CN113753935B - Method and device for co-producing nano barium sulfate and nano calcium carbonate - Google Patents
Method and device for co-producing nano barium sulfate and nano calcium carbonate Download PDFInfo
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Abstract
The invention relates to the technical field of inorganic chemical industry, in particular to a method and a device for co-producing nano barium sulfate and nano calcium carbonate, wherein barium carbonate is used as a barium source, hydrochloric acid is used as acidolysis substance, and the barium carbonate-hydrochloric acid-sulfuric acid method is used for co-producing nano calcium carbonate and nano barium sulfate, so that the feasibility of industrialization and industrialized popularization and implementation are fully considered, the co-production of nano barium sulfate and nano calcium carbonate is realized on the basis of ensuring continuous production, the emission of waste gas and waste liquid is reduced, and the environmental protection pressure is lightened; meanwhile, the particle size of the nano barium sulfate is smaller than 100nm, the average particle size is kept below 80nm, the purity is above 98%, and the whiteness is above 96%; the grain diameter of the nano calcium carbonate is less than 100nm, the average grain diameter is less than 90nm, the purity is more than 98%, and the whiteness is more than 95%.
Description
Technical Field
The invention relates to the technical field of inorganic chemical industry, in particular to a method and a device for co-producing nano barium sulfate and nano calcium carbonate.
Background
The nano barium sulfate and the nano calcium carbonate have the characteristics of high specific surface area, high activity, good dispersibility and the like, and are widely applied to the fields of rubber, printing ink, coating, papermaking, composite materials and the like. With the development of science and technology, the demand for nano barium sulfate and nano calcium carbonate is increasing, and especially the demand for nano barium sulfate is increasing.
Currently, nano barium sulfate production is mainly characterized by the following categories:
(1) According to the mechanism of preparing nano particles by precipitation, the production method of nano barium sulfate comprises the following steps: the nucleation time is prolonged and the diffusion time is shortened. Wherein, the prolonged nucleation time mainly relates to a direct precipitation method, a microemulsion method and a complexation precipitation method which reduce the concentration of raw materials and control the dropping speed; the method has high operation requirements on technicians due to low concentration of raw materials or the need of introducing other organic solvents and the like, and has high post-treatment difficulty, so that industrial production is difficult to realize. The diffusion time is shortened mainly by a micro-reactor, a hypergravity rotating bed reactor, a high-speed centrifugal millstone reactor and the like, and the nano particles are prepared by realizing the rapid and uniform mixing of raw materials under a micro scale to form explosive nucleation and controlling the growth process of precipitated particles; the method has the characteristics of small channel size of the micro-reactor, small filler pores of the super-gravity rotating bed reactor and the like, so that the channel is easy to be blocked after nano particles are gathered, the industrial production efficiency is low, and the cost is high; the high-speed centrifugal millstone reactor needs to provide higher millstone rotation speed, has high energy consumption, and has higher difficulty and high cost when amplifying and industrialized production of laboratory equipment.
(2) According to different raw material sources, the preparation method of the nano barium sulfate comprises the following steps: the barium sulfate-sulfuric acid method is characterized in that barium sulfide is used as a barium source, but barium polysulfide is easy to generate due to the instability of the barium sulfide in the air, so that the purity of the prepared barium sulfate is low, and sodium sulfide or hydrogen sulfide serving as byproducts are generated, so that the process treatment difficulty is high; the barium carbonate-sulfuric acid method is adopted, barium carbonate is used as a barium source, but because the solubility of the barium carbonate is low, the barium sulfate product is easy to form in the reaction process to protect the raw material barium carbonate, the purity of the product is low, and the difficulty of the prepared nano-scale barium sulfate is high; the barium chloride-sulfate method is adopted, wherein barium chloride is used as a barium source, and the barium sulfate prepared by the method has high purity and less impurities, but can generate chlorine-containing waste acid or salt, so that the environmental protection treatment difficulty is high; in particular: the price of the raw material of barium chloride is far higher than that of barium sulfide and barium carbonate, so that the industrialized production of nano barium sulfate is difficult to realize.
In the project research process, in order to know the progress condition of the related research of the barium sulfate in the prior art and develop the search analysis work of related existing documents, the researcher knows:
(1) the prior art study on barium sulfate has focused mainly on: submicron barium sulfate (particle size > 100 nm), superfine barium sulfate, micron barium sulfate, etc. For example: 200310122805.5 it discloses decomposing salt mud with hydrochloric acid, adding sodium sulfite as reducing agent to react to prepare turbid liquid of barium sulfate, calcium and magnesium salt, filtering, washing to obtain white precipitate barium sulfate, drying, and air-flow pulverizing to obtain superfine barium sulfate (average particle size 1.1 μm); transferring the solution, adding concentrated ammonia water, filtering, discarding the precipitate, adding surfactant into the clear solution, and adding ammonium carbonate solution to prepare superfine calcium carbonate powder (average particle size is less than 1 μm). For another example: patent No. 201010572327.8 discloses that an aqueous solution containing at least water-soluble barium salt and an aqueous solution containing at least water-soluble sulfate are subjected to coprecipitation reaction at a temperature of between 0 and 99 ℃ to obtain a mixed precipitate of barium sulfate precipitate and other inorganic salt precipitate, wherein the other inorganic salt precipitate can react with a purifying agent to be converted into water-soluble substances; mixing and standing for aging, adding a purifying agent, removing all or part of inorganic salt precipitate, washing and concentrating the rest depth, adding a surface modifying agent, mixing or reflecting, and obtaining modified micronized barium sulfate (particle size is basically smaller than 200 nm).
