CN102674428B - Preparation method and device of high-whiteness spherical nano barium sulfate - Google Patents
Preparation method and device of high-whiteness spherical nano barium sulfate Download PDFInfo
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- CN102674428B CN102674428B CN201210153790.8A CN201210153790A CN102674428B CN 102674428 B CN102674428 B CN 102674428B CN 201210153790 A CN201210153790 A CN 201210153790A CN 102674428 B CN102674428 B CN 102674428B
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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 barium sulfate and manufacture method thereof.
Background technology
Nano barium sulfate is widely used in the industries such as paint, ink, coating, fiber and plastics, meanwhile, the field such as high-grade automobile finish, solar cell film backlight and far-infrared reflection film has proposed strict requirement to the purity of nano barium sulfate, whiteness and pattern.
The preparation method of nano barium sulfate is more, and most of preparation method is owing to adding promoting agent, surface treatment agent or properties-correcting agent in system, but this kind of method brought disadvantageous effect in the production of derived product can to this product.CN101423239A discloses and a kind of sodium sulfate and bariumchloride etc. mole has been reacted by full back-mixing liquid film reactor, by regulating rotor and stator gap width and the rotating speed of this reactor, the condition that control reaction is carried out obtains the controlled barium sulfate of particle diameter, wherein sulfuric acid used and bariumchloride are analytical reagent, can cause like this cost of whole preparation to improve, industrial applications is subject to larger restriction, and while the method is the raising method of not mentioned whiteness also.
Summary of the invention
The technical problem that the present invention solves is not add other promoting agent or properties-correcting agent, by microcavity and flow the spherical BaSO that continuous synthesis technique has obtained narrow distribution
4; By acidic oxidation washing procedure, obtained high whiteness BaSO
4; And wash and obtained high purity BaSO by control
4.
Thereby first the present invention controls hydrated barta and ammonium sulfate mol ratio and the two is carried out and flow the spherical barium sulfate that successive reaction produces narrow distribution, then the impurity that utilizes hydrogen peroxide to be mixed with remove barium sulfate under acidic conditions in, particularly affect the sulfocompound of color, by cycling of elements such as ferrimanganics, be that ionic condition is dissolved in solution and is removed, by this step, make to obtain the feature that spherical barium sulfate has high whiteness; Finally high whiteness barium sulfate obtained above is washed, make impurity and ion wherein all wash and remove the spherical barium sulfate of nanometer that finally obtains high purity, high whiteness.Importantly, the present invention incites somebody to action and flows successive reaction is combined application with acidic oxidation removal step, further combined with the step of washing, make 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 by following technical solution:
A preparation method for ball shaped nano barium sulfate, comprises the steps:
(1) after barium hydroxide solution and ammoniumsulphate soln are processed respectively, with [Ba
2+]/[SO
4 2-] mol ratio be that 1.00/ (1.05～1.10) are carried out and flow successive reaction, preferred [Ba
2+]/[SO
4 2-] mol ratio be 1.00/1.08, after reaction, carry out solid-liquid separation, obtain filter cake and filtrate;
(2) filter cake step (1) being obtained is distributed in water makes slip, adds sulfuric acid to adjust pH value of solution 2.5～3.0, after add hydrogen peroxide 70～75 ℃ of reactions, reaction finishes rear solid-liquid separation and obtains filter cake 2 and filtrate; And
(3) filter cake step (2) being obtained is distributed to and in water, forms slip, adding ammonium sulfate to make ammoniumsulphate soln concentration is 0.04-0.07mol/L, the concentration of preferably sulfuric acid ammonium is 0.05mol/L, adjusting pH is 6.5～7.5, preferably pass into ammonia and adjust pH7.0, after at 75～80 ℃ of temperature, wash, solid-liquid separation obtains filter cake, filter cake obtains ball shaped nano barium sulfate product through evaporation, after drying.
