CN104986796A - Device system and preparation technology for preparing submicron material through continuous hydrothermal method - Google Patents
Device system and preparation technology for preparing submicron material through continuous hydrothermal method Download PDFInfo
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- B01D9/02—Crystallisation from solutions
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C01G23/047—Titanium dioxide
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- C01G23/00—Compounds of titanium
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- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
Abstract
The invention provides a device system and preparation technology for preparing a submicron material through a continuous hydrothermal method. The device system comprises burdening kettles, a preheater, a first crystallizer and a second crystallizer. The first burdening kettle is communicated with the first crystallizer through a first feeding pump and the preheater, and the second burdening kettle is communicated with the first crystallizer through a second feeding pump. The first crystallizer is communicated with the second crystallizer, a discharging opening of the second crystallizer is communicated with an inlet of a heat exchanger, one outlet of the heat exchanger is communicated with an outer circulating unit and then communicated with an inlet of the second crystallizer, and the other outlet of the heat exchanger is communicated with an aftertreatment unit and a slurry collector. The first crystallizer is a tubular reaction crystallizer, and the second crystallizer is a continuous crystallizer. The device system is adopted in the preparation technology. According to the device system and preparation technology, the device cost is low, meanwhile, the submicron material with even particle size distribution and the high degree of crystallinity can be prepared continuously, and the device system and preparation technology are suitable for industrial production.
Description
Technical field
The present invention relates to the Liquid preparation methods technique of submicron material, particularly a kind of serialization hydrothermal method prepares apparatus system and the preparation technology thereof of submicron material.
Background technology
Ultra-fine powder technology is the new branch of science that 20 century 70s grow up mid-term, and superfine powder is almost applied to all industries of national economy.It is transformation and the basis promoting the new industry development such as paint, information recode medium, fine ceramics, electronic technology, novel material and biotechnology, is the starting point of modern high technology, increasingly becomes the emphasis of various countries' research.Along with the super-refinement of material, its Electronic Structure and crystalline structure there occurs change, create the surface effects that bulk material does not possess, small-size effect, quantum effect and macro quanta tunnel effect, thus make superfine powder have physics, the chemical property of a series of excellence compared with conventional particulate materials.And the physicochemical property of these uniquenesses make it have a wide range of applications in various fields such as electronics, chemical, life science, medical science.According to the difference of material particle size, generally acknowledge that being less than 1nm is elementide in the world, 1nm ~ 100nm is nanometer-scale spatial, and 100nm ~ 1 μm is submicron system, and 1 μm ~ 10 μm is powder body, and 10 μm ~ 45 μm is fine powder body.Submicron order material is an important system in super-fine material, can be divided into again deep-submicron (100nm ~ 500nm) and submicron order (500nm ~ 1 μm).
For a certain specific superfine powder, only above-mentioned division is not accurate enough, and the size distribution of general superfine powder is normal distribution law.Such as: a kind of superfine powder, have 70% to be less than 1 μm, belong to submicron powder, also have 30% to be greater than 1 μm and belong to micro-powder, how to determine that above-mentioned powder is micron or submicron powder.Should from the application point of certain material, adopt the volume fraction of D95 particle diameter or the volume fraction of D97 particle diameter, even the volume fraction of D50 particle diameter is less than a certain value to define is belong to micro-powder or submicron powder or nano-powder.Submicron order powder in this patent adopts D50, PDI (size distribution coefficient), and three indexs of D97 < 1 μm determine the particle diameter system of product jointly.
Super-fine material has excellent physico-chemical property, and these character are subject to the size of super-fine material, the impact of appearance structure, therefore its control synthesis of realization of industrialization and relation between its structure and properties of studying are applied all significant for fundamental research and technology.Hydrothermal method is a kind of important method that liquid phase reaction crystallization processes prepares super-fine material, hydrothermal crystallisation methods is in special closed reactor, adopt the aqueous solution as reaction system, by heating reaction system, pressurizeing (or spontaneous vapour pressure), create the reaction environment of a relatively-high temperature, high pressure, make usual indissoluble or insoluble substance dissolves, chemical reaction occurs, and recrystallization and carry out a kind of effective ways of Inorganic synthese and material processing.Product performance stablize, simple to operate, process and quality product controlled, the product powder thing of preparation is mutually homogeneous, and purity is high, grain diameter is little and be evenly distributed, and is applicable to the preparation of superfine function material.
