Titanium gel coagulant, composite titanium salt coagulant, preparation method and application

Abstract

The application belongs to the technical field of coagulants, and discloses a titanium gel coagulant, a composite titanium salt coagulant, a preparation method and application. The titanium gel coagulant is a mixture of TiCl4-ethanol-acetylacetone-water, and the composite titanium salt coagulant is a composite preparation of the titanium gel coagulant and a coagulant aid. The titanium gel coagulant and the composite titanium salt coagulant have the characteristics of low material price, simple synthesis, good turbidity removal effect and the like. In addition, the titanium gel coagulant and the composite titanium salt coagulant not only enrich the research content of coagulants, but also provide a new technical selection for the water treatment field, and have stable properties and can be stored for a long time.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coagulants, in particular to a titanium gel coagulant, a composite titanium salt coagulant, a preparation method and application. BACKGROUND

[0002] Coagulation process plays a crucial role in water treatment, and its effect is significantly influenced by the type of coagulant and the water environment. Although traditional inorganic coagulants, such as aluminum salts and iron salts, are widely used due to their extensive application, they also have some significant shortcomings in practical use. First, the aggregation speed of traditional inorganic coagulants is slow, resulting in small volume of formed flocs, thereby reducing the treatment efficiency. Second, aluminum salt coagulants have a greater impact on the pH value of water, often requiring additional pH adjustment measures to ensure optimal purification effect. Third, the use of these inorganic coagulants produces a large amount of sludge, increasing the difficulty and cost of subsequent sludge treatment.

[0003] With the continuous improvement of effluent water quality standards, the shortcomings of these traditional coagulants become increasingly prominent, therefore, it is imperative to develop new and efficient coagulants. Compared with traditional aluminum salt and iron salt coagulants, titanium gel coagulant has the advantages of low cost, good performance, advantages in sludge treatment, environmental protection and health, etc. These advantages make titanium gel coagulant have broad application prospects in the field of water treatment. Among them, titanium gel coagulant (TXC) as a new coagulant has many advantages. Therefore, how to provide a titanium gel coagulant, a composite titanium salt coagulant, a preparation method and application is a problem to be solved at present. SUMMARY

[0004] The embodiments of the present application provide a titanium gel coagulant, a composite titanium salt coagulant, a preparation method and application to solve the above technical problems in the prior art.

[0005] To have a basic understanding of some aspects of the disclosed embodiments, a brief summary is given below. This summary is not a general overview, nor is it intended to determine key / important elements or delineate the scope of these embodiments. Its only purpose is to present some concepts in a simple form as a prelude to the detailed description that follows.

[0006] According to a first aspect of the embodiments of the present application, a titanium gel coagulant is provided.

[0007] In one embodiment, the titanium gel coagulant is a mixture of TiCl4-ethanol-acetylacetone-water, wherein the molar ratio of acetylacetone to TiCl4 is any one of 1:2, 1:4 or 1:16, the water is ultrapure water, and the molar ratio of ultrapure water to TiCl4 is any one of 8:1, 4:1 or 2:1.

[0008] In one embodiment, the method for preparing the titanium gel coagulant comprises:

[0009] Step one, drop TiCl4 into the mixed solution of ethanol and acetylacetone, and mix well at room temperature with a magnetic stirrer to obtain a mixed solution of TiCl4-ethanol-acetylacetone;

[0010] Step two, drop the mixed solution of ethanol and ultrapure water into the mixed solution of TiCl4-ethanol-acetylacetone, and continuously stir to obtain a light yellow and uniform sol;

[0011] Step three, dry the sol in a constant temperature dryer until the sol becomes a gel with constant weight to obtain a titanium gel coagulant.

[0012] In one embodiment, the molar ratio of acetylacetone to TiCl4 in step one is any one of 1:2, 1:4 or 1:16.

[0013] In one embodiment, the molar ratio of ultrapure water to TiCl4 in step two is any one of 8:1, 4:1 or 2:1.

[0014] In one embodiment, the time for continuous stirring in step two is 90 min.

[0015] In one embodiment, the drying temperature of the constant temperature dryer in step three is 50°C.

[0016] In one embodiment, the titanium gel coagulant or the titanium gel coagulant prepared by the method for preparing the titanium gel coagulant is applied in high turbidity wastewater treatment.

[0017] According to a second aspect of the embodiments of the present application, a composite titanium salt coagulant is provided.

