Preparation method of barium sulfate for storage battery and application of barium sulfate

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 the manufacture of chemical engineering materials, and specifically relates to a method for manufacturing barium sulfate for a storage battery, barium sulfate based thereon, and its applications.

Background Art

[0002] Barium sulfate is widely used as a filler in industries such as paints, plastics, and paper manufacturing, and is also used as a cathode additive in lead-acid batteries. By forming a barium sulfate film, it can change the properties of the battery solution and affect mechanisms such as the reaction rate, thereby having an important impact on battery performance. In a storage battery, barium sulfate increases the capacity, extends the cycle life, suppresses self-discharge, improves durability, and increases the output of the battery.

Summary of the Invention

Problems to be Solved by the Invention

[0003] However, the conventional production process of barium sulfate is carried out by the black ash glauber's salt method, and the product particle size is small and it is easy to agglomerate. In this method, generally additional modifiers or dispersants are required to give better gloss and dispersibility to barium sulfate. The barium sulfate produced in this way is mainly suitable for the manufacture of powder paints and plastics, but not suitable for storage batteries. This is because various indicators such as the iron content, chloride ions, and dissolved substances in the production process of barium sulfate, as well as the introduced modifiers and dispersants, affect the performance of lead-acid batteries. Therefore, a method for manufacturing barium sulfate suitable for lead-acid batteries is needed.

[0004] Therefore, in order to overcome the above-mentioned disadvantages of the prior art, the present disclosure aims to provide a method for manufacturing barium sulfate for a battery, barium sulfate based thereon, and its applications 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 Problems

[0005] To achieve the above object, the present disclosure adopts the following technical solutions to achieve it.

[0006] On one side, it includes the steps of adding a barium ion solution to a sulfate ion solution while stirring, reacting, aging, taking out the precipitate, washing with water, and pickling with acid to obtain barium sulfate. The sulfate ion solution is obtained by keeping an aqueous solution with a sulfate ion content of 1.8 - 2.0 mol / L at 80 °C or higher. The barium ion solution is obtained by keeping an aqueous solution with a barium ion content of 0.9 - 1.0 mol / L at 80 °C or higher. The reaction is carried out at a rotation speed of 20 - 40 r / min. A method for manufacturing barium sulfate for a storage battery is provided.

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

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

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

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

[0011] Control the mass ratio of the sulfate ion to the barium ion at the end of the reaction to be (1 - 1.1):1.

[0012] The water 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 pickling is carried out by adding acid to adjust the pH value to 4 - 5 and stirring for 30 minutes.

[0014] In another aspect of the present disclosure, there is provided barium sulfate produced by the above manufacturing 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 manufacturing method in the manufacture of lead-acid batteries.

Advantages of the Invention

[0016] According to the present disclosure, compared with the prior art, it has the following beneficial effects.

[0017] By the method for manufacturing barium sulfate for a storage battery according to the present disclosure, effect (1): By appropriately controlling the contents of sulfate ions and barium ions, high-temperature retention, low-speed stirring, and aging process, barium sulfate can maintain good dispersibility and prevent aggregation without adding a modifier or a dispersant. Effect (2): By maintaining the temperature for a long time, precipitates grow, accumulate, and sedimentation is formed. Effect (3): Keeping the temperature under high-temperature conditions of 80 °C or higher is advantageous for the growth of the particle size of barium sulfate. Effect (4): By washing the precipitate with water, the chloride ions in the product are minimized, the influence of chloride ions on the life of the storage battery is prevented, the water-soluble substances in the barium sulfate are reduced, and the mixing of harmful substances into the storage battery is prevented. Effect (5): By pickling and removing sulfur ions in the precipitate, the influence of sulfur ions on the storage battery is prevented. In addition, the particle size of the barium sulfate produced by this method is 0.85 to 0.95 μm. When the concentrations of sulfide ions, chloride ions, and water-soluble substances in the prepared barium sulfate were tested, it was found that they were all lower than the concentrations of high-grade products prepared by the black-gray mirabilite method, and it conforms to the GB / T2899-2017 standard and is suitable for the manufacture of lead-acid batteries.

