Manufacturing method and application of barium sulfate for storage batteries

Abstract

To provide a preparation method of barium sulfate for a storage battery, the barium sulfate, and application of the barium sulfate.SOLUTION: The water solution with the sulfate ion content of 1.8 to 2.0 mol / L is subjected to heat preservation under the condition that the temperature is larger than or equal to 80°C, a sulfate ion solution is obtained, the water solution with the barium ion content of 0.9 to 1.0 mol / L is subjected to heat preservation under the condition that the temperature is larger than or equal to 80°C, and a barium ion solution is obtained. Adding the barium ion solution into the sulfate ion solution in a stirring state, reacting and curing under the condition that the rotating speed is 20 to 40r / min, and washing and pickling precipitates to obtain barium sulfate. According to the method, it can be ensured that the barium sulfate has good dispersity without adding a modifying agent or a dispersing agent. Impurities in barium sulfate are removed through water washing and acid pickling, and the influence of the impurities on the storage battery is prevented. The barium sulfate prepared by this method is suitable for preparation of lead-acid storage batteries.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure belongs to the technical field of manufacturing chemical materials, and specifically relates to a method for manufacturing barium sulfate for storage batteries, and barium sulfate and its applications based on the method. [Background technology]

[0002] Barium sulfate is widely used as a filler in industries such as paint, plastics, and papermaking, and as a cathode additive in lead-acid batteries. By forming a barium sulfate film, it changes the properties of the battery solution and affects mechanisms such as reaction rate, thereby significantly affecting battery performance. In batteries, barium sulfate increases capacity, extends cycle life, suppresses self-discharge, improves durability, and increases battery output. Summary of the Invention [Problem to be solved by the invention]

[0003] However, the traditional barium sulfate production process uses the Glauber's salt process, which results in small particle size and prone to agglomeration. This process generally requires additional modifiers and dispersants to impart better luster and dispersibility to the barium sulfate. Barium sulfate produced in this manner is primarily suitable for the production of powder coatings and plastics, but is not suitable for batteries. This is because various indicators, such as iron content, chloride ions, and dissolved materials, as well as the modifiers and dispersants added during the barium sulfate production process, affect the performance of lead-acid batteries. Therefore, a method for producing barium sulfate suitable for lead-acid batteries is needed.

[0004] Therefore, in order to overcome the above-mentioned drawbacks of the prior art, the present disclosure aims to provide a method for producing barium sulfate for batteries, and barium sulfate and its applications based thereon, in order to solve the technical problem that barium sulfate produced by the conventional production process cannot be used in lead-acid batteries. [Means for solving the problem]

[0005] To achieve the above objectives, the present disclosure adopts the following technical solutions to achieve them:

[0006] In one aspect, there is provided a method for producing barium sulfate for a storage battery, the method comprising the steps of adding a barium ion solution to a sulfate ion solution with stirring to react and age the solution, and then recovering the precipitate, washing with water, and pickling to obtain barium sulfate, wherein the sulfate ion solution is obtained by keeping an aqueous solution having a sulfate ion content of 1.8 to 2.0 mol / L at 80°C or higher, and the barium ion solution is obtained by keeping an aqueous solution having a barium ion content of 0.9 to 1.0 mol / L at 80°C or higher, and the reaction is carried out at a rotational speed of 20 to 40 r / min.

[0007] Preferably, the sulfate ion solution is a sodium sulfate aqueous solution or a sulfuric acid solution, and the barium ion solution is a barium sulfate aqueous solution, a barium chloride aqueous solution, a barium hydroxide aqueous solution or a barium nitrate aqueous solution.

[0008] Preferably, the aging time is ≧6 hours.

[0009] Preferably, after the acid washing, the solid content is adjusted to 300 to 500 g / L, the pH value is adjusted to 6 to 7, and the moisture content of the final product is adjusted to 0.15% or less and the fineness is adjusted to 0.06% or less.

[0010] Preferably, both the sulfate ion solution and the barium ion solution are filtered through a filtration device with a mesh size of 300 or more after incubation.