Continuous hydrothermal method has been subject to the whole world as low cost preparation technology and has more and more paid close attention to, the domestic relevant report also not having continuous prodution, most methods of domestic employing are the periodical operation of autoclave pressurized vessel, and such operation also exists: 1. wall heat transfer coefficient is low, heat-up time is long, and energy consumption is high; 2. in slip, powder granule is easy to sticky wall, more reduces heat transfer efficiency; 3. under high-temperature and high-pressure conditions, kettle sealing difficulty, may there is non-uniform phenomenon in kettle local pressure, temperature, security is lower; 4. full-scale plant and lab scale, pilot plant product performance difference are large.
Why continuous hydrothermal method is also adopted by wide sending out in actual applications, and we think and are mainly how controlling correlation parameter to control the physical and chemical performance of crystal product in the mechanism of liquid phase water thermal response crystallisation process and Practical Project process.Liquid phase water thermal response crystallisation process is a chemistry and crystallization two process compositions, relate to the second process (assemble, grow dispersion, slaking etc.) of chemical reaction, crystal nucleation, crystal growth and crystal, chemical reaction produces degree of supersaturation, the speed of chemical reaction and along with the change etc. of solution ph all directly affect crystallisation process; Secondly, because the particle diameter of product is less, there is larger specific surface, crystal is very easy to occur to assemble growth; Thirdly, due to the singularity of presoma, affect the dissolution rate problem also relating to presoma of chemical reaction process, and the granularity of the speed of dissolution rate and presoma, temperature rise rate etc. is correlated with, and the homogeneity of crystallisation process and degree of supersaturation and distribution thereof is closely related.Generally speaking, this is a quite complicated complex process, require that we mask some fully and (some parameter values are stabilized in optimum range to the larger factor of product physical and chemical performance impact fluctuation on the equipment Design of reality, it is avoided to produce great effect to crystallisation process), focus in the control to crystallization, accomplish to control single or several factor just energy stable crystalline product as far as possible.In brief, high degree of supersaturation and be evenly distributed that to control ultra-fine grain surface potential be the key preparing even submicron material simultaneously.
Summary of the invention
The invention provides apparatus system and preparation technology thereof that a kind of serialization hydrothermal method prepares submicron material, this apparatus system and preparation technology solve continuous hydrothermal legal system for problems such as the device of submicron material and Technology is immature, crystalline rate is low, easy reunions, are applicable to the industrial continuous hydrothermal method of submicron material and produce.
According to an aspect of the present invention, provide a kind of serialization hydrothermal method to prepare the apparatus system of submicron material, comprise the first batching kettle, the second batching kettle, preheater, the first crystallizer, the second crystallizer and interchanger.Wherein, the first batching kettle is communicated with the first fresh feed pump and preheater successively by pipeline, and the second batching kettle is communicated with the second fresh feed pump by pipeline, and preheater and the second fresh feed pump are all communicated with the feeding mouth of the first crystallizer by pipeline.The discharge port of the first crystallizer is communicated with the feeding mouth of the second crystallizer by pipeline, the discharge port of the second crystallizer is communicated with the entrance of described interchanger by pipeline, the outlet of interchanger is divided into two, an outlet outer circulation unit of interchanger is communicated with the entrance of the second crystallizer again, and another outlet post-processing unit of interchanger is communicated with slip collector again.Wherein, the first crystallizer is pipe reaction crystallizer, and the second crystallizer is successive type reaction crystalizer.
Its beneficial effect is, owing to adding preheater, can heat in advance, realize being rapidly heated to the solution be placed in the first batching kettle.The first crystallizer increased can the pre-mixing of realization response solution and using pre-nucleating, is conducive to better crystallization and control size distribution in the second crystallizer.Owing to being communicated with interchanger outside the second crystallizer, after solution enters interchanger, can degree of supersaturation be produced, device can be reduced to the cost producing degree of supersaturation.The external circulating system arranged can improve crystalline rate and degree of crystallinity.In addition, according to the reactive crystallization mechanism of nanocrystal, pipe reaction crystallizer and successive type reaction crystalizer series combination are got up, ground submicron crystal homogeneous nucleation, growth and avoiding improving the degree of crystallinity of submicron particles under the prerequisite of assembling growth under high degree of supersaturation can be realized preferably.