Wherein, step (1) is described barium hydroxide solution is processed is to be to filter at 30～35 ℃ in temperature, and preferably filtering is 0.4-0.7 μ m with the aperture of filter membrane; Preferably aperture is 0.5 μ m; It is to filter that described ammoniumsulphate soln is processed; Preferably filtering is 0.4-0.7 μ m with the aperture of filter membrane; Preferably aperture is 0.5 μ m.
Wherein, in the described barium hydroxide solution of step (1), barium ion concentration is 0.20～0.30mol/L, preferred 0.25～0.30mol/L, and barium hydroxide solution flow is 2000～6000L/h, preferably 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 ammoniumsulphate soln flow is at 2000～10000L/h scope, preferably 4000～6000L/h, more preferably 5000L/h.
Wherein, step (1) is described and flow in successive reaction, and stirring velocity is 400～1500rpm, preferably 1000～1200rpm.
Wherein, the described filtrate of step (1) adds after CaO, reclaims NH
3.
Wherein, the amount that adds hydrogen peroxide in step (2) is that every cubic metre of slip adds 2-3 liter, preferably 2.5 liters.
Wherein, the reaction times 70～75 ℃ of reactions described in step (2) is 1-3 hour, preferably 2 hours.
Wherein, step (3) is described, and at 75～80 ℃ of temperature, to wash washing time be 0.5-2 hour, is preferably 1 hour.
Wherein, the described water of step (2) and step (3) is deionized water, and preferred steps (2) and step (3) add the quality of water to be respectively 5-8 times of filter cake quality, preferably adds the quality of water to be respectively 6 times of filter cake quality.
A ball shaped nano barium sulfate, 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 as follows:
(1) barium sulfate content that the inventive method prepares is all higher than 99.1%, preferably higher than 99.3%; Manganese content is lower than 1.0ppm; Iron level is lower than 1.0ppm; Whiteness is greater than 98.5%, is preferably greater than 99.0%; Fineness is less than 0.10% in 325 screen residues; The particle size range of primary particle is 20 ~ 40nm.
(2) processing condition of the present invention are gentle, and ammonia has been carried out reclaiming by three steps can reach and control barium sulfate and reach the ball shaped nano level that purity is high, whiteness is high and must ask.
Accompanying drawing explanation:
Fig. 1: reaction process schema of the present invention;
Fig. 2: and flow successive reaction equipment schematic diagram;
In figure, each numbering is expressed as follows respectively: 1-reactor body; 2-the first material inlet; 3-material outlet; 4-also flows reaction chamber; 5-stir chamber; 6-current limiting plate; 7-the first spray hole; 8-agitating vane; 9-baffle plate; 10-reservoir; 11-the second material inlet; 12-the second spray hole; 13-conical flow guiding cap; 14-motor; 15-metering hole; 16-reactor body bottom; 17-also flows reaction chamber bottom.
Embodiment
The present invention prepares the method for high whiteness ball shaped nano barium sulfate, by following chemical reaction, realizes:
Ba
2++SO
4 2-→BaSO
4↓
S
2- X+1+H
2O
2+H
+→SO
4 2-+H
2O
Wherein the present invention reacts the method for the spherical barium sulfate so of the high whiteness of preparation with hydrated barta and ammonium sulfate, by following chemical reaction, realizes:
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 is achieved through the following technical solutions:
The preparation method of ball shaped nano barium sulfate of the present invention comprises the steps:
(1) after barium hydroxide solution and ammoniumsulphate soln are processed respectively, with [Ba
2+]/[SO
4 2-] mol ratio is that 1.00/ (1.05～1.10) are carried out and flow successive reaction, carries out solid-liquid separation after reaction, obtains filter cake and filtrate; It is to be to filter at 30～35 ℃ in temperature that wherein said ammoniumsulphate soln is processed, and preferably with 0.5 μ m aperture accurate filter, filters; It is with 0.5 μ m aperture secondary filter that described ammoniumsulphate soln is processed; In wherein said barium hydroxide solution, barium ion concentration is 0.20～0.30mol/L, preferably 0.25～0.30mol/L; The concentration of ammoniumsulphate soln is 0.05～0.50mol/L, preferably 0.25～0.30mol/L; Wherein said and to flow barium hydroxide solution flow in successive reaction be 2000～6000L/h, preferably 4000～5000L/h; Ammoniumsulphate soln flow is at 2000～10000L/h scope, preferably 4000～6000L/h; Stirring velocity is 400～1500rpm, preferably 1000～1200rpm; Wherein said mother liquor adds after CaO, reclaims NH
3.