[0011] The mass ratio of the sulfate ions to the barium ions at the end of the reaction is controlled to be (1 to 1.1:1).

[0012] The washing is carried out using distilled water or deionized water until the pH value of the water outside the frame is 8.0 or less.

[0013] The acid washing is carried out by adding an acid to adjust the pH value to 4 to 5 and stirring for 30 minutes.

[0014] Another aspect of the present disclosure provides barium sulfate produced by the above-described production method, wherein the particle size of the barium sulfate is 0.85 to 0.95 μm.

[0015] In another aspect of the present disclosure, there is provided an application of barium sulfate produced by the above-described production method to the production of lead acid batteries. [Effects of the Invention]

[0016] The present disclosure has the following beneficial effects compared to the prior art.

[0017] The manufacturing method for barium sulfate for storage batteries according to the present disclosure provides the following effect: (1) By appropriately controlling the content of sulfate ions and barium ions, high-temperature maintenance, slow stirring, and aging process, barium sulfate can maintain good dispersion and prevent aggregation without the addition of modifiers or dispersants. (2) By maintaining the temperature for a long period of time, precipitates grow and accumulate, forming sediments. (3) By maintaining the temperature at high temperatures of 80°C or higher, the particle size of barium sulfate can be grown. (4) By washing the precipitate with water, chloride ions in the product can be minimized, preventing their impact on the battery's lifespan and reducing water-soluble substances in the barium sulfate, preventing the incorporation of harmful substances into the battery. (5) By pickling and removing the sulfur ions from the precipitate, the impact of sulfur ions on the battery can be prevented. Furthermore, the particle size of the barium sulfate produced by this method is 0.85 to 0.95 μm, and tests on the concentrations of sulfide ions, chloride ions, and water-soluble substances in the prepared barium sulfate revealed that all of these were lower than the concentrations in high-quality barium sulfate prepared by the dark gray Glauber's salt method. This conforms to the GB / T2899-2017 standard and is suitable for the production of lead-acid batteries.

[0018] Furthermore, by setting the aging time to 6 hours or more, the particle size of the barium sulfate grows, forming a regular shape and becoming almost spherical.

[0019] Furthermore, if the storage battery is used in a strongly acidic environment or has an alkaline pH, it is harmful to the battery, consuming hydrogen ions and attracting impurities. If the pH is too low, the barium sulfate will corrode the production equipment severely, affecting production safety. By adjusting the pH value to 6-7 after pickling, production safety is ensured while the quality of the storage battery is guaranteed. The moisture content of the finished product is controlled to 0.15% or less, and the fineness is controlled to 0.06% or less, improving the dispersion of barium sulfate within the lead-acid battery.

[0020] Furthermore, the sodium sulfate aqueous solution and barium sulfide aqueous solution are filtered and reused to remove impurities in the raw materials and further guarantee the quality of the produced barium sulfate.

[0021] Furthermore, by controlling the pH value of the flameout water to 8.0 or less, the amount of water-soluble substances in the barium sulfate can be minimized. DETAILED DESCRIPTION OF THE INVENTION

[0022] In order to enable those skilled in the art to understand the features and advantages of the present invention, the following provides general explanations and definitions for the terms and phrases used in the patent specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the meanings commonly understood by those skilled in the art in the context of the present invention. In the event of any discrepancy in the interpretation of terms, the definitions set forth herein shall prevail.

[0023] The theories and mechanisms described and disclosed herein, whether correct or incorrect, are not intended to limit the scope of the present invention in any way, and the subject matter of the present invention can be practiced without being bound by any particular theory or mechanism.

[0024] Properties (e.g., numerical values, amounts, contents, concentrations) expressed in the form of numerical ranges or percentage ranges are described herein for brevity and convenience, and therefore, the description of a numerical range or percentage range should be considered to have specifically disclosed all possible subranges and individual numerical values ​​(including integers and fractions) within the range.