In some embodiments, the second crystallizer is DTB type crystallizer.Its beneficial effect is, because draft tube baffle crystallizer is a kind of high efficiency career crystallizer, be widely used in the industrial crystallization fields such as cooling, vacuum, its inside has good flow field, degree of supersaturation is little and evenly, provides a gentle condition for further crystallization improves degree of crystallinity.
In some embodiments, pipe reaction crystallizer is that the line mixer having a same inner diameter by multistage forms, and the caliber of pipe reaction crystallizer is DN25 ~ DN125mm.Its beneficial effect is, because pipe reaction crystallizer is made up of multistage line mixer, the manufacturing cost of pipe reaction crystallizer not only can be reduced, also convenient for dismounting and washing, also according to the needs of reaction soln, total length and the caliber size of tubular mold can be adjusted flexibly simultaneously.
In some embodiments, outer circulation unit comprises recycle pump.Post-processing unit comprises the condenser, strainer and the bleeder valve that are communicated with successively.Its beneficial effect is that recycle pump can be outer circulation and provides power.Condenser can fast cooling, and the crystal cluster that filters out particles is grown up because of gathering, ensure that the homogenization of product granularity.
In some embodiments, outer circulation unit also comprises waterpower ultra-sonic generator, and waterpower ultra-sonic generator is located between recycle pump and the second crystallizer.Bleeder valve is back pressure valve.Its beneficial effect is, vibrates and produces Hydrodynamic cavitation effect, Granular composite can be opened because waterpower ultrasonic device relies on the high speed of vibrating reed, avoids assembling growth.Back pressure valve can control load flexibly, and back pressure valve price is low, is applicable to industrial production and uses.
In some embodiments, be equipped with under meter near the first fresh feed pump, the second fresh feed pump and recycle pump, the pipeline of the outer circulation of the second crystallizer is provided with pH detector and pH value feeding liquid variable valve.Its beneficial effect is, because the under meter increased conveniently monitors flow.Due in crystallization process, the pH of solution can change along with the carrying out of reaction, increases the pH of pH detector convenient monitoring solution, increases the pH that pH value feeding liquid variable valve is used for real-time regulator solution, solution particles surface Zeta potential can be controlled, avoid particle agglomeration.
According to another aspect of the present invention, provide the preparation technology that a kind of serialization hydrothermal method prepares submicron material, this technique uses the apparatus system in above-mentioned embodiment, and this technique comprises the steps:
Splendid attire enters preheater preheats to certain temperature in the first stock liquid of the first batching kettle after the first fresh feed pump conveying, splendid attire in the second batching kettle the second stock liquid through second fresh feed pump conveying and with the first stock liquid after preheating according to a certain volume example enter the first crystallizer, obtain slip, slip with after certain flow rate for some time, enters the second crystallizer in the first crystallizer;
Slip enters the second crystallizer and carries out crystallization, part slip flows out from the discharge port of the second crystallizer, through interchanger heat exchange, the second crystallizer is again entered after mixing with the slip from the first crystallizer under the driving of recycle pump, form an outer circulation, react for some time in the second crystallizer after, obtain suspension magma;
Suspension magma flows out from the discharge port of the second crystallizer, and through interchanger heat exchange, after condenser condenses to certain temperature, the crystal cluster of being grown up because of gathering on a small quantity by strainer filtering, ensure that the homogenization of product granularity; Under the effect of bleeder valve, magma is stablized discharging and is collected in slip collector.
Wherein, the first stock liquid is precursor solution, and the second stock liquid is the aqueous solution or another precursor solution; In crystallization process, the pH regulating and controlling the magma in the second crystallizer, to control the Zeta potential on suspended crystal surface, avoids the particle aggregation of magma to grow.