The equation reacting with barium hydroxide solution and ammoniumsulphate soln is as follows:
Ba(OH)
2+(NH
4)
2SO
4→BaSO
4↓+2NH
4OH
The object of this step is first to carry out after suitable processing containing hydrated barta and ammoniumsulphate soln, again with certain concentration and flow make the two and flow flow reactor in react, after carry out solid-liquid separation and obtain filter cake and mother liquor, mother liquor is reclaimed to ammonia after treatment.
(2) filter cake step (1) being obtained is distributed in water makes slip, adds sulfuric acid to adjust pH value of solution 2.5～3.0, after add hydrogen peroxide 70～75 ℃ of reactions, reaction finishes rear solid-liquid separation and obtains filter cake and filtrate; Wherein said to add the amount of hydrogen peroxide be that every cubic metre of slip adds 2-3 liter, preferably 2.5 liters; The time of wherein said reaction is 1-3 hour, preferably 2 hours.And
In this step, concrete reaction equation is as follows:
S
2- X+1+H
2O
2+H
+→SO
4 2-+H
2O
The object of this step is to react with the sulfur compound impurities being mixed with in barium sulfate under acidic conditions with hydrogen peroxide, negatively charged ion is wherein converted into sulfate radical, the metal ion that simultaneously metallic impurity elements such as ferrimanganic is converted into solubility makes it to enter in solution and separates by solid-liquid separation, remove the impurity being mixed with in barium sulfate, particularly affect the sulfocompound of color, to be converted into ionic condition and be dissolved in solution and be removed, by this step, make to obtain the feature that spherical barium sulfate has high whiteness.
(3) filter cake step (2) being obtained is distributed in water and forms slip, adds after ammonium sulfate, and adjusting pH is 6.5～7.5, preferably pass into ammonia and adjust pH, after at 75～80 ℃ of temperature, wash, solid-liquid separation obtains filter cake, filter cake obtains ball shaped nano barium sulfate product through evaporation, after drying; Wherein said washing time is 0.5-2 hour, is preferably 1 hour.
The object of this step is to wash obtaining barium sulfate solid in step (2), the object that wherein adds ammonium sulfate in solution is that sulfate ion concentration is increased, utilize the common-ion effcet of barium sulfate, thereby the concentration of the barium ion while reducing balance in solution suppresses crystal growth, but general just by increasing wherein a kind of growth of crystal of control of the concentration barium sulfate of ion, and can not add two kinds of ions simultaneously, prevented the barium sulfate of the coated original generation of newly-generated vitriol; In this step, also acid ion is neutralized, and wash under neutral or near neutral condition, not only make the barium sulfate that obtains for neutral, and removed foreign ion that barium sulfate the adheres to content of the metallic element ions such as ferrimanganic that further improved purity drop.
More particularly, to prepare the method for high whiteness ball shaped nano barium sulfate as follows in the present invention:
By Ba (OH)
2solution temperature is adjusted to 30～35 ℃ of scopes, [Ba
2+] 0.20～0.30mol/L, preferably 0.25～0.30mol/L, filters stand-by with 0.5 μ m aperture accurate filter.
By (NH
4)
2sO
4solution is adjusted into 0.05～0.50mol/L scope, preferred 0.25～0.30mol/L, and under normal temperature, 0.5 μ m aperture secondary filter is stand-by.
Control synthesizer stirring velocity at 400～1500rpm scope, preferably 1000～1200rpm.
With constant flow pump, control barium hydroxide solution flow at 2000～6000L/h scope, preferably 4000～5000L/h.
With constant flow pump, control (NH
4)
2sO
4solution flow is at 2000～10000L/h scope, preferably 4000～6000L/h.
Control building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/(1.05～1.10) scope.
