standard sieve;
The mensuration of product pattern: JSM-6490LV type sem, NEC's corporate system.
The particle size determination of primary particle: JSM-6490LV type sem, NEC's corporate system.
The pH pH-value determination pH adopts PHS-3C type precision acidity meter, by Shanghai precision instrumentation manufactured.
The device that flash distillation is used is the fast rotational flash dryer of the model of Changzhou sudden peal of thunder drying plant ltd manufacturing as XZG.
Elemental analysis method: inductively coupled plasma (ICP) atomic emission spectrometry;
Atomic Absorption SpectrophotometerICP: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system.
The technical grade ydrogen peroxide 50: mass percentage concentration is 27.5%, and Jiangshan City, Zhejiang Province ydrogen peroxide 50 company produces.
Constant flow pump: the east of a river, Suzhou precision instrument ltd.
Technical grade hydrated barta: Ba (OH)
2Content>=98%.
Technical grade ammonium sulfate: (NH
4)
2SO
4Content>=95%.
Step among the following embodiment (1) and flow successive reaction can through routine and flow flow reactor reaction, also can be through shown in Figure 2 and flow flow reactor and accomplish.
Embodiment 1
Combine the present invention of explanation shown in the process flow sheet of Fig. 1 to prepare the process of high whiteness ball shaped nano permanent white down, with technical grade hydrated barta (Ba (OH)
2>=98%) add deionized water preparation baryta water, making barium ion concentration is 0.20mol/L, with this Ba (OH)
2Solution temperature is adjusted into 30 ℃, filters for use with 0.4 μ m aperture accurate filter.With technical grade ammonium sulfate ((NH
4)
2SO
4>=95%) preparation ammonium sulfate solution, wherein (NH
4)
2SO
4Strength of solution is 0.05mol/L, and normal temperature filters for use with 0.4 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 400rpm, uses constant flow pump control barium hydroxide solution flow to be 2000L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 8400L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.05, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the successive reaction equipment and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the common acid-resistant container, adds deionized water by material-water ratio 1: 5 (mass ratio of slip and water) and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.5, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 70 ℃; Stirring oxidation rinsing solid-liquid separation after 1 hour under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 5, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.04mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 6.5, chuck is warming up to 75 ℃, agitator treating under this temperature after 0.5 hour solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 1
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 2
The technical grade hydrated barta joined prepare baryta water in the deionized water, wherein barium ion concentration is 0.25mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 33 ℃, filters for use with 0.5 μ m aperture accurate filter.With the preparation of technical grade ammonium sulfate ammonium sulfate solution, wherein (NH
4)
2SO
4Strength of solution is 0.25mol/L, and normal temperature filters for use with 0.5 μ m aperture accurate filter down.The rotating speed of setting motor 12 is 1100rpm; Setting barium hydroxide solution uses the flow of constant flow pump to be 4000L/h; The flow of setting the used constant flow pump of ammoniumsulphate soln (figure does not show) is 4200L/h; The agitator motor power supply is connected in the back; Connect the power supply of above-mentioned two constant flow pumps (figure do not show) simultaneously, first material inlet 2 of the bottom 16 of the baryta water that constant flow pump just disposes through being located at reactor body 1 join in the reactor body 1 according to flow be 4000L/h constantly through first spray hole 7, it is that 4200L/h constantly is injected to through second spray hole 12 and flows in the reaction chamber 4 that the ammonium sulfate solution of configuration is joined in the reservoir 10 according to flow through second material inlet 11; Two kinds of solution moment contact hybrid reactions, [Ba in the control synthetic reaction process
2+]/[SO
4 2-] mol ratio is 1.00/1.08.Post reaction mixture is being located at and is being flowed under the effect of taper fairing cap 13 of reaction chamber bottom 17; Constantly through have in the middle of the current limiting plate 6 metering hole 15 enter into stir chamber 5; The power that material provides through motor 14 in stir chamber 5 mixes said mixture between agitating vane 8, mix in the process, and lower floor's blade mixture after being mixed stops that the lower section mixture comes back in lower floor's blade and stirs once more baffle plate 9; The partial confounding compound continues to move upward; Under the agitating vane effect of upper strata, continue to be stirred, be uniformly dispersed through upper strata agitating vane mixture after being mixed, in the reaction process constantly through spraying in material outlet 3 slave units; Carry out solid-liquid separation behind the slurry of collection ejection and obtain filter cake and mother liquor, gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water at 1: 6 by material-water ratio and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.7, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2.5 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 70 ℃; Stirring oxidation rinsing solid-liquid separation after 2 hours under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 6, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 7.0, chuck is warming up to 73 ℃, agitator treating under this temperature after 1 hour solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 2
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 3
With the technical grade hydrated barta preparation baryta water that is added to the water, wherein barium ion concentration is 0.30mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 32 ℃, filters for use with 0.6 μ m aperture accurate filter.With the preparation of technical grade ammonium sulfate ammonium sulfate solution, wherein (NH
4)
2SO
4Strength of solution is 0.50mol/L, and normal temperature filters for use with 0.5 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 1000rpm, uses constant flow pump control barium hydroxide solution flow to be 6000L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 3960L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.06, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the flow reactor and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water at 1: 7 by material-water ratio and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.8, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2.3 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 72 ℃; Stirring oxidation rinsing solid-liquid separation after 1.5 hours under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 6, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.06mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 6.8, chuck is warming up to 75 ℃, agitator treating under this temperature after 1.2 hours solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 3
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 4