[0025] In this specification, unless otherwise specified, the terms "comprise," "include," "contain," "have," etc. include the meanings of "consist of" and "consist essentially of." For example, "A includes a" includes the meanings of both "A includes a and other things" and "A includes only a."

[0026] For the sake of brevity, this specification does not describe in detail all possible combinations of each technical feature in each embodiment or example. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be arbitrarily combined. All possible combinations should be considered to be within the scope described in this specification.

[0027] The present disclosure provides a method for producing barium sulfate for batteries, comprising the steps of: 1) A barium ion solution with a barium ion content of 0.9-1.0 mol / L is collected and purified by heating at 80°C or higher for 12 hours. The purified solution is then filtered through a filtration device with a mesh size of 300 or larger for use in producing barium sulfate. This barium ion solution can be a barium sulfide aqueous solution, a barium chloride aqueous solution, a barium hydroxide aqueous solution, or a barium nitrate aqueous solution. 2) A sulfate ion solution with a sulfate ion content of 1.8-2.0 mol / L is collected, adjusted to a pH of 11 or less, and purified by incubating at 80°C or higher for 12 hours. The solution is then filtered through a filtration device with a mesh size of 300 or larger and used to produce barium sulfate. The sulfate ion solution is a sodium sulfate solution or a sulfuric acid solution. 3) During the reaction, first add the sulfate ion solution treated in step 2 and stir at a rotation speed of 20-40 r / min. Then, while still stirring, add the barium ion solution treated in step 1 and react for 15-20 minutes at a temperature of 80°C or higher. The reaction is completed when the two substances are in equal amounts, or the ratio of sulfate ions to barium ions is 1.1:1, and then the mixture is aged. The aging time should be at least 6 hours. 4) After the maturation time is over, the precipitated barium sulfate slurry is taken out and the impurities in the barium sulfate slurry are separated using a separator such as a centrifuge or a squeeze filter.The barium sulfate cake is then washed with distilled or deionized water to reduce the content of water-soluble substances and chloride ions in the barium sulfate, and the pH value of the discharge water is controlled to 8.0 or less. 5) After washing, the barium sulfate cake is concentrated and acid washed, the pH is adjusted to 4-5, and the cake is stirred for 30 minutes to remove the sulfur ions. Water is then added to adjust the solid content to 300-500 g / L, the pH to 6-7, and the cake is dried. The moisture content of the finished product is controlled to 0.15% or less, and the fineness to 0.06% (325 mesh) or less.

[0028] The present invention will be described in more detail below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and do not limit the scope of the present invention. After reading the contents of the present invention, those skilled in the art may make various modifications and alterations to the present invention. These equivalent forms are also intended to be included in the scope defined by the appended claims of this application.

[0029] The following examples use instruments and devices commonly used in this field. Experimental methods for which no specific conditions are described are carried out according to standard conditions or conditions recommended by the manufacturer. Unless otherwise specified, the various raw materials used in the following examples are commercially available standard products, and their specifications are those commonly used in this field. In the present specification and the following examples, "%" indicates percentage by weight unless otherwise specified.

[0030] Example 1 Raw material pretreatment (1) A barium sulfide aqueous solution with a barium ion content of 0.9 mol / L is kept at 80°C for 12 hours, passed through a 400-mesh sieve, and used to produce barium sulfate.

[0031] (2) A sodium sulfate aqueous solution with a pH value of 11 and a sulfate ion content of 1.8 mol / L is kept at 80°C for 12 hours, and then passed through a 400-mesh sieve for use in producing barium sulfate.

[0032] Barium sulfate production (1) Add an aqueous sodium sulfate solution to a reaction vessel and set the stirring speed to 30-40 r / min. Then, add an aqueous barium sulfate solution to the reaction vessel and stir at 80°C for 20 minutes. After aging for 7 hours, confirm that the amounts of the aqueous sodium sulfate solution and the aqueous barium sulfide solution are equal at the end of the reaction. The aged product is centrifuged, and the resulting precipitate (barium sulfate slurry) is recovered. The separated supernatant can be used to produce industrial sodium sulfide.