Its beneficial effect is, when the second stock liquid mixes with the first stock liquid through preheating in the first crystallizer, because the temperature of the first stock liquid is high, can carry out heat temperature raising fast, improve degree of supersaturation in mixing moment to the first stock liquid.Stock liquid after preliminary crystallization produces a large amount of sub-micron grade particle in the first crystallizer, enters further crystallization in the second crystallizer, and part slip enters interchanger and produces degree of supersaturation, is convenient to nucleus and is formed and grain growth.Slip carries out outer circulation by recycle pump outside the second crystallizer, can improve crystalline rate and degree of crystallinity.Magma cools through condenser, can fast cooling, avoids particle agglomeration.
In some embodiments, the first stock liquid is 100 ~ 350 DEG C through the preheating temperature of preheater.
In some embodiments, the first stock liquid after the second stock liquid and preheating enters the first crystallizer by the volume ratio of 1: 1 ~ 1: 10.Its beneficial effect is, by controlling the ratio of stock liquid, the suspension density in controllable slurry or grain number density, avoid particle aggregation.
In some embodiments, the flow velocity of slip in the first crystallizer pipe is 0.25 ~ 1.0m/s, and the residence time is 1 ~ 30min.Be 0.5 ~ 24h in the reaction times of the second crystallizer, the temperature after condenser is 25 ~ 60 DEG C.The filter screen precision of strainer is 1.0 μm.Its beneficial effect is, controls suspension density in the first crystallizer or grain number density, avoid particle aggregation by coutroi velocity and reaction times.In addition, controlling velocity in pipes also can avoid inside pipe wall to scab phenomenon.The effect of strainer is the granularity in order to control submicron order product.
Reactive crystallization control principle of the present invention is: according to the mechanism of hydro-thermal reaction crystallisation process, nucleation and growth are separated, improve nucleation rate, crystallization (slaking) under low degree of supersaturation also by gathering that is chemical and physical method control ultrafine particle, obtains the submicron material of even particle size distribution continuously.
Accompanying drawing explanation
Fig. 1 is that a kind of serialization hydrothermal method of an embodiment of the present invention prepares the apparatus system of submicron material and the process flow diagram of preparation technology;
The submicron order titanium dioxide particle size distribution figure of Fig. 2 prepared by embodiment 1;
Fig. 3 prepared by embodiment 3 submicron order iron lithium phosphate particle size distribution figure.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is further detailed explanation.
Be that a kind of serialization hydrothermal method of the present invention prepares the apparatus system of submicron material and the process flow diagram of preparation technology see Fig. 1.Serialization hydrothermal method prepares an apparatus system for submicron material, comprises the first batching kettle 1, second batching kettle 2, preheater 5, first crystallizer 6, second crystallizer 7 and interchanger 9.Wherein, the first batching kettle 1 and the second batching 2 stills are respectively used to splendid attire first solution and the second solution.First batching kettle 1 is communicated with the first fresh feed pump 3 successively by pipeline and preheater 5, second batching kettle 2 is communicated with the second fresh feed pump 4 by pipeline, and preheater 5 is all communicated with the feeding mouth of the first crystallizer 6 with the second fresh feed pump 4 by pipeline.The discharge port of the first crystallizer 6 is communicated with the feeding mouth of the second crystallizer 7 by pipeline, the discharge port of the second crystallizer 7 is communicated with the entrance of interchanger 9 by pipeline, the outlet of interchanger 9 has two, and an outlet of interchanger 9 enters the entrance of the second crystallizer 7 again by outer circulation unit; Another outlet of interchanger 9 is communicated with post-processing unit by pipeline and is communicated with slip collector 15 again.
Second crystallizer 7 is successive type reaction crystalizer, preferably DTB type crystallizer.Agitator or water screw can be set up, to promote to expect in crystallizer that oar moves upward in second crystallizer 7.First crystallizer 6 can be pipe reaction crystallizer, and the line mixer that pipe reaction crystallizer can have a same inner diameter by multistage forms different lengths, and line mixer can be assembled into arbitrary structures, and usually, the structure that pipe reaction crystallizer forms is U-shaped structure.Pipe reaction crystallizer is vertical or horizontal arrangement, and preferably, pipe reaction crystallizer is horizontal arrangement.The caliber preferably DN25 ~ DN125mm of pipe reaction crystallizer.
