A composite material for water pollution control

Abstract

The present application relates to sewage treatment technical field, specifically for a kind of composite material for water pollution treatment, including traditional Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube, basic oxide and binder, the weight ratio of traditional Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube, basic oxide and binder is 10-30:1-5:0.5-2.5:3-6, the composite material prepared in the present application can effectively reduce the content of toxic heavy metal ions in acidic wastewater, improve pH value, and the treatment effect is remarkable and efficient.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, in particular to a composite material for water pollution treatment. BACKGROUND

[0002] The acidic wastewater discharged by factories is a kind of industrial wastewater with low pH, high concentration and rich in toxic heavy metal elements, which can cause soil acidification, plant death and groundwater pollution if not treated in time.

[0003] Ion adsorption method is currently recognized as a relatively economical method for treating acidic wastewater, which has the advantages of multiple types of adsorbents and wide sources. Currently, the commonly used adsorbents are porous solid composite materials, including biochar, zeolite, diatomite, coal ash powder, chitosan and aluminum oxide, etc. However, the treatment efficiency of single adsorbent is low, and the adsorption effect is difficult to meet the requirements. SUMMARY

[0004] The present application provides a composite material for water pollution treatment.

[0005] The technical scheme adopted is as follows:

[0006] The composite material for water pollution treatment comprises traditional Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotubes, basic oxides and a binder.

[0007] Further, the weight ratio of the traditional Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotubes, basic oxides and binder is 10-30:1-5:0.5-2.5:3-6.

[0008] Further, the preparation method of the traditional Chinese medicine residue-based activated carbon is as follows:

[0009] After drying the traditional Chinese medicine residue, mix and crush it with Zn-MOFs into powder, pre-carbonize the powder at 450-550 DEG C for 1-3 hours, then recover to room temperature, soak in dilute hydrochloric acid, dry, and then carbonize at 800-900 DEG C for 1-3 hours, and recover to room temperature.

[0010] Further, the weight ratio of the dried traditional Chinese medicine residue and Zn-MOFs is 5-10:1.

[0011] Further, the speed of the first temperature rise is 1-10 DEG C / min, and the speed of the second temperature rise is 1-10 DEG C / min.

[0012] Further, the preparation method of the ionic liquid modified titanate nanotubes is as follows:

[0013] The titanate nanotube is mixed with the ionic liquid, and then is ball milled for more than 5 hours with acetone as the ball milling medium.

[0014] Further, the weight ratio of the titanate nanotube to the ionic liquid is 1:5-10.

[0015] Further, the ionic liquid is an imidazole ionic liquid, and the anion of the imidazole ionic liquid is a tetrafluoroborate ion or a hexafluorophosphate ion.

[0016] Further, the basic oxide is any one or a combination of sodium oxide, calcium oxide, potassium oxide, magnesium oxide, ferrous oxide, copper oxide, barium oxide, and aluminum oxide.

[0017] Further, the binder is any one or a combination of coal tar, honey, starch, sodium carboxymethyl cellulose, and polyacrylamide.

[0018] The present application has the following beneficial effects:

[0019] The present application provides a composite material for water pollution treatment, a bio-based material is a common raw material for preparing activated carbon, and traditional Chinese medicine residues are waste in the process of medicine production, which will cause environmental problems if directly discarded or incinerated, and the traditional Chinese medicine residues can be used as raw materials for producing activated carbon, so that the traditional Chinese medicine residues can be recycled, Zn-MOFs has a special porous structure, and can be carbonized and maintain a regular network pore structure and unique morphology to a certain extent, during pre-carbonization, zinc ions are oxidized into zinc oxide, and part of the zinc oxide is reduced by carbon, during the soaking in dilute hydrochloric acid, the zinc oxide and zinc react with the dilute hydrochloric acid to generate zinc chloride, the zinc chloride is doped in the activated carbon, and the activated carbon is activated during secondary high-temperature carbonization to increase the specific surface area and pore volume of the activated carbon, so that the activated carbon has better adsorption treatment performance.