The technical grade hydrated barta joined prepare baryta water in the deionized water, wherein barium ion concentration is 0.30mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 35 ℃, filters for use with 0.7 μ m aperture accurate filter.With the preparation of technical grade ammonium sulfate ammonium sulfate solution, wherein (NH
4)
2SO
4Strength of solution is 0.50mol/L, and normal temperature filters for use with 0.7 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 600rpm, uses constant flow pump control barium hydroxide solution flow to be 6000L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 2000L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.07, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the flow reactor and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water at 1: 7 by material-water ratio and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 3.0, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 3 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 75 ℃; Stirring oxidation rinsing solid-liquid separation after 1.5 hours under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 6, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.06mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 7.5, chuck is warming up to 80 ℃, agitator treating under this temperature after 1.5 hours solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 4
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 5
The technical grade hydrated barta joined prepare baryta water in the deionized water, wherein barium ion concentration is 0.27mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 33 ℃, filters for use with 0.5 μ m aperture accurate filter.Ammonium sulfate preparation ammonium sulfate solution, wherein (NH with technical grade
4)
2SO
4Strength of solution is 0.30mol/L, and normal temperature filters for use with 0.6 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 1000rpm, uses constant flow pump control barium hydroxide solution flow to be 5000L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 10000L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.07, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the flow reactor and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water at 1: 6 by material-water ratio and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.9, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2.3 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 72 ℃; Stirring oxidation rinsing solid-liquid separation after 2.5 hours under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 8, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.04mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 6.9, chuck is warming up to 78 ℃, agitator treating under this temperature after 1.5 hours solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 5
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 6
The technical grade hydrated barta joined prepare baryta water in the deionized water, wherein barium ion concentration is 0.25mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 32 ℃, filters for use with 0.7 μ m aperture accurate filter.Ammonium sulfate preparation ammonium sulfate solution, wherein (NH with technical grade
4)
2SO
4Strength of solution is 0.05mol/L, and normal temperature filters for use with 0.5 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 400rpm, uses constant flow pump control barium hydroxide solution flow to be 4000L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 2000L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.06, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the flow reactor and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water by material-water ratio 1:6 and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.8, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2.5 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 70 ℃; Stirring oxidation rinsing solid-liquid separation after 1 hour under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 6, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 7.0, chuck is warming up to 78 ℃, agitator treating under this temperature after 1 hour solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 6
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 7
The technical grade hydrated barta joined prepare baryta water in the deionized water, wherein barium ion concentration is 0.25mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 32 ℃, filters for use with 0.7 μ m aperture accurate filter.Ammonium sulfate preparation ammonium sulfate solution, wherein (NH with technical grade
4)
2SO
4Strength of solution is 0.05mol/L, and normal temperature filters for use with 0.5 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 400rpm, uses constant flow pump control barium hydroxide solution flow to be 4000L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 6000L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.06, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the flow reactor and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water at 1: 6 by material-water ratio and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.8, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2.5 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 70 ℃; Stirring oxidation rinsing solid-liquid separation after 1 hour under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 6, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 7.0, chuck is warming up to 78 ℃, agitator treating under this temperature after 1 hour solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 7
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
Embodiment 8
The hydrated barta of technical grade joined prepare baryta water in the deionized water, wherein barium ion concentration is 0.25mol/L in the barium hydroxide solution, with this Ba (OH)
2Solution temperature is adjusted into 33 ℃, filters for use with 0.5 μ m aperture accurate filter.With technical grade ammonium sulfate preparation ammonium sulfate solution (please replenish the requirement of the aspects such as source, purity of ammonium sulfate), wherein (NH
4)
2SO
4Strength of solution is 0.25mol/L, and normal temperature filters for use with 0.5 μ m aperture accurate filter down.Controlling and flowing continuous synthesizer stirring velocity is 1100rpm, uses constant flow pump control barium hydroxide solution flow to be 4500L/h, with constant flow pump control (NH
4)
2SO
4Solution flow is 5000L/h, control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.08, with the Ba after the above-mentioned processing (OH)
2Solution and (NH
4)
2SO
4Solution is ejected into and flows in the flow reactor and react, and carries out solid-liquid separation behind the continuous collection slurry in the reaction process and obtains filter cake and mother liquor, and gas was carried recovery NH after mother liquor replenished The addition of C aO
3, filter cake gets into next-step operation;
The filter cake that a last step is obtained places in the acid-resistant container, adds deionized water at 1: 6 by material-water ratio and processes slip, dispersed with stirring; Add a small amount of sulfuric acid adjustment pH value of solution to 2.7, the back adds ydrogen peroxide 50, chuck heat temperature raising in the ratio that every cubic metre of slip adds 2.5 liters of technical grade ydrogen peroxide 50; Hierarchy of control temperature is 70 ℃; Stirring oxidation rinsing solid-liquid separation after 2 hours under this temperature, filtrating is handled discharging, and filter cake gets into next-step operation.