Building-up reactions slurry carries out solid-liquid separation, stripping recovery NH after the supplementary the addition of C aO of mother liquor
3, filter cake enters next-step operation:
Filter cake is placed in acid-resistant container, by material-water ratio, 1:6 adds deionized water, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution 2.5～3.0, in every cubic metre of slip 2-3, rise the preferably ratio of 2.5 liters and add technical grade hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 70～75 ℃ of scopes, stirring oxidation rinsing solid-liquid separation after 2 hours, filtrate is processed discharge, and filter cake enters next-step operation.
Filter cake is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4, make [SO in solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, passes into NH
3adjust slip pH6.5～7.5 scope, chuck is warming up to 75～80 ℃ of scopes, and agitator treating is solid-liquid separation after 1 hour, and filtrate is processed discharge, and filter cake flash evaporation drying obtains spherical nano barium sulfate product.
Embodiment
When first, high whiteness ball shaped nano barium sulfate preparation process in embodiment below and product are analyzed, determinator and measuring method used is described as follows:
What about part measuring method in barium sulfate product analysis, use is standard SN/T 0480-1995(outlet barite analytical procedure) in measuring method;
Specifically, barium sulfate content is measured the method adopting in SN/T 0480.5-1995;
The measuring brightness instrument that the model that measuring brightness adopts Jinan MICHAEL DRAKE Instrument Ltd. to produce is DRK103A (adopt 200 mesh sieves, measure after 105 ℃ of oven dry) is measured according to disclosed method in 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 scanning electronic microscope, NEC company system.
The particle size determination of primary particle: JSM-6490LV type scanning electronic microscope, NEC company system.
PH pH-value determination pH adopts PHS-3C type precision acidity meter, and by Shanghai, precision instrumentation company manufactures.
The device that flash distillation is used is the fast rotational flash dryer that the model of Changzhou sudden peal of thunder drying plant company limited manufacture is 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.
Technical grade hydrogen peroxide: mass percentage concentration is 27.5%, Jiangshan City, Zhejiang Province hydrogen peroxide company produces.
Constant flow pump: the east of a river, Suzhou precision instrument company limited.
Technical grade hydrated barta: Ba (OH)
2content>=98%.
Technical grade ammonium sulfate: (NH
4)
2sO
4content>=95%.
Step in following embodiment (1) and flow successive reaction can by routine and flow flow reactor and react, also can by shown in Fig. 2 and flow flow reactor and complete.
Shown in the process flow sheet of lower combination Fig. 1, illustrate that the present invention prepares the process of high whiteness ball shaped nano barium sulfate, by technical grade hydrated barta (Ba (OH)
2>=98%) add deionized water preparation baryta water, making barium ion concentration is 0.20mol/L, by this Ba (OH)
2solution temperature is adjusted into 30 ℃, with 0.4 μ m aperture accurate filter, filters stand-by.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, under normal temperature, with 0.4 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 400rpm, and with constant flow pump, controlling barium hydroxide solution flow is 2000L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 8400L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.05, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in successive reaction equipment and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in common acid-resistant container, by material-water ratio 1: the mass ratio of 5(slip and water) add deionized water to make slip, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.5, after in every cubic metre of slip, add the ratio of 2 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 70 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 1 hour, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 5, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.04mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 6.5, chuck is warming up to 75 ℃, at this temperature agitator treating after 0.5 hour solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 1
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
Technical grade hydrated barta is joined in deionized water and prepares baryta water, and wherein in barium hydroxide solution, barium ion concentration is 0.25mol/L, by this Ba (OH)
2solution temperature is adjusted into 33 ℃, with 0.5 μ m aperture accurate filter, filters stand-by.With the preparation of technical grade ammonium sulfate ammonium sulfate solution, wherein (NH
4)
2sO
4strength of solution is 0.25mol/L, under normal temperature, with 0.5 μ m aperture accurate filter, filters stand-by.The rotating speed of setting motor 12 is 1100rpm, setting barium hydroxide solution is 4000L/h with the flow of constant flow pump, the flow of setting ammoniumsulphate soln constant flow pump (not shown) used is 4200L/h, rear connection agitator motor power supply, connect the power supply of above-mentioned two constant flow pump (not shown) simultaneously, the baryta water that constant flow pump just configures is that 4000L/h is constantly by the first spray hole 7 by being located at that the first material inlet 2 of the bottom 16 of reactor body 1 joins in reactor body 1 according to flow, it is that 4200L/h is constantly injected to by the second spray hole 12 and flows in reaction chamber 4 according to flow that the ammonium sulfate solution of configuration is joined in reservoir 10 by the second material inlet 11, two kinds of solution moment contact hybrid reactions, control [Ba in synthetic reaction process