[0020] The titanate nanotube has a large specific surface area and excellent ion exchange performance, and exhibits high adsorption performance on toxic heavy metal ions, and after being combined with the traditional Chinese medicine residue-based activated carbon, the composite material can improve the adsorption treatment effect on acidic wastewater, and can also serve as a nano skeleton to improve the mechanical strength of the composite material, prevent the composite material from being broken due to external force or mutual extrusion during transportation and storage, and the anionic acidic groups introduced on the surface of the titanate nanotube after ionic liquid modification are more conducive to the adsorption of toxic heavy metal cations, and the removal effect of the heavy metal ions is improved.

[0021] The basic oxide can be neutralized with the acid sewage to increase the pH of the acid sewage, and as the basic oxide is consumed, more and more pores are formed in the composite material, further improving the adsorption and removal effect of heavy metal ions.

[0022] The composite material prepared in the application can effectively reduce the content of toxic heavy metal ions in the acid sewage and increase the pH value, and the treatment effect is remarkable and efficient. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 A real photo of the composite material prepared in Example 1. DETAILED DESCRIPTION

[0024] Unless otherwise specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. Unless otherwise specified, the reagents or instruments used are conventional products that can be purchased on the market. The techniques not mentioned in the application refer to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel tests, and the same treatment steps and parameters are used. Example 1

[0025] A composite material for water pollution treatment, comprising traditional Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotubes, calcium oxide and coal tar at a weight ratio of 25:2.5:1:5.

[0026] The preparation method of the traditional Chinese medicine residue-based activated carbon is as follows:

[0027] After drying the traditional Chinese medicine residue at a weight ratio of 8:1, it is uniformly mixed with Zn-MOF-10 (Xi'an Rixi Biology) and crushed into powder. The powder is placed in a high-temperature tube furnace and heated to 520 DEG C at a rate of 10 DEG C / min for 2h, and then cooled to room temperature. After being soaked in 1 mol / L dilute hydrochloric acid for 24h, it is filtered and dried. Then, it is heated to 880 DEG C at a rate of 2 DEG C / min for 2h, and then cooled to room temperature.

[0028] The preparation method of the ionic liquid modified titanate nanotubes is as follows:

[0029] After the 2.5g titanium dioxide and 200ml 10mol / L sodium hydroxide solution are uniformly mixed, hydrothermal reaction is carried out in a polytetrafluoroethylene container at 120 DEG C for 48h. The product is adjusted to pH 1 with 0.1mol / L hydrochloric acid, stirred for 30 min, and the precipitate is filtered and washed with deionized water and dried to obtain titanate nanotubes. The titanate nanotubes and 1-butyl-3-vinylimidazole tetrafluoroborate are mixed at a weight ratio of 1:6, and then ball milled with a ball mill, with acetone as the ball milling medium and the ball mill rotating at 200r / min. After 8h of ball milling, the obtained mixture is dried.

[0030] The preparation method of the composite material is as follows:

[0031] First, the Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube and calcium oxide are uniformly mixed, then the coal tar is added, and after being fully kneaded, the composite material is formed by pressing on a pressure forming machine at a pressure of 100 MPa. Example 2

[0032] A composite material for water pollution treatment, comprising Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube, calcium oxide and coal tar in a weight ratio of 30:5:2.5:6.

[0033] The preparation method of the Chinese medicine residue-based activated carbon and the ionic liquid modified titanate nanotube is the same as that in Example 1.

[0034] The preparation method of the composite material is as follows:

[0035] First, the Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube and calcium oxide are uniformly mixed, then the coal tar is added, and after being fully kneaded, the composite material is formed by pressing on a pressure forming machine at a pressure of 100 MPa. Example 3

[0036] A composite material for water pollution treatment, comprising Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube, calcium oxide and coal tar in a weight ratio of 10:1:1:4.

[0037] The preparation method of the Chinese medicine residue-based activated carbon and the ionic liquid modified titanate nanotube is the same as that in Example 1.