[0018] In one embodiment, the composite titanium salt coagulant is composed of the above-mentioned titanium gel coagulant and a single coagulant aid.

[0019] In one embodiment, the single coagulant aid includes any one of cationic PAM, anionic PAM, non-ionic PAM, GS-A6 or CTAB.

[0020] In one embodiment, the method for preparing the composite titanium salt coagulant comprises compounding and mixing the titanium gel coagulant with the single coagulant aid to obtain the composite titanium salt coagulant.

[0021] In one embodiment, the concentration ratio between the titanium gel coagulant and the single coagulant aid in the composite titanium salt coagulant is 10:1.

[0022] In one embodiment, the application provides a use of the composite titanium salt coagulant or the composite titanium salt coagulant prepared by the method for treating high-turbidity wastewater.

[0023] According to a third aspect of the embodiments of the present application, a composite titanium salt coagulant is provided.

[0024] In one embodiment, the composite titanium salt coagulant is composed of the titanium gel coagulant and a plurality of coagulant aids.

[0025] In one embodiment, the plurality of coagulant aids includes at least two of cationic PAM, anionic PAM, non-ionic PAM, GS-A6 or CTAB.

[0026] In one embodiment, the method for preparing the composite titanium salt coagulant includes compounding the titanium gel coagulant with a plurality of coagulant aids to obtain the composite titanium salt coagulant.

[0027] In one embodiment, the application provides a use of the composite titanium salt coagulant or the composite titanium salt coagulant prepared by the method for treating high-turbidity wastewater.

[0028] The technical solutions provided by the embodiments of the present application can have the following beneficial effects:

[0029] The titanium gel coagulant is synthesized by a sol-gel method, and the titanium gel coagulant with the best coagulation performance can be obtained by adjusting the molar ratio of acetylacetone, titanium tetrachloride (TiCl4), ethanol and water and optimizing the preparation conditions. On this basis, the titanium gel coagulant with the best performance is selected and compounded with a plurality of coagulant aids (including cationic PAM, anionic PAM, non-ionic PAM, GS-A6 and CTAB) to explore the coagulation effect under different compounding conditions, so that a composite titanium salt coagulant with better performance can be obtained. In summary, the titanium gel coagulant and the composite titanium salt coagulant are prepared by the sol-gel method, which not only enriches the research content of coagulants, but also provides a new technical choice for the field of water treatment. In the future, with the deepening of research and the improvement of technology, the titanium gel coagulant is expected to play a more important role in the field of water treatment.

[0030] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present application. BRIEF DESCRIPTION OF DRAWINGS

[0031] The accompanying drawings, which are incorporated into and form part of the specification, illustrate embodiments consistent with the present application and, together with the specification, serve to explain the principles of the application.

[0032] Figure 1 is a flow chart of a method for preparing a titanium gel coagulant according to an exemplary embodiment;

[0033] Figure 2 is a comparison chart of turbidity removal rates of different ratios of titanium gel coagulants (0, 20, 40, 60, 80, 100 mg / L) according to an exemplary embodiment;

[0034] Figure 3 is a comparison chart of turbidity removal rates of different ratios of composite titanium salt coagulants (using a single coagulant aid) according to an exemplary embodiment;

[0035] Figure 4 is a comparison chart of turbidity removal rates of different ratios of composite titanium salt coagulants (using multiple coagulant aids) according to an exemplary embodiment. DETAILED DESCRIPTION

[0036] The following description and drawings are illustrative of the specific embodiments herein and are not intended to be limiting. Parts and features of some embodiments can be included or replaced by parts and features of other embodiments. The scope of the embodiments herein includes the whole scope of the claims and all available equivalents of the claims. In this document, the terms "first", "second", etc. are used merely to distinguish one element from another and do not require or imply any actual relationship or order between the elements. In fact, the first element could be named the second element and vice versa without changing the meaning of direct dependence based on the context in which these terms are used. Also, the terms "comprises", "comprising", or any other variations thereof are intended to cover a non-exclusive inclusion, such that a structure, device, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such structure, device, or apparatus. An element proceeded by "comprises... a" does not, without more constraints, exclude the existence of additional identical elements in the structure, device, or apparatus that includes the element. The embodiments are described in a progressive manner, each emphasizing the differences from other embodiments, and the same or similar parts between embodiments are cross-referenced.

[0037] In this document, the term "plurality" means two or more, unless otherwise specified.