(2) In the aspect of raw material selection, the prior art focuses on researches on barium chloride and barium carbonate as barium sources, such as: patent application number 201910803811.8 discloses that barium chloride solution and dilute sulfuric acid solution are slowly poured into the barium chloride solution according to the molar mass ratio of 1:1, a glass rod is stirred, standing is carried out for 30-60min, filtering, washing, drying and grinding are carried out, and barium sulfate is obtained (impurities are not introduced into precipitation, so that the purity of the barium sulfate is higher, and the grinding ensures the quality of the barium sulfate); adding barium carbonate into the filtrate, stirring until the barium carbonate is dissolved, adding a dilute sulfuric acid solution for reaction, preparing barium sulfate, realizing the secondary preparation of barium chloride, saving resources, reusing the filtrate, completing the cyclic utilization of chloride ions, ensuring the high purity of the barium chloride, and further ensuring the purity of the barium sulfate; however, in the research, there is no research on how much of the barium sulfate can be formed into a quality, how much of the purity can be achieved, whether the nano-grade barium sulfate can be prepared, and the like, and the purpose of the research is to utilize the barium chloride and the barium carbonate together as a barium source to realize the cyclic utilization of chloride ions and fully utilize the barium chloride-sulfate method to prepare the barium sulfate product, but in the method, carbon dioxide gas and the like are easy to be discharged, so that the cost in the industrial and industrialized production is high, and the environmental protection pressure is high. For another example: the patent number 201710719060.2 discloses that barium carbonate or barium hydroxide is stirred into suspension, hydrochloric acid solution is slowly injected, so that the barium carbonate or barium hydroxide is completely dissolved, the pH value of a solution system is kept to be less than or equal to 1.0, alkali slag is added according to the content of sulfuric acid ions, barium sulfate is generated by reaction, hydrochloric acid is added at any time in the stirring process, the pH value is regulated, the pH value is kept to be always less than 1.0, solid-liquid separation, washing and drying are carried out, a barium sulfate product is prepared, and meanwhile, a light calcium carbonate product is prepared from filtrate, so that the recycling utilization of the barium sulfate is realized. However, no study is made in this document as to whether or not a product of nano-sized barium sulfate and nano-sized calcium carbonate can be produced.
In view of the above, in order to meet the application requirements of nano barium sulfate, the researcher realizes the purpose of industrial and industrialized production of nano barium sulfate, prepares nano barium sulfate by using a barium carbonate-hydrochloric acid-sulfuric acid method on the basis of fully guaranteeing the quality of nano barium sulfate, realizes the co-production of nano barium sulfate and nano calcium carbonate, guarantees the quality of nano barium sulfate, and provides a new process for nano barium sulfate production.
Disclosure of Invention
The invention provides a method and a device for co-producing nano barium sulfate and nano calcium carbonate, which can effectively improve the characteristics of particle size, whiteness, purity and the like of nano barium sulfate products and reduce the production cost of nano barium sulfate.
The method is realized by the following technical scheme:
the method for co-producing nano barium sulfate and nano calcium carbonate comprises the following steps:
s1: adding hydrochloric acid into barium carbonate serving as a barium source to prepare a barium chloride solution, and collecting carbon dioxide gas;
s2: delivering carbon dioxide and calcium hydroxide slurry into an improved Taylor reactor for gas-liquid precipitation reaction, filtering, washing, drying and crushing to prepare nano calcium carbonate, and collecting the filtered filtrate and washing water to be mixed into water for preparing calcium hydroxide slurry;
s3: the barium chloride solution and sulfuric acid are sent into an improved Taylor reactor for liquid-liquid precipitation reaction, then filtered, washed, dried and crushed to prepare nano barium sulfate, the filtered filtrate and the washing solution are collected and mixed to obtain hydrochloric acid solution, and the hydrochloric acid solution is concentrated and returned to the step S1; the improved Taylor reactor is conical.
The barium carbonate is used as a barium source, the hydrochloric acid is used as acidolysis substance, the barium carbonate-hydrochloric acid-sulfuric acid method is used for co-producing nano calcium carbonate and nano barium sulfate, the feasibility of industrialization and industrialized popularization and implementation is fully considered, the co-producing production of the nano barium sulfate and the nano calcium carbonate is realized on the basis of guaranteeing continuous production, the emission of waste gas and waste liquid is reduced, and the environmental protection pressure is lightened; meanwhile, the particle size of the nano barium sulfate is smaller than 100nm, the average particle size is kept below 80nm, the purity is above 98%, and the whiteness is above 96%; the grain diameter of the nano calcium carbonate is less than 100nm, the average grain diameter is less than 90nm, the purity is more than 98%, and the whiteness is more than 96%.
Preferably, the molar concentration of the hydrochloric acid is 0.4-3.4mol/L, and the molar concentration of the barium chloride solution is 0.2-1.7mol/L.
Preferably, the temperature of the step S1 is 10-50 ℃. More preferably 30 DEG C
Preferably, the reaction temperature of the step S2 is 2-15 ℃, and the rotating speed of the improved Taylor reactor is 1000-2500rpm. Preferably, the reaction temperature of the step S2 is 5-10 ℃, and the rotating speed of the improved Taylor reactor is 1500-2000rpm. More preferably 5 ℃.
Preferably, the reaction temperature in the step S3 is 30 ℃, and the rotating speed of the improved Taylor reactor is 1000-2500rpm.
The second purpose of the invention is to provide the nano barium sulfate prepared by the method.
The invention provides a device for co-producing nano barium sulfate and nano calcium carbonate, which comprises: acidolysis pool, liquid-liquid reaction pool, gas-liquid reaction pool, nano calcium carbonate storage tank and nano barium sulfate storage tank; the top of the acidolysis reaction tank is provided with a gas discharge hole, the gas-liquid reaction tank is provided with a gas inlet, and the gas discharge hole is communicated with the gas inlet; the bottom of the acidolysis reaction tank is provided with a liquid discharge hole, the liquid-liquid reaction tank is provided with a liquid inlet, and the liquid discharge hole is communicated with the liquid inlet; the acidolysis reaction tank is provided with a hydrochloric acid inlet pipe and a barium carbonate inlet near the top, the hydrochloric acid inlet pipe is connected with a hydrochloric acid storage tank through a pipeline, and the barium carbonate inlet is connected with the barium carbonate storage tank; the gas-liquid reaction tank is provided with a slurry inlet which is connected with a calcium hydroxide storage tank through a pipeline; the gas-liquid reaction tank is provided with a slurry outlet, the slurry outlet is connected with a filtering and washing tower a, the filtrate outlet end of the filtering and washing tower a is connected with the hydrogen oxidation storage tank, the filter cake outlet end of the filtering and washing tower a is connected with a drying tower a, and the drying tower a is communicated with the nano calcium carbonate storage tank; a sulfuric acid inlet is arranged on the liquid-liquid reaction tank, and the sulfuric acid inlet is connected with a sulfuric acid storage tank through a pipeline; the liquid-liquid reaction tank is provided with a reaction slurry discharge port, the reaction slurry discharge port is connected with a filtering and washing tower b through a pipeline, the filtrate discharge end of the filtering and washing tower b is connected with a concentration tank through a pipeline, and the discharge end of the concentration tank is communicated with the hydrochloric acid inlet pipe; the filter cake discharge end of the filtering and washing tower b is connected with a drying tower b, and the drying tower b is communicated with the nano barium sulfate storage tank; the improved Taylor reactor is conical.