2+]/[SO
4 2-] mol ratio is 1.00/1.08.Reacted mixture is being located at and is being flowed under the effect of conical flow guiding cap 13 of reaction chamber bottom 17, constantly by the middle of current limiting plate 6, have metering hole 15 enter into stir chamber 5, the power that material provides by motor 14 in stir chamber 5 is uniformly mixed said mixture between agitating vane 8, be uniformly mixed in process, mixture after lower floor's blade stirring part mixture under the stopping of baffle plate 9 comes back in lower floor's blade and again stirs, part mixture continues to move upward, under the agitating vane effect of upper strata, continue to be stirred, mixture after upper strata agitating vane stirs is uniformly dispersed, in reaction process constantly by spraying in material outlet 3 slave units, after the slurry of collection ejection, carry out solid-liquid separation and obtain filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor
3, filter cake enters next-step operation,
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio, add deionized water to make slip at 1: 6, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.7, after in every cubic metre of slip, add the ratio of 2.5 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 70 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 2 hours, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 7.0, chuck is warming up to 73 ℃, at this temperature agitator treating after 1 hour solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 2
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
By the technical grade hydrated barta preparation baryta water that is added to the water, wherein in barium hydroxide solution, barium ion concentration is 0.30mol/L, by this Ba (OH)
2solution temperature is adjusted into 32 ℃, with 0.6 μ m aperture accurate filter, filters stand-by.With the preparation of technical grade ammonium sulfate ammonium sulfate solution, wherein (NH
4)
2sO
4strength of solution is 0.50mol/L, under normal temperature, with 0.5 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 1000rpm, and with constant flow pump, controlling barium hydroxide solution flow is 6000L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 3960L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.06, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in flow reactor and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio, add deionized water to make slip at 1: 7, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.8, after in every cubic metre of slip, add the ratio of 2.3 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 72 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 1.5 hours, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.06mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 6.8, chuck is warming up to 75 ℃, at this temperature agitator treating after 1.2 hours solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 3
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
Technical grade hydrated barta is joined in deionized water and prepares baryta water, and wherein in barium hydroxide solution, barium ion concentration is 0.30mol/L, by this Ba (OH)
2solution temperature is adjusted into 35 ℃, with 0.7 μ m aperture accurate filter, filters stand-by.With the preparation of technical grade ammonium sulfate ammonium sulfate solution, wherein (NH
4)
2sO
4strength of solution is 0.50mol/L, under normal temperature, with 0.7 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 600rpm, and with constant flow pump, controlling barium hydroxide solution flow is 6000L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 2000L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.07, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in flow reactor and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio, add deionized water to make slip at 1: 7, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 3.0, after in every cubic metre of slip, add the ratio of 3 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 75 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 1.5 hours, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.06mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 7.5, chuck is warming up to 80 ℃, at this temperature agitator treating after 1.5 hours solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 4
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
Technical grade hydrated barta is joined in deionized water and prepares baryta water, and wherein in barium hydroxide solution, barium ion concentration is 0.27mol/L, by this Ba (OH)
2solution temperature is adjusted into 33 ℃, with 0.5 μ m aperture accurate filter, filters stand-by.Ammonium sulfate preparation ammonium sulfate solution, wherein (NH with technical grade
4)
2sO
