Novel medicament capable of respectively removing thallium and fluorine under different pH values, preparation method and wastewater treatment method

Abstract

The invention discloses a novel agent capable of removing thallium and fluorine under different pH values, a preparation method and a wastewater treatment method, and the wastewater treatment method comprises the following steps: detecting the pH value of wastewater when the wastewater needs to be subjected to thallium removal; if the pH value of the wastewater is less than 5.5, adjusting the pH value of the wastewater to 5.5-14, and adding a novel agent into the wastewater; when defluorination needs to be carried out on the wastewater, detecting the pH value of the wastewater; and if the pH value of the wastewater is greater than 7, adjusting the pH value of the wastewater to 1-7, and adding a novel agent into the wastewater. The novel agent provided by the invention can stably play a role under different pH conditions, and the purpose of removing thallium and fluorine at the same time can be achieved by the same agent. And the agent can adapt to various complex wastewater environments, the agent preparation method is simple, the treatment effect is remarkably improved, and environmental friendliness is achieved.

Description

Technical Field

[0001] The invention relates to the field of wastewater treatment, and in particular to a novel agent capable of removing thallium and fluorine at different pH values, a preparation method and a wastewater treatment method. Background Art

[0002] In the rapid development of modern industry, the generation and discharge of thallium- and fluorine-containing wastewater has become an environmental issue that cannot be ignored. Although thallium is a highly toxic heavy metal with a relatively low content in nature, it is extremely harmful to the human body and the ecosystem due to its release during the mining and processing of certain specific mineral resources. Fluorine, as an element widely present in nature, will inevitably enter the wastewater system during the production process of many industrial fields such as chemical industry, metallurgy, electronics, glass manufacturing, etc. Excessive fluoride will also cause many adverse effects on the human body and the ecosystem.

[0003] At present, although there are various technical means for treating thallium-containing and fluoride-containing wastewater, they all have shortcomings to varying degrees. For example, some methods have strict limitations on pH values ​​and can only work within a very narrow pH range. Once the pH of the wastewater changes, the treatment effect will be greatly reduced. At the same time, existing technical means are often difficult to balance between removal efficiency and cost. Although some methods are highly efficient, they are costly; while some lower-cost methods have unsatisfactory treatment effects. In addition, the preparation process of many traditional agents is complicated and may involve the use of hazardous chemicals, which increases production costs and supply risks. Summary of the invention

[0004] The main purpose of the present invention is to provide a new agent, a preparation method and a wastewater treatment method which can respectively remove thallium and fluorine at different pH values, in order to solve the above technical problems.

[0005] To achieve the above object, the present invention proposes a novel preparation method for a medicament capable of removing thallium and fluorine at different pH values, comprising:

[0006] Step S1, adding weighed iron salt, aluminum salt and manganese compound to an appropriate amount of deionized water in sequence, stirring and mixing well to form solution A;

[0007] Step S2, dripping 25-30% NaOH solution into solution A dropwise while stirring;

[0008] Step S3, aging at room temperature for 18 to 30 hours;

[0009] Step S4, taking out the precipitate and placing it in a constant temperature drying oven at 100-110° C. to dry for 12-36 hours to form a pharmaceutical precursor;

[0010] Step S5, placing the drug precursor in a muffle furnace for calcination at a temperature of 200 to 600° C. for a calcination time of 2 to 4 hours;

[0011] Step S6: The product is cooled to room temperature to obtain a novel agent, which can be added to water bodies within different pH ranges to achieve thallium removal and fluoride removal, respectively.

[0012] In one embodiment, the iron salt includes ferric chloride hexahydrate, ferric nitrate nonahydrate, and ferric sulfate.

[0013] In one embodiment, the aluminum salt includes aluminum chloride hexahydrate, aluminum nitrate nonahydrate, and aluminum sulfate.

[0014] In one embodiment, the manganese compound includes manganese dioxide, manganese chloride, and manganese sulfate.

[0015] In one embodiment, the pH of solution A in step S2 is 5-12.

[0016] In addition, the present invention also provides a novel agent, which is prepared by the novel agent preparation method as described above, which can respectively remove thallium and fluorine at different pH values.