In present embodiment, outer circulation unit comprises recycle pump 10.Post-processing unit comprises the condenser 12, strainer 13 and the bleeder valve 14 that are communicated with successively.Power is provided because recycle pump 10 can be outer circulation unit.Condenser 12 can fast cooling, and strainer 13 can filter out the crystal cluster of growing up because of gathering, ensure that the homogenization of product granularity, and bleeder valve 14 ensures to stablize discharging.
In order to avoid the particle agglomeration in external circulating system, outer circulation unit also comprises waterpower ultra-sonic generator 11, and waterpower ultra-sonic generator 11 is between recycle pump 10 and the second crystallizer 7.Waterpower ultrasonic device 11 relies on the high speed of vibrating reed and vibrates generation Hydrodynamic cavitation effect, Granular composite can be opened, and avoids reuniting.Slip through waterpower ultra-sonic generator 11 enters in the second crystallizer 7 together with the slip from the first crystallizer 6, carries out continuous circulation flowing.Bleeder valve 14 can be discharging pump or back pressure valve, and preferably, bleeder valve 14 is back pressure valve.
Conveniently control, be equipped with under meter near the first fresh feed pump 3, second fresh feed pump 4 and recycle pump 10, the pipeline of the outer circulation of the second crystallizer 7 is provided with pH detector to detect the pH value of the slip in external circulating system.The pipeline of outer circulation is also connected with pH value feeding liquid variable valve 8, in order to the inlet of control engineering liquid PL, engineering liquid PL is engineering acid solution or alkali lye.PH value feeding liquid variable valve 8 is preferably arranged on the take-off line between the second crystallizer 7 and interchanger 9.
Serialization hydrothermal method prepares a preparation technology for submicron material, and this technique comprises the steps:
Splendid attire enters preheater 5 in the first stock liquid of the first batching kettle 1 and is preheated to certain temperature after the first fresh feed pump 3 is carried, splendid attire in the second batching kettle 2 the second stock liquid through the second fresh feed pump 4 carry and with the first stock liquid after preheating according to a certain volume example enter the first crystallizer 6, obtain slip, slip with after certain flow rate for some time, enters the second crystallizer 6 in the first crystallizer 6;
Slip enters the second crystallizer 6 and carries out crystallization, part slip flows out from the discharge port of the second crystallizer 6, through interchanger 9 heat exchange, the second crystallizer 7 is again entered after mixing with the slip from the first crystallizer 6 under the driving of recycle pump 10, form an outer circulation, react for some time in the second crystallizer 7 after, obtain suspension magma;
Suspension magma flows out from the discharge port of the second crystallizer 7, and through interchanger 9 heat exchange, after condenser 12 is condensed to certain temperature, the crystal cluster of being grown up because of gathering on a small quantity by strainer 13 filtering, ensure that the homogenization of product granularity; Under the effect of bleeder valve 14, magma is stablized discharging and is collected in slip collector 15.
Wherein, the first stock liquid is precursor solution, and the second stock liquid is the aqueous solution or another precursor solution, the preferably aqueous solution.In crystallization process, regulate and control the pH of the magma in the second crystallizer 7, by the inlet of adjust ph feeding liquid variable valve 8 control engineering liquid PL, to control the Zeta potential on suspended crystal surface, avoid the particle aggregation of magma to grow.
Optionally, the first stock liquid is 100 ~ 350 DEG C through the preheating temperature of preheater 5.
Optionally, the first stock liquid after the second stock liquid and preheating enters the first crystallizer by the volume ratio of 1: 1 ~ 1: 10.
Optionally, the flow velocity of slip in the first crystallizer 6 pipe is 0.25 ~ 1.0m/s, and the residence time is 1 ~ 30min.
Optionally, the temperature of reaction of the second crystallizer 7 is not more than the temperature of reaction of described first crystallizer 8.