The invention provides an improved Taylor reactor suitable for producing nano barium sulfate and/or nano calcium carbonate, which comprises an outer cone and an inner cone, wherein the inner cone can rotate, and the outer cone is fixed; a gap is formed between the outer wall of the inner cone and the inner wall of the outer cone, and a plurality of small holes are formed in the inner cone; the small hole is communicated with the gap and the interior of the inner cone; the outer cone is provided with a first feeding pipe extending into the gap, the inner cone is provided with a second feeding pipe extending into the inner cone, and the bottom of the outer cone is provided with a discharge hole.
Preferably, a vertical downward rotating shaft is arranged at the bottom of the inner cone, and the rotating shaft penetrates through the bottom of the outer cone to be connected with a power source; a first bearing is arranged between the rotating shaft and the outer cone, a through hole is formed in the top of the inner cone, and a second bearing is arranged in the through hole; the second feeding pipe is inserted into the inner cone from the second bearing, and the outer wall of the second feeding pipe is tightly attached to the inner wall of the second bearing.
Preferably, a vertical downward rotating shaft is arranged at the bottom of the inner cone, penetrates out of the bottom of the outer cone from the discharge hole and is connected with a power source; the top of the inner cone is provided with a through hole, and a second bearing is arranged in the through hole; the second feeding pipe is inserted into the inner cone from the second bearing, and the outer wall of the second feeding pipe is tightly adhered to the inner wall of the second bearing; a gap for discharging the mixed materials is formed between the inner wall of the discharge hole 19 and the outer wall of the rotating shaft 23.
Preferably, the power source is selected from, but not limited to, an electric motor, a diesel engine, a gasoline engine, a water turbine, and the like.
Preferably, a fixed column is arranged in the second bearing, the fixed column is hollow, and the second feeding pipe can be inserted into the inner cone from the hollow of the fixed column.
Preferably, the rotating shaft and the bottom of the inner cone are integrally formed.
Compared with the prior art, the invention has the technical effects that:
(1) The barium carbonate is used as a barium source, an acidolysis process is adopted to convert the barium carbonate into a barium chloride solution, then the barium chloride solution and sulfuric acid are subjected to liquid-liquid precipitation reaction, and hydrochloric acid is recovered and recycled, so that the whole process has no waste liquid or salt discharge such as waste acid and the like, the recycling of chloride ions in a reaction system is realized, and the environmental protection pressure is reduced; the carbon dioxide is collected and recycled, so that the preparation of the nano calcium carbonate product is realized, the whole process has no exhaust emission, the nano calcium carbonate product with higher added value is produced, and the production cost of the whole process is reduced.
(2) The Taylor reactor is improved to adopt a conical Taylor reactor structure by utilizing the reaction principle of the Taylor reactor, so that the uniformity and rapidity of material mixing are enhanced, materials react to form explosive nucleation to prepare nano-scale particles, the added value of a precipitation product is improved, the blockage of a reaction channel is avoided, and the method is suitable for industrialized production and industrialized application.
(3) The process flow and the device have simple structure, easy control, high production efficiency, no exhaust gas and waste liquid emission and can meet the requirements of green and environment-friendly chemical process routes.
Drawings
FIG. 1 is a process flow diagram of the inventive method.
FIG. 2 is a schematic diagram of the overall structure of the inventive device.
FIG. 3 is a schematic diagram of an improved construction of a tapered Taylor reactor in accordance with the present invention.
Fig. 4 is a schematic view of the partial cross-sectional structure of fig. 3.
Fig. 5 is a schematic view of the partial enlarged structure of fig. 3.
Fig. 6 is an SEM image of the barium sulfate of example 1.
1-acidolysis tank 2-liquid reaction tank 3-gas-liquid reaction tank 4-sulfuric acid storage tank 5-calcium hydroxide storage tank 6-filtration washing tower a 7-drying tower a 8-nano calcium carbonate storage tank 9-nano barium sulfate storage tank 10-drying tower b 11-filtration washing tower b 12-concentration tank 13-hydrochloric acid storage tank 14-barium carbonate storage tank 15-outer cone 16-inner cone 17-gap 18-small hole 19-discharge port 20-first feed pipe 21-second feed pipe 22-fixed column 23-rotating shaft 24-first bearing 25-second bearing.
In the figure: the direction indicated by the arrow is the material conveying direction.
Detailed Description
The technical solution of the present invention is further defined below with reference to the accompanying drawings and specific embodiments, but the scope of the claims is not limited to the description.
As shown in figure 1, the method for co-producing nano barium sulfate and nano calcium carbonate provided by the invention comprises the steps of taking barium carbonate as a barium source, utilizing hydrochloric acid to acidolysis barium carbonate powder, reacting to generate barium chloride solution and carbon dioxide gas, utilizing the barium chloride solution as the barium source, preparing nano barium sulfate by a barium chloride-sulfuric acid method, and producing nano calcium carbonate by a carbon dioxide-calcium hydroxide method, wherein in the reaction process, a Taylor reactor is adopted to realize uniform mixing of materials and explosive nucleation, so that the diffusion time is shortened, and the prepared nano barium sulfate has the particle size smaller than 100nm, the average particle size is about 50nm, the nano calcium carbonate has the particle size smaller than 100nm, and the average particle size is about 35nm.