[0017] In addition, the present invention also provides a wastewater treatment method, the wastewater treatment method comprising:

[0018] When it is necessary to remove thallium from wastewater, the pH value of the wastewater is tested;

[0019] If the pH value of the wastewater is less than 5.5, the pH value of the wastewater is adjusted to 5.5-14, and the novel agent as described above is added to the wastewater;

[0020] When it is necessary to defluorinate the wastewater, test the pH value of the wastewater;

[0021] If the pH value of the wastewater is greater than 7, the pH value of the wastewater is adjusted to 1-7, and the novel agent as described above is added to the wastewater.

[0022] In the technical solution of the present invention, the new agent prepared according to the new agent preparation method can stably function under different pH conditions, so that the same agent can simultaneously solve the purpose of removing thallium and removing fluorine. It can also adapt to various complex wastewater environments, the agent preparation method is simple, the treatment effect is significantly improved, and it is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0024] Figure 1 The present invention is a schematic flow chart of a novel preparation method for a novel agent capable of removing thallium and fluorine at different pH values;

[0025] Figure 2 This is the effect diagram of thallium removal under different pH experimental conditions;

[0026] Figure 3 This is a diagram of fluoride removal effect under different pH experimental conditions.

[0027] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0028] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0030] In addition, in the present invention, descriptions such as "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0031] Furthermore, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in the field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0032] The invention provides a novel preparation method of a medicament which can respectively realize thallium removal and fluorine removal at different pH values.

[0033] like Figure 1 As shown, the method for preparing a novel agent that can remove thallium and fluoride at different pH values ​​provided by the embodiment of the present invention comprises sequentially adding weighed iron salt, aluminum salt and manganese compound into an appropriate amount of deionized water, stirring and mixing them evenly to form a solution A;

[0034] Step S2, dripping 25-30% NaOH solution into solution A dropwise while stirring;

[0035] Step S3, aging at room temperature for 18 to 30 hours;

[0036] Step S4, taking out the precipitate and placing it in a constant temperature drying oven at 100-110° C. to dry for 12-36 hours to form a pharmaceutical precursor;

[0037] Step S5, placing the drug precursor in a muffle furnace for calcination at a temperature of 200 to 600° C. for a calcination time of 2 to 4 hours;

[0038] Step S6: The product is cooled to room temperature to obtain a novel agent, which can be added to water bodies within different pH ranges to achieve thallium removal and fluoride removal, respectively.

[0039] In the present application, the preparation method of the novel agent is simple, and the raw materials required are not only easy to obtain, but also widely available. It exhibits considerable processing capacity for thallium and fluorine, and can achieve efficient removal of thallium and fluorine respectively in a wide pH range.

[0040] The prepared new agent can work stably under different pH conditions, achieving the purpose of removing thallium and fluorine at the same time. It can adapt to various complex wastewater environments, has a simple preparation method, significantly improves treatment effects and is environmentally friendly.

[0041] The novel agent of the present invention comprises an iron salt, an aluminum salt and a manganese compound, wherein the iron salt is ferric chloride hexahydrate, but not limited thereto, such as ferric nitrate nonahydrate and ferric sulfate; the aluminum salt is aluminum chloride hexahydrate, but not limited thereto, such as aluminum nitrate nonahydrate and aluminum sulfate; the manganese compound is manganese dioxide, but not limited thereto, such as manganese chloride and manganese sulfate.

[0042] In a preferred embodiment, the stirring method of the preparation process of the present invention can be stirred and mixed by magnetic stirring, but is not limited thereto; wherein the stirring time can be 30 to 60 minutes, and its typical but non-limiting duration is, for example, 30 minutes, 40 minutes, 50 minutes, and 60 minutes, which is more conducive to the dissolution of ferric chloride hexahydrate and aluminum chloride hexahydrate.