[0038] In this document, the character " / " means that the objects before and after it are in an "or" relationship. For example, A / B means A or B.

[0039] Herein, the term “and / or” is a descriptive term that describes a relationship between objects, indicating that three relationships can exist. For example, A and / or B indicates that three relationships of A or B, or A and B can exist.

[0040] It should be understood that, although the steps in the flowchart are shown in a sequential order following the arrows, the steps are not necessarily executed in the order indicated by the arrows. Unless otherwise explicitly stated herein, the execution of the steps is not strictly limited in order, and the steps can be executed in other orders. Moreover, at least a part of the steps in the figure can include multiple sub-steps or multiple stages, which are not necessarily executed at the same time, but can be executed at different times, and the execution order of the sub-steps or stages is not necessarily sequential, but can be alternately or alternately executed with at least a part of other steps or sub-steps or stages of other steps.

[0041] In the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0042] Figure 1 A method for preparing a titanium gel coagulant is shown.

[0043] In this optional embodiment, the method for preparing a titanium gel coagulant comprises:

[0044] Step S101, TiCl4 (3.1 mL) is added dropwise to a mixed solution of ethanol (20 mL) and acetylacetone (the molar ratio of acetylacetone / TiCl4 is 1 / 16, 1 / 4, 1 / 2), and the mixed solution of TiCl4-ethanol-acetylacetone is fully mixed at room temperature by using a magnetic stirrer; Step S103, a mixed solution of ethanol and ultrapure water (the molar ratio of TiCl4 / ultrapure water is 1 / 8, 1 / 4, 1 / 2) is added dropwise to the mixed solution of TiCl4-ethanol-acetylacetone, and the mixed solution is continuously stirred for 90 minutes to obtain a light yellow and uniform sol; Step S105, the sol is placed in a 50℃ constant temperature dryer for drying until the sol becomes a gel with a constant weight, to obtain a titanium gel coagulant.

[0045] The present application also provides the use of the titanium gel coagulant and the composite titanium salt coagulant compounded with different coagulants (including cationic PAM, anionic PAM, non-ionic PAM, GS-A6 and CTAB) in different proportions for removing turbidity of sewage.

[0046] The titanium gel coagulant and the composite titanium salt coagulant of the present application have the advantages of simple preparation and can quickly and efficiently remove turbidity.

[0047] In order to facilitate the understanding of the above technical solutions of the present application, the present application will be explained in more detail below through the following examples. The following examples are only illustrative, and it should be understood that the present application is not limited by the following examples.

[0048] Example 1

[0049] (Scheme 1) The ratio of titanium gel coagulant No. 1 is: acetylacetone / TiCl4=1 / 16, ultrapure water / TiCl4=8 / 1. When different concentrations of No. 1 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 84.7%-91.1%.

[0050] (Scheme 2) The ratio of titanium gel coagulant No. 2 is: acetylacetone / TiCl4=1 / 16, ultrapure water / TiCl4=4 / 1. When different concentrations of No. 2 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 87.9%-94.6%.

[0051] (Scheme 3) The ratio of titanium gel coagulant No. 3 is: acetylacetone / TiCl4=1 / 16, ultrapure water / TiCl4=2 / 1. When different concentrations of No. 3 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 91.6%-97.3%.

[0052] (Scheme 4) The ratio of titanium gel coagulant No. 4 is: acetylacetone / TiCl4=1 / 4, ultrapure water / TiCl4=8 / 1. When different concentrations of No. 4 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 86.8%-92.2%.

[0053] (Scheme 5) The ratio of titanium gel coagulant No. 5 is: acetylacetone / TiCl4=1 / 4, ultrapure water / TiCl4=4 / 1. When different concentrations of No. 5 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 96.4%-99.4%.

[0054] (Scheme 6) The ratio of titanium gel coagulant No. 6 is: acetylacetone / TiCl4=1 / 4, ultrapure water / TiCl4=2 / 1. When different concentrations of No. 6 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 96.7%-99.6%.

[0055] (Recipe 7) The ratio of titanium gel coagulant No. 7 is: acetylacetone / TiCl4 = 1 / 2, ultrapure water / TiCl4 = 8 / 1. When different concentrations of No. 7 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 93.0%-96.6%.

[0056] (Recipe 8) The ratio of titanium gel coagulant No. 8 is: acetylacetone / TiCl4 = 1 / 2, ultrapure water / TiCl4 = 4 / 1. When different concentrations of No. 8 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 99.0%-99.5%.