Optionally, be 0.5 ~ 24h in the reaction times of the second crystallizer 8, the temperature after condenser 12 is 25 ~ 60 DEG C, and the filter screen precision of strainer is 1.0 μm.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation technology that serialization hydrothermal method provided by the invention prepares submicron material being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
Prepare submicron order titanium dioxide for sulfuric acid process, serialization hydrothermal method prepares the preparation technology of submicron titanium dioxide, as follows:
First stock liquid is titanium sulfate liquid precursor solution, and the second stock liquid is the aqueous solution.TiO in titanium sulfate liquid precursor solution
2concentration 260g/L, acidity quotient F value (effective acid and total TiO
2the ratio of concentration) be 2.0, iron titanium ratio (in titanium liquid the concentration of iron ion and the ratio of total titanium concentration) is 0.21, titanium liquid stability > 500, and clarity is better, and temperature is 40 DEG C.Temperature out through the preheating water of preheater 5 is 125 DEG C, and the volume ratio entering titanium sulfate liquid precursor solution in the first crystallizer 6 and preheating water is the caliber of the 1: 4, first crystallizer 6 is DN25.The flow of precursor solution is 250L/h, and the flow of water is 1000L/h.The velocity in pipes of the first crystallizer 6 is 0.75m/s, and the residence time is 5min, and piping arrangement adopts Horizontal U-shaped arrangement, and pipeline overall length is 200m, and maintaining temperature in pipe is 108 DEG C, and the second crystallizer 7 temperature is 105 DEG C, is 5h in the residence time of the second crystallizer 7.TiO
2iso-electric point be about 4.3, it is 7.2 that the pH value of the second crystallizer 7 inner suspension magma controls, and away from iso-electric point, avoid particle aggregation to grow, the control pressure of bleeder valve 14 is 0.1MPa, and condenser 12 temperature out is 40 DEG C, and the filter screen of strainer 14 is 1.0 μm.
By prepare above collect obtain metatitanic acid precipitation through the later stage calcining after obtain submicron order titanium dioxide.See the submicron order titanium dioxide particle size distribution figure that Fig. 2 is prepared, the particle diameter D50=271.3nm of product, PDI=0.367, D97=378.1nm.
Embodiment 2
Serialization hydrothermal method prepares the preparation technology of submicron titanium dioxide, as follows:
First stock liquid is titanium sulfate liquid precursor solution, and the second stock liquid is the aqueous solution.TiO in titanium sulfate liquid precursor solution
2concentration 300g/L, acidity quotient F value (effective acid and total TiO
2the ratio of concentration) be 1.8, iron titanium ratio (in titanium liquid the concentration of iron ion and the ratio of total titanium concentration) is 0.21, titanium liquid stability > 500, and clarity is better, and temperature is 30 DEG C.Temperature out through the preheating water of preheater 5 is 180 DEG C, and the volume ratio entering titanium sulfate liquid precursor solution in the first crystallizer 6 and preheating water is the caliber of the 1: 1, first crystallizer 6 is DN125.The flow of precursor solution is 5500L/h, and the flow of water is 5500L/h.The velocity in pipes of the first crystallizer 6 is 0.25m/s, and the residence time is 30min, and the piping arrangement of pipe reaction crystallizer adopts Horizontal U-shaped arrangement, pipeline overall length is 480m, maintaining temperature in pipe is 105 DEG C, and the second crystallizer 7 temperature is 102 DEG C, is 24h in the residence time of the second crystallizer 7.TiO
2iso-electric point be about 4.3, it is 7.5 that the pH value of the second crystallizer 7 inner suspension magma controls, and away from iso-electric point, avoid particle aggregation to grow, the control pressure of bleeder valve 14 is 0.1MPa, and condenser 12 temperature out is 25 DEG C, and the filter screen of strainer 14 is 1.0 μm.
By prepare above collect obtain metatitanic acid precipitation through the later stage calcining after obtain submicron order titanium dioxide, the particle diameter D50=286.5nm of prepared product, PDI=0.335, D97=352.6nm.