4strength of solution is 0.30mol/L, under normal temperature, with 0.6 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 1000rpm, and with constant flow pump, controlling barium hydroxide solution flow is 5000L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 10000L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.07, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in flow reactor and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio, add deionized water to make slip at 1: 6, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.9, after in every cubic metre of slip, add the ratio of 2.3 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 72 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 2.5 hours, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 8, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.04mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 6.9, chuck is warming up to 78 ℃, at this temperature agitator treating after 1.5 hours solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 5
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
Technical grade hydrated barta is joined in deionized water and prepares baryta water, and wherein in barium hydroxide solution, barium ion concentration is 0.25mol/L, by this Ba (OH)
2solution temperature is adjusted into 32 ℃, with 0.7 μ m aperture accurate filter, filters stand-by.Ammonium sulfate preparation ammonium sulfate solution, wherein (NH with technical grade
4)
2sO
4strength of solution is 0.05mol/L, under normal temperature, with 0.5 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 400rpm, and with constant flow pump, controlling barium hydroxide solution flow is 4000L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 2000L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.06, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in flow reactor and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio 1:6, add deionized water to make slip, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.8, after in every cubic metre of slip, add the ratio of 2.5 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 70 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 1 hour, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 7.0, chuck is warming up to 78 ℃, at this temperature agitator treating after 1 hour solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 6
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
Technical grade hydrated barta is joined in deionized water and prepares baryta water, and wherein in barium hydroxide solution, barium ion concentration is 0.25mol/L, by this Ba (OH)
2solution temperature is adjusted into 32 ℃, with 0.7 μ m aperture accurate filter, filters stand-by.Ammonium sulfate preparation ammonium sulfate solution, wherein (NH with technical grade
4)
2sO
4strength of solution is 0.05mol/L, under normal temperature, with 0.5 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 400rpm, and with constant flow pump, controlling barium hydroxide solution flow is 4000L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 6000L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.06, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in flow reactor and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio, add deionized water to make slip at 1: 6, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.8, after in every cubic metre of slip, add the ratio of 2.5 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 70 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 1 hour, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 7.0, chuck is warming up to 78 ℃, at this temperature agitator treating after 1 hour solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 7
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
The hydrated barta of technical grade is joined in deionized water and prepares baryta water, and wherein in barium hydroxide solution, barium ion concentration is 0.25mol/L, by this Ba (OH)
2solution temperature is adjusted into 33 ℃, with 0.5 μ m aperture accurate filter, filters stand-by.With technical grade ammonium sulfate preparation ammonium sulfate solution (please supplement the requirement of the aspects such as source, purity of ammonium sulfate), wherein (NH
4)
2sO
4strength of solution is 0.25mol/L, under normal temperature, with 0.5 μ m aperture accurate filter, filters stand-by.Controlling and flowing continuous synthesizer stirring velocity is 1100rpm, and with constant flow pump, controlling barium hydroxide solution flow is 4500L/h, with constant flow pump, controls (NH
4)
2sO
4solution flow is 5000L/h, controls building-up reactions [Ba
2+]/[SO
4 2-] mol ratio is 1.00/1.08, by the Ba after above-mentioned processing (OH)
2solution and (NH
4)
2sO
4solution is ejected into and flows in flow reactor and react, and carries out solid-liquid separation and obtains filter cake and mother liquor, stripping recovery NH after the supplementary the addition of C aO of mother liquor in reaction process after continuous collection slurry
3, filter cake enters next-step operation;
Filter cake obtained in the previous step is placed in acid-resistant container, by material-water ratio, add deionized water to make slip at 1: 6, dispersed with stirring, add a small amount of sulfuric acid to adjust pH value of solution to 2.7, after in every cubic metre of slip, add the ratio of 2.5 liters of technical grade hydrogen peroxide to add hydrogen peroxide, chuck heat temperature raising, hierarchy of control temperature is 70 ℃, at this temperature, stir oxidation rinsing solid-liquid separation after 2 hours, filtrate is processed discharge, and filter cake enters next-step operation.