The filter cake that the last step was obtained places in the washing pot, presses material-water ratio and adds deionized water at 1: 6, and dispersed with stirring adds an amount of (NH simultaneously
4)
2SO
4Make [SO in the solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, the back feeds NH
3Adjustment slip pH to 7.0, chuck is warming up to 73 ℃, agitator treating under this temperature after 1 hour solid-liquid separation obtain filter cake and filtrating, filtrating is handled discharging, filter cake flash distillation oven dry obtains spherical nano barium sulfate product 8
#, it is carried out barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is seen table 1.
The barium sulfate product property testing result that table 1 embodiment of the invention prepares
Result through in the last table shows that the content of the permanent white that the embodiment of the invention prepares is all greater than 99.0%, and wherein the content of the permanent white among the embodiment 2,5 and 8 is greater than 99.3%; Mn content and Fe content that embodiment 1-8 prepares in the permanent white all are lower than 1.0ppm, and whiteness is all greater than 98.5%, and fineness all is lower than 0.10% in 325 screen residues; The median size of the permanent white for preparing all reaches 20-40nm, and the median size of the permanent white of embodiment 2-5,7 and 8 preparations all reaches 20-30nm, and particle morphology is sphere.The permanent white of above-mentioned digital proof the present invention preparation has high whiteness, high purity, and particle diameter has reached nano level characteristic.
The present invention has carried out above-mentioned description to some preferred implementation and embodiment; To help the public in the embodiment of the present invention process, to use suitable experimental technique; Obtain experiment effect preferably, this does not get rid of the experimental technique of not enumerating among the present invention that is equal to also can embodiment of the present invention.It will be appreciated by those skilled in the art that the present invention except specifically described mode, can also be applicable to distortion and modification.Should be understood that, the present invention includes all these distortion and modification.Further, denomination of invention, title or similar part are in order to strengthen the understanding of the public to this paper, should not regarded as the qualification to protection domain of the present invention.
Make a general survey of whole specification sheets and claims, only if context needs, otherwise word " comprises ", and " comprising " and similar speech are interpreted as the implication that comprises but not the implication of getting rid of that is to say that looking like is " including, but are not limited to ".
Claims (14)
1. the preparation method of a ball shaped nano permanent white comprises the steps:
(1) barium hydroxide solution and ammoniumsulphate soln are handled respectively after, with [Ba
2+]/[SO
4 2-] mol ratio be that 1.00/ (1.05～1.10) are carried out and flowed successive reaction, preferred [Ba
2+]/[SO
4 2-] mol ratio be 1.00/1.08, carry out solid-liquid separation after the reaction, obtain filter cake and filtrating;
(2) filter cake that step (1) is obtained is distributed to and processes slip in the water, adds sulfuric acid adjustment pH value of solution 2.5～3.0, and the back adds ydrogen peroxide 50 70～75 ℃ of reactions, and reaction finishes the back solid-liquid separation and obtains filter cake and filtrating; And
(3) filter cake that step (2) is obtained is distributed to and forms slip in the water; It is 0.04-0.07mol/L that adding ammonium sulfate makes ammoniumsulphate soln concentration, and the concentration of preferably sulfuric acid ammonium is 0.05mol/L, and adjustment pH is 6.5～7.5; The preferred ammonia adjustment pH7.0 that feeds; Wash under 75～80 ℃ of temperature the back, and solid-liquid separation obtains filter cake, and filter cake obtains the ball shaped nano barium sulfate product after evaporation, oven dry.
2. the preparation method of ball shaped nano permanent white as claimed in claim 1, wherein described barium hydroxide solution is handled of step (1) is to be 30～35 ℃ in temperature to filter down that preferred the filtration uses the aperture of filter membrane to be 0.4-0.7 μ m; Preferred aperture is 0.5 μ m; It is to filter that described ammoniumsulphate soln is handled; The preferred filtration uses the aperture of filter membrane to be 0.4-0.7 μ m; Preferred aperture is 0.5 μ m.