[0038] The preparation method of the composite material is as follows:

[0039] First, the Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube and calcium oxide are uniformly mixed, then the coal tar is added, and after being fully kneaded, the composite material is formed by pressing on a pressure forming machine at a pressure of 100 MPa. Example 4

[0040] A composite material for water pollution treatment, comprising Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotube, calcium oxide and coal tar in a weight ratio of 15:2:2:5.

[0041] The preparation method of the Chinese medicine residue-based activated carbon and the ionic liquid modified titanate nanotube is the same as that in Example 1.

[0042] The preparation method of the composite material is as follows:

[0043] The Chinese medicine residue-based activated carbon, the ionic liquid modified titanate nanotube and calcium oxide are mixed uniformly, then the coal tar is added, and after being fully kneaded, the mixture is pressed into a shape on a pressure forming machine at a pressure of 100 MPa.

[0044] Comparative Example 1: substantially the same as Example 1, except that the Chinese medicine residue-based activated carbon is prepared without adding Zn-MOF-10.

[0045] Comparative Example 2: substantially the same as Example 1, except that the ionic liquid modified titanate nanotube is not added.

[0046] Comparative Example 3: substantially the same as Example 1, except that the titanate nanotube is not modified by an ionic liquid.

[0047] Performance test: the composite materials prepared in Examples 1-4 and Comparative Examples 1-3 of the application are respectively used as samples;

[0048] The test water sample is simulated acidic wastewater, the pH value is adjusted to 4.0, and the concentrations of Pb 2+ , Ni 2+ , Cd 2+ and Mn 2+ are all 40 mg / L, 1 g of the sample is added into 250 ml of the test water sample, and the adsorption is carried out at room temperature under the condition of 150 r / min for 180 min, then the residual concentration values of Pb 2+ , Ni 2+ , Cd 2+ and Mn 2+ in the test water sample are determined, the removal rate is calculated, and the pH value change of the simulated water sample is measured.

[0049] The test results are shown in Table 1:

[0050] Table 1:

[0051] ;

[0052] As shown in Table 1, the composite material prepared in the application can effectively reduce the content of toxic heavy metal ions in acidic wastewater, increase the pH value, and has a remarkable and efficient treatment effect.

[0053] The above examples are only used to illustrate the technical solutions of the application, but not limit the application; although the application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.

Claims

1. A composite material for water pollution remediation, characterized by, The base material comprises Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotubes, alkaline oxide and binder; The weight ratio of the Chinese medicine residue-based activated carbon, ionic liquid modified titanate nanotubes, alkaline oxide and binder is 10-30:1-5:0.5-2.5:3-6; The preparation method of the Chinese medicine residue-based activated carbon is as follows: After drying the Chinese medicine residue, mix it with Zn-MOFs, crush into powder, pre-carbonize at 450-550℃ for 1-3h, recover room temperature, soak in dilute hydrochloric acid, dry, carbonize at 800-900℃ for 1-3h, recover room temperature, and then it is ready; The preparation method of the ionic liquid modified titanate nanotubes is as follows: Mix the titanate nanotubes with ionic liquid, use acetone as ball milling medium, grind for more than 5h, dry the obtained mixture after grinding, and then it is ready. The ionic liquid is imidazole ionic liquid, and the anion of the imidazole ionic liquid is tetrafluoroborate ion or hexafluorophosphate ion.

2. The composite material for water pollution treatment according to claim 1, wherein, The weight ratio of the dried Chinese medicine residue and Zn-MOFs is 5-10:

1.

3. The composite material for water pollution treatment according to claim 1, wherein The speed of the first temperature rising is 1-10℃ / min, and the speed of the second temperature rising is 1-10℃ / min.

4. The composite material for water pollution treatment according to claim 1, wherein The weight ratio of the titanate nanotubes and ionic liquid is 1:5-10.

5. The composite material for water pollution treatment according to claim 1, wherein The alkaline oxide is any one or combination of multiple of sodium oxide, calcium oxide, potassium oxide, magnesium oxide, ferrous oxide, copper oxide, barium oxide and aluminum oxide.

6. The composite material for water pollution treatment according to claim 1, wherein The binder is any one or combination of multiple of coal tar, honey, starch, sodium carboxymethyl cellulose and polyacrylamide.

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