The filter cake that upper step is obtained is placed in washing pot, by material-water ratio, adds deionized water at 1: 6, and dispersed with stirring adds appropriate (NH simultaneously
4)
2sO
4make [SO in solution
4 2-] concentration reaches 0.05mol/L to suppress crystal growth, after pass into NH
3adjust slip pH to 7.0, chuck is warming up to 73 ℃, at this temperature agitator treating after 1 hour solid-liquid separation obtain filter cake and filtrate, filtrate is processed discharge, filter cake flash evaporation drying obtains spherical nano barium sulfate product 8
#, it is carried out to barium sulfate content, Mn content, Fe content, whiteness, fineness (325 screen residue), the mensuration of particle diameter and particle morphology is in Table 1.
The barium sulfate product property testing result that table 1 embodiment of the present invention prepares
By the result in upper table, show, the content of the barium sulfate that the embodiment of the present invention prepares is all greater than 99.0%, and wherein the content of the barium sulfate in embodiment 2,5 and 8 is greater than 99.3%; Embodiment 1-8 prepares Mn content in barium sulfate and Fe content all lower than 1.0ppm, and whiteness is all greater than 98.5%, and fineness is in 325 screen residues, all lower than 0.10%; The median size of the barium sulfate preparing all reaches 20-40nm, and the median size of the barium sulfate of embodiment 2-5,7 and 8 preparations all reaches 20-30nm, and particle morphology is spherical.Barium sulfate prepared by above-mentioned digital proof the present invention has high whiteness, high purity, and particle diameter has reached nano level feature.
The present invention has carried out above-mentioned description to some preferred implementation and embodiment, to help the public to use suitable experimental technique in implementing process of the present invention, obtain good experiment effect, this does not get rid of the experimental technique being equal to of not enumerating in the present invention also can implement the present invention.It will be appreciated by those skilled in the art that the present invention is except specifically described mode, can also be applicable to distortion and revise.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 public to understanding herein, should not regarded as limiting the scope of the present invention.
Make a general survey of whole specification sheets and claims, unless context needs, otherwise word " comprises ", " comprising " and similar word, and the implication that is interpreted as comprising but not the implication got rid of that is to say, look like for " including, but are not limited to ".
Claims (20)
1. a preparation method for ball shaped nano barium sulfate, comprises the steps:
(1) after barium hydroxide solution and ammoniumsulphate soln are processed respectively, with [Ba
2+]/[SO
4 2-] mol ratio be that 1.00/ (1.05～1.10) are carried out and flow successive reaction, after reaction, carry out solid-liquid separation, obtain filter cake and filtrate;
(2) filter cake step (1) being obtained is distributed in water makes slip, adds sulfuric acid to adjust pH value of solution 2.5～3.0, after add hydrogen peroxide 70～75 ℃ of reactions, reaction finishes rear solid-liquid separation and obtains filter cake and filtrate; And
(3) filter cake step (2) being obtained is distributed to and in water, forms slip, adding ammonium sulfate to make ammoniumsulphate soln concentration is 0.04-0.07mol/L, adjusting pH is 6.5～7.5, after at 75～80 ℃ of temperature, wash, solid-liquid separation obtains filter cake, and filter cake obtains ball shaped nano barium sulfate product after evaporation, oven dry.
2. the preparation method of ball shaped nano barium sulfate as claimed in claim 1, wherein step (1) [Ba
2+]/[SO
4 2-] mol ratio be 1.00/1.08.
3. the preparation method of ball shaped nano barium sulfate as claimed in claim 1, described barium hydroxide solution is processed is to be to filter at 30～35 ℃ in temperature; It is to filter that described ammoniumsulphate soln is processed.
4. the preparation method of ball shaped nano barium sulfate as claimed in claim 3, is wherein 0.4-0.7 μ m by barium hydroxide solution processing and ammoniumsulphate soln processing filtration with the aperture of filter membrane.
5. the preparation method of ball shaped nano barium sulfate as claimed in claim 1, in the described barium hydroxide solution of step (1), barium ion concentration is 0.20～0.30mol/L, barium hydroxide solution flow is
2000～6000L/h; The concentration of ammoniumsulphate soln is 0.05～0.50mol/L, and ammoniumsulphate soln flow is in 2000～10000L/h scope.