Specifically, in the operation process, the method comprises the following steps:
s1: adding hydrochloric acid into barium carbonate serving as a barium source to prepare a barium chloride solution, and collecting carbon dioxide gas; baCO 3 +2HCl＝BaCl 2 +CO 2 ↑+H 2 O
S2: delivering carbon dioxide and calcium hydroxide slurry into an improved Taylor reactor for gas-liquid precipitation reaction, filtering, washing, drying and crushing to prepare nano calcium carbonate, and collecting the filtered filtrate and washing water to be mixed into water for preparing calcium hydroxide slurry;
CO 2 ↑+Ca(OH) 2 ＝CaCO 3 ↓+H2O
s3: the barium chloride solution and sulfuric acid are sent into an improved Taylor reactor for liquid-liquid precipitation reaction, then filtered, washed, dried and crushed to prepare nano barium sulfate, the filtered filtrate and the washing solution are collected and mixed to obtain hydrochloric acid solution, and the hydrochloric acid solution is concentrated and returned to the step S1; the improved Taylor reactor is conical. BaCl 2 +H 2 SO 4 ＝BaSO 4 ↓+2HCl
The invention realizes the co-production process of nano calcium carbonate and nano barium sulfate through the selection of the raw materials of the barium source and the integration of the preparation process, fully realizes the full recycling of waste gas (carbon dioxide) and waste liquid (washing liquid and filtrate) generated in the production process, avoids the discharge of acid, alkali waste water and carbon dioxide gas, is beneficial to process environmental protection, reduces the production cost of the barium sulfate, realizes the effect of hydrochloric acid serving as a 'recycling iteration' in the whole process, and reduces the cost brought by the barium source and the chlorine source produced by the product; and by combining the process, the Taylor reactor is introduced to realize instant uniform mixing of materials, shorten the diffusion time between the materials, ensure that the materials are fully contacted and quickly undergo nuclear reaction, improve the crystal phase quality of nano barium sulfate and nano calcium carbonate, and facilitate the realization of industrialization and industrialized popularization.
In the research process, when the barium carbonate is taken as a barium source and decomposed by hydrochloric acid, the hydrochloric acid is added according to the theoretical value of molar quantity and the 2:1 molar ratio of the combination between chloride ions and barium ions, the hydrochloric acid is stirred in the adding process, so that the barium carbonate is quickly dissolved, the barium carbonate is completely dissolved, the molar concentration of the hydrochloric acid is 0.4-3.4mol/L in the reaction process, and the molar concentration of the barium chloride solution is 0.2-1.7mol/L.
In the process for decomposing barium carbonate by hydrochloric acid, whether the temperature causes the burden of the whole process is emphasized, so that the temperature of the step S1 is any temperature value between 10 ℃ and 50 ℃ in combination with the decomposition reaction process can meet the requirement; of course, outside the temperature value range, the invention can be used on the basis of not influencing the whole process treatment burden as long as other reasonable and proper technical means can be adopted, and the invention mainly considers and limits the temperature to 10-50 ℃ in the research process so as to reduce the process burden and ensure the low cost of the industrialized implementation process.
In the preparation process of the nano calcium carbonate, in order to ensure that the nucleation particle size of the nano calcium carbonate is uniform and the quality of a crystalline phase is excellent, so that the particle size of the nano calcium carbonate is less than 100nm, the processing burden of the whole process is reduced, and the industrialized and industrialized production cost is reduced, the reaction temperature in the step S2 is any temperature value between 2 and 15 ℃, the rotating speed of the improved Taylor reactor is any rotating speed between 1000 and 2500rpm, and the requirements can be met, and the values outside the temperature and rotating speed range can be selected as long as the values with the same and corresponding objective functions can be achieved. In a preferred embodiment, the step S2 reaction temperature is 5-10deg.C and the modified Taylor reactor speed is 1500-2000rpm. More preferably 5 ℃. For example: during the study it was found that: (1) The solid content of calcium hydroxide slurry is 1g/L, after carbon dioxide is introduced into the slurry, the constant concentration of the carbon dioxide is maintained to be 50%, the reaction temperature is controlled to be 5 ℃, the rotating speed is 1500rpm, and the average grain diameter of the obtained nano calcium carbonate product is about 35nm; the reaction temperature is controlled to be 5 ℃ and the rotating speed is controlled to be 2000rpm, and the average grain diameter of the obtained nano calcium carbonate product is 30nm; the reaction temperature is controlled to be 5 ℃ and the rotating speed is controlled to be 1000rpm, and the average grain diameter of the obtained nano calcium carbonate product is 66nm; the reaction temperature is controlled to be 15 ℃ and the rotating speed is controlled to be 1500rpm, and the average grain diameter of the obtained nano calcium carbonate product is 85nm; the reaction temperature is controlled to be 10 ℃ and the rotating speed is controlled to be 1500rpm, and the average grain diameter of the obtained nano calcium carbonate product is 50nm. (2) Controlling the reaction temperature to be 5 ℃ and the rotating speed to be 1500rpm, adopting the solid content of calcium hydroxide slurry to be 10g/L, and maintaining the constant concentration of carbon dioxide to be 50% after carbon dioxide is introduced into the slurry, wherein the average particle size of the obtained nano calcium carbonate product is about 68nm; adopting calcium hydroxide slurry with solid content of 30g/L, and maintaining constant concentration of carbon dioxide at 50% after carbon dioxide is introduced into the slurry, wherein the average particle size of the obtained nano calcium carbonate product is about 81nm; the solid content of the calcium hydroxide slurry is 30g/L, and after carbon dioxide is introduced into the slurry, the constant concentration of the carbon dioxide is maintained to be 70%, so that the average particle size of the obtained nano calcium carbonate product is about 83nm. Therefore, under the mixed reaction condition of the improved Taylor reactor, the parameters are strictly matched, and if the parameters are incorrectly matched, the average particle size of the obtained nano calcium carbonate product is directly influenced, but the preparation of the nano calcium carbonate can be realized.