[0057] (Recipe 9) The ratio of titanium gel coagulant No. 9 is: acetylacetone / TiCl4 = 1 / 2, ultrapure water / TiCl4 = 2 / 1. When different concentrations of No. 9 titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are added to turbid water, the turbidity removal rate is 98.1%-99.4%.

[0058] Figure 2 The turbidity removal rates of different ratios of titanium gel coagulant (0, 20, 40, 60, 80, 100 mg / L) are compared. From the figure Figure 2 It can be clearly seen that when the titanium gel coagulant is added, the turbidity removal rate of No. 8 ratio of titanium gel coagulant can be maintained at 99% and above, compared with other ratios, No. 8 ratio of titanium gel coagulant has better and stable performance, which can provide a new treatment method for turbidity removal.

[0059] Example 2

[0060] (Recipe 1) The ratio of composite titanium salt coagulant No. 1 is: No. 8 ratio of titanium gel coagulant (10 mg / L), cationic PAM (0.2, 0.4, 0.6, 0.8, 1.0, 1.2 mg / L). When No. 1 composite titanium salt coagulant is added to turbid water, the turbidity removal rate is 95.70%-99.89%.

[0061] (Recipe 2) The ratio of composite titanium salt coagulant No. 2 is: No. 8 ratio of titanium gel coagulant (10 mg / L), anionic PAM (0.2, 0.4, 0.6, 0.8, 1.0, 1.2 mg / L). When No. 2 composite titanium salt coagulant is added to turbid water, the turbidity removal rate is 98.85%-99.68%.

[0062] (Example 3) The ratio of the composite titanium salt coagulant No. 3 is: the titanium gel coagulant No. 8 (10 mg / L), and the non-ionic PAM (0.2, 0.4, 0.6, 0.8, 1.0, 1.2 mg / L). When the composite titanium salt coagulant No. 3 is added to the turbid water, the turbidity removal rate is 99.30%-99.89%.

[0063] (Example 4) The ratio of the composite titanium salt coagulant No. 4 is: the titanium gel coagulant No. 8 (10 mg / L), and CTAB (0.2, 0.4, 0.6, 0.8, 1.0, 1.2 mg / L). When the composite titanium salt coagulant No. 4 is added to the turbid water, the turbidity removal rate is 98.42%-99.32%.

[0064] (Example 5) The ratio of the composite titanium salt coagulant No. 5 is: the titanium gel coagulant No. 8 (10 mg / L), and GS-A6 (0.2, 0.4, 0.6, 0.8, 1.0, 1.2 mg / L). When the composite titanium salt coagulant No. 5 is added to the turbid water, the turbidity removal rate is 99.28%-99.74%.

[0065] Figure 3 The turbidity removal rates of different concentrations of the composite titanium salt coagulant (using a single coagulant aid) are compared. Figure 3 It can be clearly seen that, after the composite titanium salt coagulant is added, the turbidity removal rate of the composite titanium salt coagulant No. 3 (10 mg / L of the titanium gel coagulant No. 8 compounded with different concentrations of the non-ionic PAM) can be maintained at 99% or above, and the turbidity removal rate of the composite titanium salt coagulant using 10 mg / L of the titanium gel coagulant No. 8 compounded with 1.0 mg / L of the non-ionic PAM can reach 99.89%. Compared with other composite titanium salt coagulants, the composite titanium salt coagulant No. 3 has better performance and more stable turbidity removal effect, which can provide a new treatment scheme for turbidity removal.

[0066] Example 3

[0067] (Example 1) The ratio of the composite titanium salt coagulant No. 6 is: the titanium gel coagulant No. 8 (10 mg / L), the non-ionic PAM (1.0 mg / L), and CTAB (0.2 mg / L). When the composite titanium salt coagulant No. 6 is added to the turbid water, the turbidity removal rate is 99.65%.

[0068] (Example 2) The ratio of the composite titanium salt coagulant No. 7 is: the titanium gel coagulant No. 8 (10 mg / L), the non-ionic PAM (1.0 mg / L), and GS-A6 (0.6 mg / L). When the composite titanium salt coagulant No. 7 is added to the turbid water, the turbidity removal rate is 99.67%.

[0069] (Example 3) The ratio of the composite titanium salt coagulant No. 8 is: titanium gel coagulant No. 8 (10 mg / L), CTAB (0.2 mg / L), GS-A6 (0.6 mg / L). When the composite titanium salt coagulant No. 8 is added to the turbid water, the turbidity removal rate is 99.74%.