6. the preparation method of the ball shaped nano barium sulfate as described in claim 1-5 any one, wherein step (1) is described and flow in successive reaction, and stirring velocity is 400～1500rpm.
7. the preparation method of the ball shaped nano barium sulfate as described in claim 1-5 any one, wherein the described filtrate of step (1) adds after CaO, reclaims NH
3.
8. the preparation method of the ball shaped nano barium sulfate as described in claim 1-5 any one, the amount that wherein adds hydrogen peroxide in step (2) is that every cubic metre of slip adds 2-3 liter.
9. the preparation method of ball shaped nano barium sulfate as claimed in claim 6, the amount that wherein adds hydrogen peroxide in step (2) is that every cubic metre of slip adds 2-3 liter.
10. the preparation method of the ball shaped nano barium sulfate as described in claim 1-5 any one, is wherein 1-3 hour in the reaction times of 70～75 ℃ of reactions in step (2).
The preparation method of 11. ball shaped nano barium sulfate as described in claim 1-5 any one, wherein the described washing time of washing at 75～80 ℃ of temperature of step (3) is 0.5-2 hour.
The preparation method of 12. ball shaped nano barium sulfate as claimed in claim 10, wherein the described washing time of washing at 75～80 ℃ of temperature of step (3) is 0.5-2 hour.
The preparation method of 13. ball shaped nano barium sulfate as described in claim 1-5 any one, wherein the described water of step (2) and step (3) is deionized water.
The preparation method of 14. ball shaped nano barium sulfate as described in claim 1-5 any one, rapid (2) and step (3) add the quality of water to be respectively 5-8 times of filter cake quality.
The preparation method of 15. ball shaped nano barium sulfate as claimed in claim 13, rapid (2) and step (3) add the quality of water to be respectively 5-8 times of filter cake quality.
16. 1 kinds for claim 1-15 any one method for preparing nano barium sulfate step (1) Suo Shu and that flow 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 flows reaction chamber (4) and stir chamber (5) separates by current limiting plate (6); In the middle of current limiting plate (4), open metering hole (15); And flow reaction chamber (4) and surrounded by the sidewall that also flows bottom (17), current limiting plate (4) and the reactor body (1) of reaction chamber; Bottom (16) in reactor body (1) is provided with the first material inlet (2); In reactor body (1) lower, outer perimeter, around reactor body (1), be provided with reservoir (10), on reservoir (10) wall, have the second material inlet (11); On the top of reactor body (1), be provided with material outlet (3); Bottom (17) described and that flow reaction chamber (4) is provided with the first spray hole (7) and fairing cap (13); And flow on reactor body (1) sidewall at reaction chamber 4 places and have at least two the second spray holes (12).
17. is as claimed in claim 16 and flow successive reaction equipment, wherein in stir chamber (5), between adjacent agitating vane (8), on reactor body (1) wall, is provided with symmetrically baffle plate (9).
18. is as described in claim 16 or 17 and flow successive reaction equipment, and wherein fairing cap (8) is taper, and it is located at and flows bottom (17) central authorities of reaction chamber (4).
19. is as described in claim 16 or 17 and flow successive reaction equipment, wherein said and flow reaction chamber (4) bottom (17) and offer at least two the first spray holes (7).
20. is as claimed in claim 19 and flow successive reaction equipment, at the top of reactor body (1), is also provided with motor (14).
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| CN104512923A (en) * | 2013-09-30 | 2015-04-15 | 上海梅山钢铁股份有限公司 | Preparation method of nano-barium sulfate |
| CN103626219B (en) * | 2013-12-19 | 2015-02-11 | 贵州红星发展股份有限公司 | Nano barium sulfate and preparation method thereof |
| CN105789656B (en) * | 2016-04-14 | 2019-04-23 | 扬州大学 | A kind of resource utilization method of the sulfuric acid solution of barium sulfate-containing |
| 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 |
| 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 |
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