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

[0019] Furthermore, the operating environment of the storage battery is strongly acidic, and an alkaline pH value is harmful to the battery, consuming hydrogen ions and attracting impurities. If the pH value is too low, the corrosion of the barium sulfate production equipment will intensify, affecting production safety. By adjusting the pH value after pickling to 6 - 7, while ensuring production safety, the quality of the storage battery is guaranteed. Control the moisture content of the finished product to be 0.15% or less and the fineness to be 0.06% or less to improve the dispersibility of barium sulfate in the lead-acid battery.

[0020] Furthermore, by filtering and reusing the aqueous sodium sulfate solution and the aqueous barium sulfide solution, impurities in the raw materials are removed, further guaranteeing the quality of the produced barium sulfate.

[0021] Furthermore, by controlling the pH value of the frame-out water to be 8.0 or less, the water-soluble substances in the barium sulfate can be minimized.

Embodiments for Carrying Out the Invention

[0022] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general explanation and definition of the terms and words used in the patent specification and claims. Unless otherwise explicitly stated, all technical terms and scientific terms used in this specification shall have the meanings commonly understood by those skilled in the art with respect to the present invention. In case of any conflict in the interpretation of terms, the definitions described in this specification shall prevail.

[0023] The theories and mechanisms described and disclosed in this specification, regardless of their correctness, do not limit the scope of the present invention in any form. The content of the present invention can be implemented without being restricted by specific theories and mechanisms.

[0024] In this specification, characteristics (such as numerical values, quantities, contents, concentrations, etc.) presented in the form of numerical ranges or percentage ranges are described for the sake of brevity and convenience. Therefore, the description of numerical ranges or percentage ranges should be regarded as specifically disclosing all possible sub-ranges and individual numerical values (including integers and fractions) within the ranges.

[0025] In this specification, unless otherwise specified, terms such as "comprising", "including", "containing", "having", etc. include the meanings of "consisting of" and "substantially consisting of". For example, "A comprises a" includes both the meanings of "A includes a and other things" and "A includes only a".

[0026] In this specification, for the sake of brevity, not all possible combinations of all technical features in each embodiment or example are described in detail. 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 regarded as being within the scope described in this specification.

[0027] The present disclosure provides a method for manufacturing barium sulfate for a storage battery, including the following steps: 1) Take a barium ion solution with a barium ion content of 0.9 - 1.0 mol / L, keep it warm at 80°C or higher for 12 hours for purification, then filter it using a filtering device with 300 mesh or more, and use it for the production of barium sulfate. This barium ion solution is an aqueous solution of barium sulfide, barium chloride, barium hydroxide, or barium nitrate. 2) Take a sulfate ion solution with a sulfate ion content of 1.8 - 2.0 mol / L, adjust the pH to 11 or less, keep it warm at 80°C or higher for 12 hours for purification, then filter it using a filtering device with 300 mesh or more, and use it for the production of barium sulfate. Also, the sulfate ion solution is an aqueous solution of sodium sulfate or a sulfuric acid solution. 3) During the reaction, first add the sulfate ion solution treated in Step 2, and stir it under the condition of a rotation speed of 20 - 40 r / min. Then, while stirring, add the barium ion solution treated in Step 1, and react it for 15 - 20 minutes under the condition of a temperature of 80°C or higher. The reaction end point is to confirm that the two substances are in equal amounts or the molar ratio of sulfate ions to barium ions is 1.1:1, and then age it. The aging time shall be 6 hours or more. 4) When the aging time is over, take the barium sulfate slurry which is the precipitate, and use a separation device such as a centrifuge or a squeeze filter to separate the impurities in the barium sulfate slurry. Then, wash the barium sulfate cake with distilled water or deionized water to reduce the content of water-soluble substances and chloride ions in the barium sulfate, and control the pH value of the effluent water to be 8.0 or less. 5) Concentrate and acid-wash the washed barium sulfate cake, adjust the pH value to 4 - 5 and stir for 30 minutes to remove sulfur ions. Then, add water to adjust the solid content to 300 - 500 g / L, adjust the pH value to 6 - 7 and dry it. Control the moisture content of the finished product to be 0.15% or less and the fineness to be 0.06% (325 mesh) or less.