[0043] In a preferred embodiment, the pH condition of the preparation process of the present invention is 10, but not limited thereto; wherein the pH can be 5 to 12, and its typical but non-limiting pH is, for example, 5, 6, 7, 8, 9, 10, 11, 12, which is more conducive to further improving the oxidation effect of the product;

[0044] In a preferred embodiment, the aging time of the preparation process of the present invention is 24 hours, but not limited thereto; wherein the aging time can be 18 to 30 hours, and its typical but non-limiting time is, for example, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, and 30 hours, which is more conducive to further improving the reaction effect;

[0045] In a preferred embodiment, the drying temperature of the preparation process of the present invention is 105°C, but not limited thereto; wherein the temperature may be 100-110°C, and typical but non-limiting temperatures are, for example, 100°C, 102°C, 104°C, 106°C, 108°C, and 110°C, which are more conducive to further improving the drying effect of the product;

[0046] In a preferred embodiment, the drying time of the preparation process of the present invention is 24 hours, but not limited thereto; wherein the drying time can be 12 to 36 hours, and its typical but non-limiting time is, for example, 12 hours, 18 hours, 24 hours, 30 hours, and 36 hours, which is more conducive to further improving the drying effect of the product;

[0047] In a preferred embodiment, the calcination conditions of the preparation process of the present invention are 350°C, but not limited thereto; wherein the calcination conditions can be 200-600°C, and typical but non-limiting temperatures are, for example, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, and 600°C, which are more conducive to further improving the oxidation effect of the product.

[0048] Furthermore, the present invention also provides a novel agent, which is prepared by the novel agent preparation method as described above, which can achieve thallium removal and fluorine removal at different pH values.

[0049] The new agent prepared by the above preparation method can be used in the process of removing thallium and fluorine from wastewater.

[0050] The details are as follows:

[0051] When it is necessary to remove thallium from wastewater, the pH value of the wastewater is tested;

[0052] If the pH value of the wastewater is less than 5.5, the pH value of the wastewater is adjusted to 5.5-14, and the novel agent as described in any one of claims 1-5 is added to the wastewater;

[0053] When it is necessary to defluorinate the wastewater, test the pH value of the wastewater;

[0054] If the pH value of the wastewater is greater than 7, the pH value of the wastewater is adjusted to 1-7, and the novel agent as described in any one of claims 1-5 is added to the wastewater.

[0055] In this application, please refer to Figure 2 When the pH of thallium-containing wastewater is less than 5.5, the existence form and chemical properties of thallium are not conducive to its removal by the agent. Therefore, adjusting the pH to 5.5-14 can change the chemical form of thallium, making it easier to react with the active ingredients in the agent, thereby improving the efficiency of thallium removal.

[0056] Under overly acidic conditions, thallium can exist in the form of ions that are difficult to precipitate or adsorb. Adjusting the pH can cause thallium to form hydroxide precipitation or a form that is more easily adsorbed by pharmaceutical agents.

[0057] In alkaline environment (pH>7):

[0058] In an alkaline environment, the metal components (iron, aluminum, manganese, etc.) in the reagent will exist in the form of hydroxides, which have a large specific surface area and strong adsorption properties. Thallium ions can undergo adsorption exchange reactions with hydroxyl groups on the surface of hydroxides, and thallium can also form hydroxide precipitation (such as Tl(OH)3).

[0059] In an acidic environment (pH between 5.5 and 7):

[0060] The metal ions in the reagent will undergo redox reactions or ion exchange reactions with thallium ions. Under acidic conditions, although hydroxide precipitation is difficult to form, the metal ions in the reagent (such as Fe 3+ 、Al 3+ , Mn 2+ etc.) can undergo ion exchange adsorption with thallium ions, or oxidize thallium ions to a valence state that is easier to remove.

[0061] At the same time, since the agent is a specially prepared compound agent, there may be synergistic effects between its internal components, which work together to remove thallium in an acidic environment.

[0062] Please refer to Figure 3 When defluorination is required, in an alkaline environment, fluorine is mainly present in the form of F - When the pH is adjusted to the acidic range, as H + The increase in concentration, F - Will be with H + Combine to form hydrofluoric acid (HF). HF is a weak acid, part of which is F - After conversion to HF, the distribution of fluorine in the solution will change.

[0063] This form of fluorine is more likely to react with metal ions in the new agent. For example, hydrofluoric acid can react with Al 3+ The reaction generates fluorine-aluminum complexes. When the pH value of these complexes is within the range of 1-7, the concentration product of the complex ions in the solution exceeds its solubility product constant, causing it to precipitate, thereby achieving the purpose of fluorine removal. Specifically, the complex refers to a complex composed of a central atom or ion (such as Al 3+ ) and the ligands around it (such as F - ) are compounds formed by coordination bonds, such as fluorine-aluminum complexes (such as AlF3, AlF4 - 、AlF5 2- wait).