Embodiment 3
To prepare the crucial LiFePO 4 of anode material of lithium ion battery, serialization hydrothermal method prepares the preparation technology of submicron iron lithium phosphate, as follows:
First stock liquid is precursor solution, and the second stock liquid is the aqueous solution.Precursor solution is 85% phosphoric acid, the 1.5mol/L LiOH aqueous solution and 0.5mol/L FeSO
4the aqueous solution, according to the suspension liquid of certain reinforced configuration smoothly, is Li through the known throw out of XRD analysis mutually
3pO
4and Fe
3(PO4)
28H
2o, the pH value of suspension liquid is 6.0, and temperature is 35 DEG C.Temperature out through the preheating water of preheater 5 is 220 DEG C, and the volume ratio of precursor solution and preheating water is 1: 5, and caliber is DN25, and presoma flow is 200L/h, and the flow of water is 1000L/h.The velocity in pipes of the first crystallizer 6 is 0.65m/s, and the residence time is 10min, and the piping arrangement of the first crystallizer 6 adopts Horizontal U-shaped arrangement, pipeline overall length is 400m, and maintaining temperature in pipe is 185 DEG C, and the second crystallizer 7 temperature is 180 DEG C, the residence time of the second crystallizer 7 is 3h, LiFePO
4iso-electric point be about 3.55, it is 6.8 that the pH value of the second crystallizer 7 inner suspension magma controls, and away from iso-electric point, avoid particle aggregation to grow, the control pressure of bleeder valve 14 is 1.0MPa, and condenser 12 temperature out is 60 DEG C, and the filter screen of strainer 13 is 1.0 μm.See the submicron order iron lithium phosphate particle size distribution figure that Fig. 3 is prepared, product cut size D50=253.7nm, PDI=0.168, D97=342nm.
Embodiment 4
Serialization hydrothermal method prepares the preparation technology of submicron iron lithium phosphate, as follows:
First stock liquid is precursor solution, and the second stock liquid is the aqueous solution.Precursor solution is 85% phosphoric acid, the 2.5mol/L LiOH aqueous solution and 1.0mol/L FeSO
4the aqueous solution, according to the suspension liquid of certain reinforced configuration smoothly, is Li through the known throw out of XRD analysis mutually
3pO
4and Fe
3(PO4)
28H
2o, the pH value of suspension liquid is 6.2, and temperature is 60 DEG C.Temperature out through the preheating water of preheater 5 is 200 DEG C, and the volume ratio of precursor solution and preheating water is 1: 10, and caliber is DN25, and presoma flow is 160L/h, and the flow of water is 1600L/h.The velocity in pipes of the first crystallizer 6 is 1.0m/s, and the residence time is 5min, and the piping arrangement of the first crystallizer 6 adopts Horizontal U-shaped arrangement, pipeline overall length is 300m, and maintaining temperature in pipe is 187 DEG C, and the second crystallizer 7 temperature is 175 DEG C, the residence time of the second crystallizer 7 is 2.5h, LiFePO
4iso-electric point be about 3.55, it is 6.8 that the pH value of the second crystallizer 7 inner suspension magma controls, and away from iso-electric point, avoid particle aggregation to grow, the control pressure of bleeder valve 14 is 0.9MPa, and condenser 12 temperature out is 50 DEG C, and the filter screen of strainer 13 is 1.0 μm.The product cut size D50=325.6nm of prepared submicron order iron lithium phosphate, PDI=0.135, D97=397nm.
Above-described is only some embodiments of the present invention.For the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (10)
1. serialization hydrothermal method prepares the apparatus system of submicron material, it is characterized in that, comprise the first batching kettle (1), the second batching kettle (2), preheater (5), the first crystallizer (6), the second crystallizer (7) and interchanger (9);
Described first batching kettle (1) is communicated with the first fresh feed pump (2) and preheater (5) successively by pipeline, described second batching kettle (2) is communicated with the second fresh feed pump (4) by pipeline, and described preheater (5) and described second fresh feed pump (4) are all communicated with the feeding mouth of described first crystallizer (6) by pipeline;
The discharge port of described first crystallizer (6) is communicated with the feeding mouth of described second crystallizer (7) by pipeline, the discharge port of described second crystallizer (7) is communicated with the entrance of described interchanger (9) by pipeline, the outlet of described interchanger (9) is divided into two, an outlet outer circulation unit of described interchanger is communicated with the entrance of described second crystallizer (7) again, and another outlet post-processing unit of described interchanger is communicated with described slip collector (15) again;
Wherein, described first crystallizer (6) is pipe reaction crystallizer, and described second crystallizer (7) is successive type reaction crystalizer.