In the preparation process of the nano barium sulfate, in order to ensure that the nucleation particle size of the nano barium sulfate is uniform and the quality of a crystalline phase is excellent, so that the particle size of the nano barium sulfate is smaller than 100nm, the processing burden of the whole process is reduced, the industrialized production cost is reduced, the reaction temperature in the step S3 is 30 ℃, and the rotating speed of the improved Taylor reactor is between 1000 and 2500rpm. Of course, values outside the above temperature and rotational speed ranges may be selected as relevant embodiments of the present invention, provided that the same, corresponding objective function is achieved. For example: during the study it was found that: (1) The concentration of barium chloride is 0.3mol/L, the concentration of sulfuric acid is 0.3mol/L, and when the barium chloride is added according to the stoichiometric amount for reaction, the average grain diameter of the nano barium sulfate is 52nm at the reaction temperature of 30 ℃ and the rotating speed of 1500 rpm; the concentration of barium chloride is 0.9mol/L, and the concentration of sulfuric acid is 0.9mol/L, so that the average particle size of the nano barium sulfate is 55nm; the concentration of barium chloride is 0.9mol/L, the concentration of sulfuric acid is 1.8mol/L, and the average particle size of the obtained nano barium sulfate is 58nm; the concentration of barium chloride is 1.2mol/L, and the concentration of sulfuric acid is 1.2mol/L, so that the average particle size of the nano barium sulfate is 62nm. (2) The concentration of barium chloride is 1.2mol/L, the concentration of sulfuric acid is 1.2mol/L, and when the barium chloride is added according to the stoichiometric amount for reaction, the average grain diameter of the nano barium sulfate is 78nm at the reaction temperature of 50 ℃ and the rotating speed of 1500 rpm; the average grain diameter of the nano barium sulfate is 72nm at the reaction temperature of 30 ℃ and the rotating speed of 1000 rpm; the average grain diameter of the nano barium sulfate is 48nm at the reaction temperature of 30 ℃ and the rotation speed of 2000rpm. It can be seen that the same conclusion as for the nano calcium carbonate preparation process appears.
The second object of the invention is to provide the nano barium sulfate prepared by the method, and SEM image analysis is carried out on the nano barium sulfate obtained in the research process to obtain that: the particle size is less than 100nm. And other quality index analysis shows that: the purity is more than or equal to 98 percent, and the whiteness is more than 96 percent.
The invention fully utilizes the advantages of the Taylor reactor, combines the establishment of the nano barium sulfate and nano calcium carbonate co-production process, reduces the cost of raw material selection, reduces the energy consumption of the production process, improves the product added value of the whole production process, reduces the environmental protection load of the whole production process, and ensures the industrialized and industrialized production of the nano barium sulfate; but also can improve the quality of the nano barium sulfate, so that the purity and whiteness of the nano barium sulfate are improved, the average particle size is improved, and a research route with market competitiveness is formed. However, the invention aims to create and utilize the improved Taylor reactor, so as to strengthen the mixing performance of the reactor and improve the mass transfer efficiency, further provide a conical Taylor reactor, and establish a device system for co-producing nano barium sulfate and nano calcium carbonate by utilizing the combination of the improved Taylor reactor,
the specific implementation process, as shown in fig. 2, includes: the acidolysis tank 1 is used for enabling hydrochloric acid and barium carbonate to serve as barium sources to be reacted and decomposed in the acidolysis tank 1 to generate barium chloride solution and carbon dioxide gas and liquid reaction tank 2, and is used for enabling the barium chloride solution and sulfuric acid solution to be subjected to liquid-liquid contact reaction to generate nano barium sulfate and gas-liquid reaction tank 3, and is used for carrying out gas-liquid mixing reaction between the carbon dioxide gas and calcium hydroxide slurry to form nano calcium carbonate and nano calcium carbonate storage tank 8, and is used for storing the prepared nano calcium carbonate product and nano barium sulfate storage tank 9 and storing the prepared nano barium sulfate product; the top of the acidolysis tank 1 is provided with a gas discharge hole (for discharging and collecting carbon dioxide), the gas-liquid reaction tank 3 is provided with a gas inlet (for inputting carbon dioxide gas), and the gas discharge hole is communicated with the gas inlet; the bottom of the acidolysis reaction tank 1 is provided with a liquid discharge hole (for discharging barium chloride solution), the liquid-liquid reaction tank 2 is provided with a liquid inlet (for inputting barium chloride solution), and the liquid discharge hole is communicated with the liquid inlet; the acidolysis reaction tank 1 is provided with a hydrochloric acid inlet pipe (for feeding hydrochloric acid) and a barium carbonate inlet (for feeding a barium source) near the top, the hydrochloric acid inlet pipe is connected with a hydrochloric acid storage tank 13 through a pipe, and the barium carbonate inlet is connected with a barium carbonate storage tank 14; a slurry inlet (for inputting calcium hydroxide slurry) is arranged on the gas-liquid reaction tank 3, and the slurry inlet is connected with a calcium hydroxide storage tank 5 through a pipeline; the gas-liquid reaction tank 3 is provided with a slurry outlet, the slurry outlet is connected with a filtering and washing tower a6 (realizing the precipitation filtration and washing of nano calcium carbonate generated by the reaction, recovering filtrate and washing water, and recycling calcium ions remained in the filtrate and the washing water to reduce waste liquid discharge), the filtrate outlet end of the filtering and washing tower a6 is connected with a calcium hydroxide storage tank 5, the filter cake outlet end of the filtering and washing tower a6 is connected with a drying tower a7, and the drying tower a7 is communicated with the nano calcium carbonate storage tank 8; a sulfuric acid inlet (for sulfuric acid feeding) is arranged on the liquid-liquid reaction tank 2, and the sulfuric acid inlet is connected with a sulfuric acid storage tank 4 through a pipeline; the liquid-liquid reaction tank 2 is provided with a reaction slurry discharge port (for discharging the reaction barium sulfate-containing precipitation slurry), the reaction slurry discharge port is connected with a filtering and washing tower b11 (for filtering and washing the nano barium sulfate precipitation generated by the reaction, recovering filtrate and washing water, and residual hydrochloric acid components in the filtrate and the washing water, recycling the hydrochloric acid and reducing the discharge of waste liquid), the filtrate discharge end of the filtering and washing tower b11 is connected with a concentration tank 12 through a pipeline, and the discharge end of the concentration tank 12 is communicated with the hydrochloric acid inlet pipe; the filter cake discharge end of the filtering and washing tower b11 is connected with a drying tower b10, and the drying tower b10 is communicated with the nano barium sulfate storage tank 9; the improved Taylor reactor is arranged in the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3, and is conical. The device not only can realize the co-production of nano barium sulfate and nano barium carbonate, but also mainly solves the problems of high cost of barium source, high chloride ion treatment difficulty, high environmental protection pressure and high cost caused by the use of the barium chloride in the nano barium sulfate; meanwhile, the defect that the purity of the obtained nano barium sulfate is low due to the fact that barium carbonate is low in solubility and barium sulfate crystals are easy to coat the barium carbonate is overcome. The purity of the nano barium sulfate prepared by the method reaches more than 98%, the process of forming barium sulfate precipitate to coat the barium carbonate is fully avoided, the recycling of hydrochloric acid can be realized, the difficulty of chloride ion treatment is reduced, and the defect of high cost of the barium chloride is avoided. In the treatment process, the processing steps are combined with the processing of the improved Taylor reactor, so that the efficiency of the industrialized production process is ensured, the defect of high cost caused by blocking of the Taylor reactor is avoided, and the quality of the nano barium sulfate is improved, so that the particle size is smaller than 100nm.