[0064] The defluorination mechanism of new agents in acidic environment is mainly based on the hydrolysis and precipitation reaction of metal ions. Taking aluminum salt as an example, under acidic conditions, Al 3+ It can hydrolyze to form various hydroxyaluminum ions, such as Al(OH) 2+ These hydroxyaluminum ions have positive charges and can attract negatively charged F - In alkaline environment, Al 3+ It is easy to form aluminum hydroxide precipitation, which reduces the effective Al2O3 3+ Therefore, in an alkaline environment, thallium ions can undergo adsorption exchange reaction with hydroxyl groups on the surface of hydroxide, and thallium can also form hydroxide precipitation.

[0065] Therefore, adjusting the pH to an acidic environment can allow aluminum salts to better exert their defluorination effect, and the same is true for iron salts and manganese.

[0066] The present invention is described below by means of specific examples.

[0067] Example 1

[0068] A novel agent capable of removing thallium and fluorine at different pH values, and its preparation and application, comprises the following steps:

[0069] Step 1: Determine the dosage of ferric chloride hexahydrate, aluminum chloride hexahydrate and manganese dioxide according to a molar ratio of 2:2:1;

[0070] Step 2: Add the weighed iron salt, aluminum salt and manganese compound to an appropriate amount of deionized water in sequence, stir and mix thoroughly to form solution A;

[0071] Step 3: Add 25-30% NaOH solution dropwise while stirring until the pH value of solution A reaches 10;

[0072] Step 4: Aging at room temperature for 24 hours;

[0073] Step 5: Take out the precipitate and place it in a constant temperature drying oven at 105°C for 24 hours to form a drug precursor;

[0074] Step 6: calcining the drug precursor in a muffle furnace at a temperature of 350° C. for 3 h;

[0075] Step 7: The product is cooled to room temperature to obtain a new drug.

[0076] Example 2

[0077] A novel agent capable of removing thallium and fluorine at different pH values, and its preparation and application, comprises the following steps:

[0078] Step 1: Determine the dosage of ferric chloride hexahydrate, aluminum chloride hexahydrate and manganese dioxide according to a molar ratio of 1:2:1;

[0079] Step 2: Add the weighed iron salt, aluminum salt and manganese compound to an appropriate amount of deionized water in sequence, stir and mix thoroughly to form solution A;

[0080] Step 3: Add 25-30% NaOH solution dropwise while stirring until the pH value of solution A reaches 10;

[0081] Step 4: Aging at room temperature for 24 hours;

[0082] Step 5: Take out the precipitate and place it in a constant temperature drying oven at 105°C for 24 hours to form a drug precursor;

[0083] Step 6: calcining the drug precursor in a muffle furnace at a temperature of 350° C. for 3 h;

[0084] Step 7: The product is cooled to room temperature to obtain a new drug.

[0085] Example 3

[0086] A novel agent capable of removing thallium and fluorine at different pH values, and its preparation and application, comprises the following steps:

[0087] According to a first aspect of the present invention, there is provided a novel agent capable of achieving thallium removal and fluoride removal at different pH values;

[0088] Step 1: Determine the dosage of ferric chloride hexahydrate, aluminum chloride hexahydrate and manganese dioxide according to a molar ratio of 2:1:1;

[0089] Step 2: Add the weighed iron salt, aluminum salt and manganese compound to an appropriate amount of deionized water in sequence, stir and mix thoroughly to form solution A;

[0090] Step 3: Add 25-30% NaOH solution dropwise while stirring until the pH value of solution A reaches 10;

[0091] Step 4: Aging at room temperature for 24 hours;

[0092] Step 5: Take out the precipitate and place it in a constant temperature drying oven at 105°C for 24 hours to form a drug precursor;

[0093] Step 6: calcining the drug precursor in a muffle furnace at a temperature of 350° C. for 3 h;

[0094] Step 7: The product is cooled to room temperature to obtain a new drug.

[0095] Comparative Example 1

[0096] Compared with Example 1, no manganese compound is added in this comparative example, which is a reagent containing only iron aluminum salt but no manganese compound. The remaining steps and process parameters are the same as those in Example 1.

[0097] Comparative Example 2

[0098] Compared with Example 1, this comparative example does not add aluminum salt, and is a reagent containing only iron salt and manganese compound but no aluminum salt. The remaining steps and process parameters are the same as those in Example 1.