2. serialization hydrothermal method according to claim 1 prepares the apparatus system of submicron material, it is characterized in that, described second crystallizer (7) is DTB type crystallizer.
3. serialization hydrothermal method according to claim 1 prepares the apparatus system of submicron material, it is characterized in that, described pipe reaction crystallizer is that the line mixer having a same inner diameter by multistage forms, and the caliber of described pipe reaction crystallizer is DN25 ~ DN125mm.
4. the serialization hydrothermal method according to claim 1 or 2 or 3 prepares the apparatus system of submicron material, it is characterized in that, described outer circulation unit comprises recycle pump (10); Described post-processing unit comprises the condenser (12), strainer (13) and the bleeder valve (14) that are communicated with successively.
5. serialization hydrothermal method according to claim 4 prepares the apparatus system of submicron material, it is characterized in that, described outer circulation unit also comprises waterpower ultra-sonic generator (11), and described waterpower ultra-sonic generator (11) is located between described recycle pump (10) and described second crystallizer (7); Described bleeder valve (14) is back pressure valve.
6. serialization hydrothermal method according to claim 5 prepares the apparatus system of submicron material, it is characterized in that, be equipped with under meter near described first fresh feed pump (3), the second fresh feed pump (4) and recycle pump (10), the pipeline of the outer circulation of described second crystallizer (7) is provided with pH detector and pH value feeding liquid variable valve (8).
7. the serialization hydrothermal method preparing the apparatus system of submicron material based on the serialization hydrothermal method described in any one of claim 4 to 6 prepares the preparation technology of submicron material, and it is characterized in that, this technique comprises the steps:
Splendid attire enters preheater (5) in the first stock liquid of the first batching kettle (1) and is preheated to certain temperature after the first fresh feed pump (3) conveying, splendid attire in the second batching kettle (2) the second stock liquid through the second fresh feed pump (4) conveying and with the first stock liquid after preheating according to a certain volume example enter the first crystallizer (6), obtain slip, slip with after certain flow rate for some time, enters the second crystallizer (7) in the first crystallizer (6);
Slip enters the second crystallizer (7) and carries out crystallization, part slip flows out from the discharge port of the second crystallizer (7), through interchanger (9) heat exchange, the second crystallizer (7) is again entered after mixing with the slip from the first crystallizer (6) under the driving of recycle pump (10), form an outer circulation, in the second crystallizer (7) after reaction for some time, obtain suspension magma;
Suspension magma flows out from the discharge port of the second crystallizer (7), through interchanger (9) heat exchange, after condenser (12) is condensed to certain temperature, filtered by strainer (13), obtain the magma of homogeneous grain diameter, under the effect of bleeder valve (14), magma is stablized discharging and is collected in slip collector (15);
Wherein, described first stock liquid is precursor solution, and described second stock liquid is the aqueous solution or another precursor solution; In crystallization process, the pH regulating and controlling the magma in described second crystallizer (7), to control the Zeta potential on suspended crystal surface, controls suspension density by coutroi velocity and reaction times, avoids the particle aggregation of magma to grow.
8. serialization hydrothermal method according to claim 7 prepares the preparation technology of submicron material, it is characterized in that, described first stock liquid is 100 ~ 350 DEG C through the preheating temperature of described preheater (5).
9. serialization hydrothermal method according to claim 7 prepares the preparation technology of submicron material, it is characterized in that, the first stock liquid after described second stock liquid and preheating enters described first crystallizer (6) by the volume ratio of 1: 1 ~ 1: 10.
10. serialization hydrothermal method according to claim 7 prepares the preparation technology of submicron material, it is characterized in that, the flow velocity of slip in described first crystallizer (6) pipe is 0.25 ~ 1.0m/s, and the residence time is 1 ~ 30min; Be 0.5 ~ 24h in the reaction times of described second crystallizer (7), described temperature after condenser (12) is 25 ~ 60 DEG C; The filter screen precision of described strainer (13) is 1.0 μm.
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| PCT/CN2015/083024 WO2016197425A1 (en) | 2015-06-09 | 2015-07-01 | Device system and preparation process for preparing submicron material by continuous hydrothermal method |
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