[0028] Hereinafter, specific examples are shown to explain the present invention in more detail. It should be understood that these examples are for explaining the present invention and do not limit the scope of the present invention. Also, after reading the content of the present invention, those skilled in the art can make various modifications and corrections to the present invention. These equivalent forms shall also be included in the scope limited by the appended claims of this application.

[0029] In the following examples, equipment and devices generally used in this field are used. For experimental methods where specific conditions are not described, they are carried out according to normal conditions or conditions recommended by the manufacturer. For various raw materials used in the following examples, unless otherwise specified, commercially available ordinary products are used, and their specifications are the normal specifications in this field. In the specification of the present invention and the following examples, unless otherwise explicitly stated, "%" indicates weight percentage.

[0030] (Example 1) Pretreatment of raw materials (1) An aqueous barium sulfide 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 for the production of barium sulfate.

[0031] (2) An aqueous sodium sulfate 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, passed through a 400-mesh sieve, and used for the production of barium sulfate.

[0032] Production of barium sulfate (1) Add the aqueous sodium sulfate solution to the reaction vessel and set the stirring speed to 30 - 40 r / min. Then, add the aqueous barium sulfide solution to the reaction vessel and stir at 80 °C for 20 minutes. Then, age for 7 hours and confirm that the amounts of substance of the aqueous sodium sulfate solution and the aqueous barium sulfide solution are equal at the end of the reaction. Centrifuge the aged product, collect the obtained precipitate (barium sulfate slurry), and the separated supernatant can be used for the production of industrial sodium sulfide.

[0033] (2) Further centrifuge the barium sulfate slurry obtained in step (1) with a centrifuge to remove impurities. Then, wash with distilled water and continue washing until the pH value of the effluent water is 8.0 or less.

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

[0035] (Example 2) Pretreatment of raw materials (1) An aqueous barium sulfide 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 for the production of barium sulfate.

[0036] (2) An aqueous sodium sulfate 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, passed through a 600-mesh sieve, and used for the production of barium sulfate.

[0037] 2. Production of Barium Sulfate (1) Add the aqueous sodium sulfate solution to the reaction vessel and set the stirring speed to 25 - 35 r / min. Then, add the aqueous barium sulfide solution to the reaction vessel and stir at 90 °C for 15 minutes. Then, age for 8 hours and confirm that the amounts of substance of the aqueous sodium sulfate solution and the aqueous barium sulfide solution are equal at the end of the reaction. Centrifuge the aged product, recover the obtained precipitate (barium sulfate slurry), and the separated supernatant can be used for the production of industrial sodium sulfide.

[0038] (2) Further centrifuge the barium sulfate slurry obtained in step (1) with a centrifuge to remove impurities. Then, wash with deionized water and continue washing until the pH value of the effluent water is 8.0 or less.

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

[0040] (Example 3) Pretreatment of Raw Materials (1) Keep an aqueous barium hydroxide solution with a content of 1.0 mol / L at 90 °C for 12 hours, pass through an 800-mesh sieve, and use it for the production of barium sulfate.

[0041] (2) Keep a sulfuric acid solution with a pH value of 12 and a content of 1.9 mol / L at 90 °C for 12 hours, pass through an 800-mesh sieve, and use it for the production of barium sulfate.

[0042] Production of Barium Sulfate (1) Add an aqueous solution of barium hydroxide to a reaction vessel and set the stirring speed to 20 - 30 r / min. Then, add a sulfuric acid solution to the reaction vessel and stir at 100 °C for 18 minutes. After that, let it age for 8 hours and confirm that the molar amount ratio of the sulfuric acid solution to the aqueous barium hydroxide solution is 1.1:1 at the reaction end point. Centrifuge the aged product and collect the obtained precipitate (barium sulfate slurry). The separated supernatant can be used in the production of industrial sodium sulfide.