As shown in fig. 3 and 4 and 5, the improved taylor reactor includes an outer cone 15 and an inner cone 16, and the inner cone 16 is rotatable, and the outer cone 15 is fixed; a gap 17 (the gap width is selected from but not limited to 1-10 mm) is formed between the outer wall of the inner cone 16 and the inner wall of the outer cone 15, and a plurality of small holes 18 (the aperture is selected from but not limited to 0.2-1 mm) are arranged on the inner cone 16; the small hole 18 is communicated with the gap 17 and the interior of the inner cone 16; the outer cone 15 is provided with a first feeding pipe 20 extending into the gap 17, the inner cone 16 is provided with a second feeding pipe 21 extending into the inner cone 16, and the bottom of the outer cone 15 is provided with a discharge outlet 19. The improved Taylor reactor is suitable for production and application of nano barium sulfate and/or nano calcium carbonate, adopts the technical means that an inner cone 16, an outer cone 15 and the inner cone 16 can rotate, and the outer cone 15 is fixed, realizes uniform material mixing, can realize explosive nucleation, shortens diffusion time, promotes reaction, improves the quality of reaction products, avoids the phenomenon of blockage easily, and ensures industrialized and industrialized production efficiency.
For the inner cone 16 can rotate, the outer cone 15 is fixed, the inner cone 16 is positioned inside the outer cone 15, a structure with a conical section as shown in fig. 3, 4 and 5 is formed, the inner cone 16 can rotate inside the outer cone 15, so that materials positioned inside the inner cone 16 enter between gaps 17 from small holes 18 under the action of centrifugal force and are mixed with materials conveyed from a first feeding pipe 20 arranged on the outer cone 15 at a high speed, the mixing contact surface of the materials is improved, the mutual diffusion time of the materials is shortened, the nucleation efficiency and the rate are improved, the coating phenomenon among particles is avoided, and the purity is improved, the granularity and the whiteness are improved.
When the improved Taylor reactor is used for preparing nano calcium carbonate, carbon dioxide gas is conveyed into the inner cone 16 through the second feeding pipe 21, the inner cone 16 is started to rotate, so that the carbon dioxide gas enters the gap 17 from the small hole 18, calcium hydroxide slurry is input into the gap 17 from the first feeding pipe 20, and then carbon dioxide forms tiny bubbles under the action of the small hole 18, so that the contact area of the carbon dioxide gas and the calcium hydroxide slurry is increased, the gas and the liquid are uniformly mixed, the gas and the liquid are subjected to precipitation reaction, the preparation of nano calcium carbonate is realized by combining the preparation process, the average particle size of the obtained nano calcium carbonate is maintained at 30-90nm, the purity of the nano calcium carbonate is more than 98%, and the whiteness is more than 96%.
When the improved taylor reactor is used for preparing nano barium sulfate, a barium chloride solution is input into the inner cone 16 through the second feed pipe 21, sulfuric acid is input into the gap 17 through the first feed pipe 20, the barium chloride solution is dispersed and mixed with the sulfuric acid through the small holes 18, the high-speed impact mixing of the barium chloride solution and the sulfuric acid is realized by utilizing the rotation of the inner cone 16 and the fixation of the outer cone 15, the liquid-liquid contact surface is improved, the mass transfer effect is improved, the preparation of nano barium sulfate is realized by combining the preparation process, the average particle size of the obtained nano barium sulfate is maintained at 45-80nm, the purity of nano calcium carbonate is up to more than 98%, and the whiteness is up to more than 96%.