[0070] (Example 4) The ratio of the composite titanium salt coagulant No. 9 is: titanium gel coagulant No. 8 (10 mg / L), non-ionic PAM (1.0 mg / L), CTAB (0.2 mg / L), GS-A6 (0.6 mg / L). When the composite titanium salt coagulant No. 9 is added to the turbid water, the turbidity removal rate is 99.82%.

[0071] Figure 4 is the turbidity removal rate of different composite titanium salt coagulants (using various coagulants) for comparison. From Figure 4 It can be clearly seen that when the composite titanium salt coagulant is added, the turbidity removal rate of the composite titanium salt coagulant No. 9 (10 mg / L titanium gel coagulant No. 8, 1.0 mg / L non-ionic PAM, 0.2 mg / L CTAB, and 0.6 mg / L GS-A6) is the best, which can reach 99.82%. Compared with other composite titanium salt coagulants (using various coagulants), the composite titanium salt coagulant No. 9 has better performance, which can provide a new treatment method for turbidity removal.

[0072] The present application is not limited to the structures already described above and shown in the drawings, and various modifications and changes can be made without departing from the scope thereof. The scope of the present application is limited only by the appended claims.

Claims

1. A composite titanium salt coagulant, characterized by, The composite titanium salt coagulant is composed of a titanium gel coagulant and a GS-A6 single coagulant aid, and the concentration ratio of the titanium gel coagulant to the GS-A6 single coagulant aid ranges from 8.33 to 50. The titanium gel coagulant is a mixture of TiCl4-ethanol-acetylacetone-water, wherein the molar ratio of acetylacetone to TiCl4 is any one of 1:2, 1:4 or 1:16, the water is ultrapure water, and the molar ratio of the ultrapure water to TiCl4 is any one of 8:1, 4:1 or 2:

1.

2. The composite titanium salt coagulant according to claim 1, characterized in that, The preparation of the titanium gel coagulant comprises: Step one, drop TiCl4 into a mixed solution of ethanol and acetylacetone, and fully mix with a magnetic stirrer at room temperature to obtain a mixed solution of TiCl4-ethanol-acetylacetone; Step two, drop a mixed solution of ethanol and ultrapure water into the mixed solution of TiCl4-ethanol-acetylacetone, and continuously stir to obtain a light yellow and uniform sol; Step three, dry the sol in a constant temperature dryer until the sol becomes a gel with a constant weight to obtain the titanium gel coagulant.

3. The composite titanium salt coagulant according to claim 2, characterized in that, In step one, the molar ratio of acetylacetone to TiCl4 is any one of 1:2, 1:4 or 1:

16.

4. The composite titanium salt coagulant according to claim 2, characterized in that, In step two, the molar ratio of the ultrapure water to TiCl4 is any one of 8:1, 4:1 or 2:

1.

5. The composite titanium salt coagulant according to claim 2, characterized in that, In step two, the time of continuous stirring is 90 min.

6. The composite titanium salt coagulant according to claim 2, characterized in that, In step three, the drying temperature of the constant temperature dryer is 50℃.

7. A method of preparing the composite titanium salt coagulant as claimed in claim 1, characterized by, The composite titanium salt coagulant is obtained by compounding and mixing the titanium gel coagulant and the GS-A6 single coagulant aid.

8. The application of the composite titanium salt coagulant of claim 1 or the composite titanium salt coagulant prepared by the method of claim 7 in high-turbidity wastewater treatment.

9. A composite titanium salt coagulant, characterized by, The composite titanium salt coagulant is composed of the titanium gel coagulant and a plurality of coagulant aids as described in claim 1, wherein the plurality of coagulant aids at least includes the GS-A6 single coagulant aid.

10. The composite titanium salt coagulant according to claim 9, characterized in that, The plurality of coagulant aids further includes at least one of a cationic PAM, an anionic PAM, a non-ionic PAM or CTAB.

11. A method of preparing the composite titanium salt coagulant according to claim 9, characterized by, The composite titanium salt coagulant is obtained by compounding and mixing the titanium gel coagulant and the plurality of coagulant aids.

12. The application of the composite titanium salt coagulant of claim 9 or the composite titanium salt coagulant prepared by the method of claim 11 in high-turbidity wastewater treatment.

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