3. according to claim 1 or claim 2 the preparation method of ball shaped nano permanent white; Wherein barium ion concentration is 0.20～0.30mol/L in the described barium hydroxide solution of step (1); Preferred 0.25～0.30mol/L, barium hydroxide solution flow are 2000～6000L/h, preferred 4000～5000L/h, more preferably 4500L/h; The concentration of ammoniumsulphate soln is 0.05～0.50mol/L, preferred 0.25～0.30mol/L, and the ammoniumsulphate soln flow is at 2000～10000L/h scope, preferred 4000～6000L/h, more preferably 5000L/h.
4. like the preparation method of each described ball shaped nano permanent white of claim 1-3, wherein in the said and stream successive reaction of step (1), stirring velocity is 400～1500rpm, preferred 1000～1200rpm.
5. like the preparation method of each described ball shaped nano permanent white of claim 1-4, after wherein the said filtrating of step (1) adds CaO, reclaim NH
3
6. like the preparation method of each described ball shaped nano permanent white of claim 1-5, the amount that wherein adds ydrogen peroxide 50 in the step (2) is that every cubic metre of slip adds 2-3 liter, preferred 2.5 liters.
7. like the preparation method of each described ball shaped nano permanent white of claim 1-6, be 1-3 hour in the reaction times of 70～75 ℃ of reactions in the step (2) wherein, preferred 2 hours.
8. like the preparation method of each described ball shaped nano permanent white of claim 1-7, wherein the said washing time of under 75～80 ℃ of temperature, washing of step (3) is 0.5-2 hour, is preferably 1 hour.
9. like the preparation method of each described ball shaped nano permanent white of claim 1-8; Wherein step (2) and the described water of step (3) are deionized water; The 5-8 that the quality that preferred steps (2) and step (3) add entry is respectively the filter cake quality doubly, the quality that preferably adds entry is respectively 6 times of filter cake quality.
10. each described preparation method of claim 1-9 prepares ball shaped nano permanent white.
11. one kind like claim 10 ball shaped nano permanent white, it is characterized in that whiteness is all greater than 98.5%, the particle diameter of primary particle is 20-40nm.
12. one kind to be used for each nanometer sulfuric acid of claim 1-9 preparing method's step (1) described and the stream successive reaction and flow successive reaction equipment; It is characterized in that; This equipment comprises reactor body (1); Reactor body (1) is provided with from top to bottom and flows reaction chamber (4) and stir chamber (5), and stream reaction chamber (4) and stir chamber (5) separate through current limiting plate (6); Open metering hole (15) in the middle of the current limiting plate (4); And stream reaction chamber (4) by and the sidewall that flows bottom (17), current limiting plate (4) and the reactor body (1) of reaction chamber surround; Bottom (16) in reactor body (1) is provided with first material inlet (2); Be provided with reservoir (10) in reactor body (1) lower, outer perimeter around reactor body (1), have second material inlet (11) on reservoir (10) wall; Be provided with material outlet (3) on the top of reactor body (1).
13. as claimed in claim 12 and stream successive reaction equipment, bottom (17) wherein said and stream reaction chamber (4) is provided with first spray hole (7) and fairing cap (13); Preferably in stir chamber (5), be provided with baffle plate (9) symmetrically on reactor body (1) wall between the adjacent agitating vane (8); More preferably wherein fairing cap (8) is taper, and it is located at and flows bottom (17) central authorities of reaction chamber (4).
14. the described and stream successive reaction equipment like claim 12 or 13, wherein said and flow reaction chamber (4) bottom (17) and offer at least two first spray holes (7); Preferably also be provided with motor (14) at the top of reactor body (1); More preferably and flow on reactor body (1) sidewall at reaction chamber 4 place and have at least two second spray holes (12).
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| CN111252795A (en) * | 2020-01-18 | 2020-06-09 | 青岛红蝶新材料有限公司 | Production process of low-sulfur barium sulfate |
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| CN114031103A (en) * | 2021-11-22 | 2022-02-11 | 湖南工程学院 | Method for preparing spherical barium sulfate from chemical nickel plating waste liquid |
| CN114031103B (en) * | 2021-11-22 | 2023-12-05 | 湖南工程学院 | Method for preparing spherical barium sulfate from chemical nickel plating waste liquid |
| CN117303428A (en) * | 2023-11-29 | 2023-12-29 | 平利县安得利新材料有限公司 | Preparation method and device for realizing barium sulfate |
| CN117303428B (en) * | 2023-11-29 | 2024-02-02 | 平利县安得利新材料有限公司 | Preparation method and device for realizing barium sulfate |
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