How the technical means of fixing the outer cone 15 for the rotation of the inner cone 16 can be realized is fully solved for the person skilled in the art, as long as the purpose of continuously inputting materials into the inner cone 16 is not affected, the purpose of continuous production is achieved, no matter what design structure is adopted to meet the technical means of rotation of the inner cone 16 and fixation of the outer cone 15, the technical means of fixing the inner cone 15 and the technical means of fixing the outer cone 15 are in accordance with the design and the inventive concept of the invention, and the technical means are considered in the scope of the invention, such as: a rotation shaft 23 capable of rotating the inner cone 16 is provided at the top, and a design structure capable of relatively sliding with the rotation of the inner cone 16 is provided for the second feed pipe 21. To enable those skilled in the art to fully understand, in connection with the actual operation, the following brief examples of the relevant embodiments in which the improved taylor reactor can operate when the inner cone 16 is rotated and the outer cone 15 is fixed will now be presented to facilitate a full understanding of the invention by those skilled in the art:
as shown in fig. 3, fig. 4 and fig. 5, the bottom of the inner cone 16 is integrally formed with a vertical downward rotation shaft 23, and the rotation shaft 23 passes through the bottom of the outer cone 15 to be connected with a power source, where the power source adopts a motor, a diesel engine, a gasoline engine or other power designs capable of driving the rotation shaft 23 to rotate, for example: water turbines and the like can also be adopted; meanwhile, the second feeding pipe 21 is inserted into the inner cone 16 from the top of the inner cone 16, and a second bearing 25 is disposed between the second feeding pipe 21 and the top wall of the inner cone 16, so that the inner cone 16 is driven to rotate in the rotation process of the rotating shaft 23, and the second feeding pipe 21 does not rotate under the action of the second bearing 25, so that feeding into the inner cone 16 can be continuously performed; for the preferred scheme, install the fixed column 22 in second bearing 25 for interior cone 16 can be around fixed column 22, and rotatory under the effect of second bearing 25, cavity in the fixed column 22, second inlet pipe 21 inserts in interior cone 16 from fixed column 22, can be convenient for in time take out second inlet pipe 21 or adjust the degree of depth of inserting, satisfies different material input's demand, improves the convenience. There are two schemes for the rotation shaft 23 and the bottom of the outer cone 15: (1) the rotating shaft 23 passes through the bottom of the outer cone 15, and a first bearing 24 is arranged between the rotating shaft 23 and the bottom of the outer cone 15, so that the rotation is realized under the action of the first bearing 24, and the stability is improved; (2) the bottom of the outer cone 15 is directly opened to form a discharge hole 19, the rotary shaft 23 penetrates out of the discharge hole 19 to be connected with a power source, and a gap for discharging the mixed material is formed between the inner wall of the discharge hole 19 and the outer wall of the rotary shaft 23. By utilizing the structural design of the inner cone 16 and the outer cone 15, when the inner cone 16 is combined to rotate, the inner material of the inner cone 16 is impacted to the material in the gap 17 at a high speed, so that the blocking after particle aggregation can be effectively avoided, and the industrialized and industrialized production efficiency is improved.
Other minor matters in the creation of the present invention may be realized by those skilled in the art with reference to the prior art or by conventional means known to those skilled in the art. For example: the pulverization can be performed by a treatment means such as jet pulverization as described in patent No. 200310122805.5. For another example: the improved taylor reactors are installed in the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3, and for how the improved taylor reactors are installed in the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3, a person skilled in the art can fully refer to conventional technical means and common general knowledge to realize, and the improved taylor reactors are well known to the person skilled in the art, and in order to make the person skilled in the art understand the improved taylor reactors more clearly, the person makes appropriate supplements and descriptions for the improved taylor reactors by combining practical application: for example, the improved taylor reactor is directly placed in the tank, so that materials flow into the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3 after being mixed in the improved taylor reactor to form slurry; or the improved Taylor reactor is directly fixed on the tank walls of the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3, so that materials flow into the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3 after being mixed in the improved Taylor reactor to form slurry; and further or directly utilizing the improved Taylor reactor as the liquid-liquid reaction tank 2 and the gas-liquid reaction tank 3.
Example 1
1015g of hydrochloric acid with the molar concentration of 0.4mol/L is taken and added into a flask with stirring, 40.0g of barium carbonate powder is added under stirring, the reaction temperature is controlled to be 30 ℃ by heating in a water bath, the mixture is stirred until the reaction solution is clear, the barium chloride solution with the molar concentration of 0.2mol/L is obtained, carbon dioxide gas escaping from the reaction is collected in the process, and the carbon dioxide gas is stored in a carbon dioxide storage tank.
Pumping 0.2mol/L barium chloride solution and 0.2mol/L sulfuric acid into a modified Taylor reactor according to a stoichiometric ratio, mixing, controlling the rotating speed to 1500rpm, reacting at 30 ℃, filtering, washing, drying and crushing the obtained slurry to obtain a barium sulfate product, and detecting and analyzing the particle size (shown in figure 4), wherein the average particle size is 50nm. In this step, the filtrate and the washing solution of the water washing were combined and concentrated to a molar concentration of 0.4mol/L hydrochloric acid, followed by recycling the barium carbonate powder.
And (3) metering carbon dioxide gas into an improved Taylor reactor through a flowmeter, pumping a calcium hydroxide solution with the concentration of 1g/L, controlling the reaction temperature to be 5 ℃, controlling the rotating speed to be 1500rpm, properly excessive calcium hydroxide, maintaining the carbon dioxide concentration to be 50%, obtaining calcium carbonate slurry when the pH value to be measured is about 7, filtering, washing, drying and crushing to obtain a calcium carbonate product, and detecting and analyzing the particle size to obtain the calcium carbonate product with the average particle size of 35nm. In this step, the filtrate obtained by filtration is mixed with a washing solution obtained by washing with water to prepare a calcium hydroxide solution as water.
Based on example 1, the present investigator further studied the influence of the changes in barium chloride concentration, sulfuric acid concentration, reaction temperature, and improved taylor reactor rotation speed on the barium sulfate particle size, specifically, the following table 1:
TABLE 1
On the basis of example 1, the present investigator further studied the influence of carbon dioxide concentration, calcium hydroxide slurry solids content, reaction temperature, and improved taylor reactor rotational speed on calcium carbonate particle size, as shown in table 2 below:
TABLE 2
The purity and whiteness of the barium sulfate and calcium carbonate products prepared in example 1-example 16 were measured and analyzed, and the results are shown in table 3:
TABLE 3 Table 3
Remarks: (1) BaSO (Baso) 4 Reference is made to GB/T2899-2017 industrial precipitated barium sulfate detection analysis;
②CaCO 3 and (3) detecting and analyzing by referring to GB/T19590-2011 nanometer calcium carbonate.