[0099] Comparative Example 3

[0100] Compared with Example 1, this comparative example does not add iron salt, and is a reagent containing only aluminum salt and manganese compound but no iron salt. The remaining steps and process parameters are the same as those in Example 1.

[0101] 1.5g of the reagents prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were added to 100mL of 300μg / L thallium-containing leaching solution, and the pH value of the thallium-containing wastewater was detected at a rotation speed of 230r / min. If the pH of the thallium-containing wastewater was less than 5.5, the pH was adjusted to 5.5-14, stirred for 6h, and the supernatant was taken to detect the thallium concentration. The test results are shown in the following table:

[0102]

[0103]

[0104] 1.5g of the reagents prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were added to 100mL of fluorine-containing leaching solution with a concentration of 80mg / L. The pH value of the fluorine-containing wastewater was detected at a rotation speed of 230r / min. If the pH of the fluorine-containing wastewater was >7, the pH was adjusted to 1 to 7, stirred for 6h, and the supernatant was taken to detect the fluorine concentration. The test results are shown in the following table:

[0105] Test items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Fluoride removal rate% 81.25 67.28 52.98 66.08 20.49 78.90

[0106] In the present embodiment and comparative example, when the ratio of iron salt: aluminum salt: manganese compound (in molar ratio) = 2:2:1, the new agent has the best adsorption effect on thallium ions and fluoride ions in wastewater, and its performance is significantly higher than that of the bimetallic agents in comparative examples 1 to 3. It can be seen that the synergistic effect between the three components of iron salt, aluminum salt and manganese compound has extremely effectively promoted the improvement of the adsorption efficiency of thallium and fluorine, providing a more potential solution for the field of wastewater treatment.

[0107] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification and drawings under the concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for preparing a novel agent capable of removing thallium and fluorine at different pH values, characterized in that: The method for preparing the novel agent capable of achieving thallium removal and fluorine removal at different pH values ​​comprises: Step S1, adding weighed iron salt, aluminum salt and manganese compound to an appropriate amount of deionized water in sequence, stirring and mixing well to form solution A; Step S2, dripping 25-30% NaOH solution into solution A dropwise while stirring; Step S3, aging at room temperature for 18 to 30 hours; Step S4, taking out the precipitate and placing it in a constant temperature drying oven at 100-110° C. to dry for 12-36 hours to form a pharmaceutical precursor; Step S5, placing the drug precursor in a muffle furnace for calcination at a temperature of 200 to 600° C. for a calcination time of 2 to 4 hours; Step S6: The product is cooled to room temperature to obtain a novel agent, which can be added to water bodies within different pH ranges to achieve thallium removal and fluoride removal, respectively.

2. The method for preparing a novel agent capable of removing thallium and fluorine at different pH values ​​according to claim 1, characterized in that: The iron salts include ferric chloride hexahydrate, ferric nitrate nonahydrate, and ferric sulfate.

3. The method for preparing a novel agent capable of removing thallium and fluorine at different pH values ​​according to claim 1, characterized in that: The aluminum salts include aluminum chloride hexahydrate, aluminum nitrate nonahydrate, and aluminum sulfate.

4. The method for preparing a novel agent capable of removing thallium and fluorine at different pH values ​​according to claim 1, characterized in that: The manganese compounds include manganese dioxide, manganese chloride and manganese sulfate.

5. The method for preparing a novel agent capable of removing thallium and fluorine at different pH values ​​according to claim, characterized in that: The pH of solution A in step S2 is 5-12.

6. A novel drug, characterized in that: The novel agent is prepared by the preparation method of any one of claims 1 to 5, which can respectively remove thallium and fluorine at different pH values.

7. A method for treating wastewater, characterized in that: The wastewater treatment method comprises: When it is necessary to remove thallium from wastewater, the pH value of the wastewater is tested; If the pH value of the wastewater is less than 5.5, the pH value of the wastewater is adjusted to 5.5-14, and the new agent as described in 6 is added to the wastewater; When it is necessary to defluorinate the wastewater, test the pH value of the wastewater; If the pH value of the wastewater is greater than 7, the pH value of the wastewater is adjusted to 1-7, and the new agent as described in 6 is added to the wastewater.

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