[0033] (2) The barium sulfate slurry obtained in step 1) is further centrifuged in a centrifuge to remove impurities, and then washed with distilled water until the pH value of the water is 8.0 or less.

[0034] (3) Add 95% concentrated sulfuric acid to the barium sulfate slurry washed in step 2) to adjust the pH to 4 and stir for 30 minutes. Then, add water to adjust the solid content to 400 g / L and the pH to 6. Finally, dry the product to control the moisture content to 0.15% or less and the fineness to 0.06% or less to obtain barium sulfate.

[0035] Example 2 Raw material pretreatment (1) A barium sulfide aqueous solution with a barium ion content of 1.0 mol / L is kept at 90°C for 12 hours, passed through a 600 mesh sieve, and used to produce barium sulfate.

[0036] (2) A sodium sulfate aqueous solution with a pH value of 13 and a sulfate ion content of 2.0 mol / L is kept at 90°C for 12 hours, and then passed through a 600-mesh sieve for use in producing barium sulfate.

[0037] 2. Production of barium sulfate (1) Add an aqueous sodium sulfate solution to a reaction vessel and set the stirring speed to 25-35 r / min. Then, add an aqueous barium sulfate solution to the reaction vessel and stir at 90°C for 15 minutes. The mixture is then aged for 8 hours, and at the end of the reaction, it is confirmed that the amounts of the aqueous sodium sulfate solution and the aqueous barium sulfide solution are equal. The aged product is centrifuged, and the resulting precipitate (barium sulfate slurry) is recovered. The separated supernatant liquid can be used to produce industrial sodium sulfide.

[0038] (2) The barium sulfate slurry obtained in step 1) is further centrifuged in a centrifuge to remove impurities, and then washed with deionized water until the pH value of the water is 8.0 or less.

[0039] (3) Add 96% concentrated sulfuric acid to the barium sulfate slurry washed in step 2) to adjust the pH to 5 and stir for 30 minutes. Then, add water to adjust the solid content to 500 g / L and the pH to 6. Finally, dry the product to control the moisture content to 0.15% or less and the fineness to 0.06% or less to obtain barium sulfate.

[0040] Example 3 Raw material pretreatment (1) A 1.0 mol / L aqueous solution of barium hydroxide is kept at 90°C for 12 hours, passed through an 800 mesh sieve, and used to produce barium sulfate.

[0041] (2) A sulfuric acid solution with a pH value of 12 and a content of 1.9 mol / L is kept at 90°C for 12 hours, and then passed through an 800-mesh sieve to be used for producing barium sulfate.

[0042] Barium sulfate production (1) Add the barium hydroxide aqueous solution to the reaction vessel and set the stirring speed to 20-30 r / min. Then, add the sulfuric acid solution to the reaction vessel and stir at 100°C for 18 minutes. After that, mature for 8 hours, and confirm that the ratio of the sulfuric acid solution to the barium hydroxide aqueous solution is 1.1:1 at the end of the reaction. The matured product is centrifuged, and the resulting precipitate (barium sulfate slurry) is recovered. The separated supernatant liquid can be used to produce industrial sodium sulfide.

[0043] (2) The barium sulfate slurry obtained in step 1) is further centrifuged in a centrifuge to remove impurities, and then washed with deionized water until the pH value of the water is 8.0 or less.

[0044] (3) Add 95% concentrated sulfuric acid to the barium sulfate slurry washed in step 2) to adjust the pH to 4, and stir for 30 minutes. Then, add water to adjust the solid content to 300 g / L and the pH to 7. Finally, dry the product to control the moisture content to 0.15% or less and the fineness to 0.06% or less, and obtain barium sulfate.

[0045] Example 4 Raw material pretreatment (1) A 0.9 mol / L aqueous solution of barium chloride is kept at 100°C for 12 hours, passed through a 500 mesh sieve, and used to produce barium sulfate.