The invention may be implemented by reference to the prior art or conventional technical means known to those skilled in the art.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The method for co-producing the nano barium sulfate and the nano calcium carbonate is characterized by comprising the following steps of:
s1: adding hydrochloric acid into barium carbonate serving as a barium source to prepare a barium chloride solution, and collecting carbon dioxide gas;
s2: delivering carbon dioxide and calcium hydroxide slurry into an improved Taylor reactor for gas-liquid precipitation reaction, filtering, washing, drying and crushing to prepare nano calcium carbonate, and collecting the filtered filtrate and washing water to be mixed into water for preparing calcium hydroxide slurry;
s3: the barium chloride solution and sulfuric acid are sent into an improved Taylor reactor for liquid-liquid precipitation reaction, then filtered, washed, dried and crushed to prepare nano barium sulfate, the filtered filtrate and the washing solution are collected and mixed to obtain hydrochloric acid solution, and the hydrochloric acid solution is concentrated and returned to the step S1;
the improved Taylor reactor is conical;
the improved Taylor reactor comprises an outer cone (15) and an inner cone (16), wherein the inner cone (16) can rotate, and the outer cone (15) is fixed; a gap (17) is formed between the outer wall of the inner cone (16) and the inner wall of the outer cone (15), and a plurality of small holes (18) are formed in the inner cone (16); the small hole (18) is communicated with the gap (17) and the interior of the inner cone (16); the outer cone (15) is provided with a first feeding pipe (20) extending into the gap (17), the inner cone (16) is provided with a second feeding pipe (21) extending into the inner cone (16), and the bottom of the outer cone (15) is provided with a discharge opening (19).
2. The method for co-producing nano barium sulfate and nano calcium carbonate according to claim 1, wherein the molar concentration of the hydrochloric acid is 0.4-3.4mol/L, and the molar concentration of the barium chloride solution is 0.2-1.7mol/L.
3. The method for co-producing nano barium sulfate and nano calcium carbonate according to claim 1, wherein the temperature of the step S1 is 10-50 ℃.
4. The method for co-producing nano barium sulfate and nano calcium carbonate according to claim 1, wherein the reaction temperature in the step S2 is 2-15 ℃, and the speed of the modified taylor reactor is 1000-2500rpm.
5. The method for co-producing nano barium sulfate and nano calcium carbonate according to claim 1 or 4, wherein the reaction temperature in the step S2 is 5-10 ℃, and the speed of the improved taylor reactor is 1500-2000rpm.
6. The method for co-producing nano barium sulfate and nano calcium carbonate according to claim 1, wherein the reaction temperature in the step S3 is 30 ℃, and the speed of the modified taylor reactor is 1000-2500rpm.
7. The nano barium sulfate prepared by the method of any one of claims 1-6.
8. An apparatus for co-producing nano barium sulfate and nano calcium carbonate, comprising: an acidolysis tank (1), a liquid-liquid reaction tank (2), a gas-liquid reaction tank (3), a nano calcium carbonate storage tank (8) and a nano barium sulfate storage tank (9); the top of the acidolysis tank (1) is provided with a gas discharge hole, the gas-liquid reaction tank (3) is provided with a gas inlet, and the gas discharge hole is communicated with the gas inlet; the bottom of the acidolysis tank (1) is provided with a liquid discharge hole, the liquid-liquid reaction tank (2) is provided with a liquid inlet, and the liquid discharge hole is communicated with the liquid inlet; a hydrochloric acid inlet pipe and a barium carbonate inlet are arranged near the top of the acidolysis tank (1), the hydrochloric acid inlet pipe is connected with a hydrochloric acid storage tank (13) through a pipe, and the barium carbonate inlet is connected with a barium carbonate storage tank (14); a slurry inlet is formed in the gas-liquid reaction tank (3), and the slurry inlet is connected with a calcium hydroxide storage tank (5) through a pipeline; the gas-liquid reaction tank (3) is provided with a slurry outlet, the slurry outlet is connected with a filtering and washing tower a (6), the filtrate outlet end of the filtering and washing tower a (6) is connected with the calcium hydroxide storage tank (5), the filter cake outlet end of the filtering and washing tower a (6) is connected with a drying tower a (7), and the drying tower a (7) is communicated with the nano calcium carbonate storage tank (8); a sulfuric acid inlet is arranged on the liquid-liquid reaction tank (2), and the sulfuric acid inlet is connected with a sulfuric acid storage tank (4) through a pipeline; a reaction slurry discharge port is formed in the liquid-liquid reaction tank (2), a filtering and washing tower b (11) is connected to the reaction slurry discharge port through a pipeline, a concentration tank (12) is connected to the filtrate discharge end of the filtering and washing tower b (11) through a pipeline, and the discharge end of the concentration tank (12) is communicated with the hydrochloric acid inlet pipe; the filter cake discharge end of the filtering and washing tower b (11) is connected with a drying tower b (10), and the drying tower b (10) is communicated with the nano barium sulfate storage tank (9); the liquid-liquid reaction tank (2) and the gas-liquid reaction tank (3) are internally provided with improved Taylor reactors which are conical;
the improved Taylor reactor comprises an outer cone (15) and an inner cone (16), wherein the inner cone (16) can rotate, and the outer cone (15) is fixed; a gap (17) is formed between the outer wall of the inner cone (16) and the inner wall of the outer cone (15), and a plurality of small holes (18) are formed in the inner cone (16); the small hole (18) is communicated with the gap (17) and the interior of the inner cone (16); the outer cone (15) is provided with a first feeding pipe (20) extending into the gap (17), the inner cone (16) is provided with a second feeding pipe (21) extending into the inner cone (16), and the bottom of the outer cone (15) is provided with a discharge opening (19).
9. The improved taylor reactor suitable for nano barium sulfate and/or nano calcium carbonate production is characterized by comprising an outer cone (15) and an inner cone (16), wherein the inner cone (16) can rotate, and the outer cone (15) is fixed; a gap (17) is formed between the outer wall of the inner cone (16) and the inner wall of the outer cone (15), and a plurality of small holes (18) are formed in the inner cone (16); the small hole (18) is communicated with the gap (17) and the interior of the inner cone (16); the outer cone (15) is provided with a first feeding pipe (20) extending into the gap (17), the inner cone (16) is provided with a second feeding pipe (21) extending into the inner cone (16), and the bottom of the outer cone (15) is provided with a discharge opening (19).
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