[0043] (2) Further centrifuge the barium sulfate slurry obtained in step (1) with a centrifuge to remove impurities. Then, wash it with deionized water and continue washing until the pH value of the effluent water is 8.0 or less.

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

[0045] (Example 4) Pretreatment of raw materials (1) Keep an aqueous solution of barium chloride with a content of 0.9 mol / L at 100 °C for 12 hours, pass it through a 500 - mesh sieve, and use it in the production of barium sulfate.

[0046] (2) Keep an aqueous solution of sodium sulfate with a pH value of 12 and a content of 1.8 mol / L at 100 °C for 12 hours, pass it through a 500 - mesh sieve, and use it in the production of barium sulfate.

[0047] 2. Production of barium sulfate (1) Add an aqueous barium chloride solution to a reaction vessel and set the stirring speed to 20 - 30 r / min. Then, add an aqueous sodium sulfate solution to the reaction vessel and stir at 90 °C for 20 minutes. Then, age for 7 hours and confirm that the amounts of substance of the aqueous sodium sulfate solution and the aqueous barium chloride solution are equal at the reaction end point. Centrifuge the aged product, collect the obtained precipitate (barium sulfate slurry), and the separated supernatant can be used in the production of industrial sodium sulfide.

[0048] (2) Further centrifuge the barium sulfate slurry obtained in step (1) with a centrifuge to remove impurities. Then, wash with deionized water and continue washing until the pH value of the effluent water is 8.0 or less.

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

[0050] For the test results of the morphology, content, moisture, oil absorption, pH value, sieve residue, iron content, and chloride ion content of the barium sulfate samples manufactured in Examples 1 - 4, please refer to Table 1.

[0051] JPEG2025110860000001.jpg220160

[0052] As can be seen from Table 1, all the manufactured barium sulfate samples are in the form of white powder, the particle size is 0.85 - 0.95 μm, and the concentrations of sulfide ions, chloride ions, and water-soluble substances in the barium sulfate are all lower than those of high-grade products manufactured by the black-gray mirabilite method. It complies with the GB / T2899 - 2017 standard and is suitable for the production of lead-acid batteries.

[0053] The above content is for exemplifying 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 solution proposed by the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. The method for producing barium sulfate for a storage battery includes a step of adding a barium ion solution to a sulfate ion solution while stirring, reacting, aging, taking out the precipitate, washing with water, and pickling with an acid to obtain barium sulfate. 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. 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. The reaction is carried out at a rotation speed of 20 to 40 r / min.

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

3. The method for producing barium sulfate for a storage battery according to claim 1, characterized in that the aging time is ≧ 6 hours.

4. After the pickling, the solid content is adjusted to 300 to 500 g / L and the pH value is adjusted to 6 to 7, and the moisture content of the final product is 0.15% or less and the powder fineness is 0.06% or less. The method for producing barium sulfate for a storage battery according to claim 1, characterized in that.

5. The sulfate ion solution and the barium ion solution are both obtained by filtering with a filtering device having a mesh size of 300 or more after incubation. The method for producing barium sulfate for a storage battery according to any one of claims 1 to 4, characterized in that.

6. 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 ion to the barium ion at the end of the reaction is controlled to be (1 to 1.1):

1.

7. The water washing is carried out using distilled water or deionized water, and the water washing is carried out until the pH value of the water outside the frame is 8.0 or less. The method for producing barium sulfate for a storage battery according to any one of claims 1 to 4, characterized in that.

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

9. Barium sulfate produced by the method according to any one of claims 1 to 4, characterized in that the particle size of the barium sulfate is 0.85 to 0.95 μm.

10. Application of barium sulfate produced by the method according to any one of Claims 1 to 4 to the production of lead-acid batteries.

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