[0046] (2) A sodium sulfate aqueous solution with a pH value of 12 and a content of 1.8 mol / L is kept at 100°C for 12 hours, and then passed through a 500-mesh sieve to be used for producing barium sulfate.

[0047] 2. Production of barium sulfate (1) Add a barium chloride aqueous solution to a reaction vessel and set the stirring speed to 20-30 r / min. Then, add a sodium sulfate aqueous solution to the reaction vessel and stir at 90°C for 20 minutes. After that, mature for 7 hours, and at the end of the reaction, confirm that the amounts of the sodium sulfate aqueous solution and the barium chloride aqueous solution are equal. The matured product is centrifuged, and the resulting precipitate (barium sulfate slurry) is collected. The separated supernatant liquid can be used to produce industrial sodium sulfide.

[0048] (2) The barium sulfate slurry obtained in step 1) is further centrifuged in a centrifuge to remove impurities, and then washed with deionized water until the pH value of the water is 8.0 or less.

[0049] (3) Add 95% concentrated sulfuric acid to the barium sulfate slurry washed in step 2) to adjust the pH to 4 and stir for 30 minutes. Then, add water to adjust the solid content to 500 g / L and the pH to 6. Finally, dry the product to control the moisture content to 0.15% or less and the fineness to 0.06% or less to obtain barium sulfate.

[0050] The barium sulfate samples prepared in Examples 1 to 4 were tested for their morphology, content, moisture content, oil absorption, pH value, sieve residue, iron content, and chloride ion content. See Table 1 for the test results.

[0051] JPEG0007818661000001.jpg220160

[0052] As can be seen from Table 1, all of the produced barium sulfate samples were in the form of white powder with particle sizes ranging from 0.85 to 0.95 μm. The concentrations of sulfide ions, chloride ions, and water-soluble substances in the barium sulfate were all lower than those of the high-quality barium sulfate produced using the dark gray Glauber's salt method. This conforms to the GB / T2899-2017 standard and is suitable for the production of lead-acid batteries.

[0053] The above content is intended to illustrate the technical idea of ​​the present invention, and does not limit the protection scope of the present invention. Any modifications made based on the technical idea and technical solutions proposed by the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. The method includes a step of adding a barium ion solution to a sulfate ion solution while stirring to cause a reaction, maturing the reaction, and then recovering the precipitate, washing it with water, and pickling it to obtain barium sulfate. The method for producing barium sulfate for a storage battery, wherein the sulfate ion solution is obtained by keeping an aqueous solution having a sulfate ion content of 1.8 to 2.0 mol / L at 80°C or higher, and the barium ion solution is obtained by keeping an aqueous solution having a barium ion content of 0.9 to 1.0 mol / L at 80°C or higher, and the reaction is carried out at a rotation speed of 20 to 40 r / min.

2. 2. The method for producing barium sulfate for a storage battery according to claim 1, wherein the sulfate ion solution is a sodium sulfate aqueous solution or a sulfuric acid solution, and the barium ion solution is a barium sulfide aqueous solution, a barium chloride aqueous solution, a barium hydroxide aqueous solution, or a barium nitrate aqueous solution.

3. 2. The method for producing barium sulfate for a storage battery according to claim 1, wherein the aging time is ≥ 6 hours.

4. 2. The method for producing barium sulfate for a storage battery according to claim 1, wherein after the acid washing, the solid content is adjusted to 300 to 500 g / L, the pH value is adjusted to 6 to 7, and the moisture content of the final product is 0.15% or less and the fineness is 0.06% or less.

5. The method for producing barium sulfate for a storage battery according to any one of claims 1 to 4, characterized in that the mass ratio of the sulfate ions to the barium ions at the end of the reaction is controlled to be (1 to 1.1):

1.

6. The method for producing barium sulfate for a storage battery according to any one of claims 1 to 4, characterized in that the acid washing is carried out by adding an acid to adjust the pH value to 4 to 5 and stirring for 30 minutes.

7. 5. The application of barium sulfate produced by the method according to any one of claims 1 to 4 to the manufacture of lead acid batteries.

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