CN110066009B - Tourmaline containing anthraquinone compound, preparation method and application - Google Patents
Tourmaline containing anthraquinone compound, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the field of water treatment, in particular to the field of treatment of wastewater containing pollutants, and relates to tourmaline containing anthraquinone compounds, a preparation method and application thereof. According to the invention, chloropropyl silane coupling agent reacts with tourmaline to obtain chloropropyl modified tourmaline, and then the chloropropyl modified tourmaline reacts with anthraquinone compound containing amino group under the action of acid-binding agent to remove hydrogen chloride to obtain tourmaline with anthraquinone compound contained on the surface. The tourmaline with anthraquinone compound on the surface can obviously accelerate the biological reduction process of azo dyes and nitrates, can be repeatedly used, has wide raw material source, less reaction steps and low cost, and can be widely used in wastewater treatment.
Description
Technical Field
The invention relates to the field of water treatment engineering, in particular to tourmaline containing anthraquinone compounds, a preparation method and application.
Background
With the development of society and economy, the population is growing continuously, the requirements of people on industrial and agricultural products are higher and higher, and more, so a large amount of chemical substances are synthesized by artificial means, and a lot of waste water containing heavy metals and pollutants which are difficult to biodegrade is discharged into the environments of animals, plants and human beings, and finally, serious harm is caused to the human health and the whole ecological circle of the nature. For example, azo dyes have become the most widely used synthetic dyes with the largest usage in printing and dyeing processes for textile and clothing due to the characteristics of simple synthetic process, low cost, outstanding dyeing performance and the like. Under special conditions, it can decompose to produce more than 20 carcinogenic aromatic amines, which can change the DNA structure of human body through activation to cause pathological changes and induce cancer. About 10-15% of the dye is lost to the printing waste water during the printing process, and the discharge of the printing waste water causes serious damage to the receiving water body, including azo dyes.
Nitrates are another class of chemicals that are highly harmful to humans and the environment. Ammonia nitrogen and nitro nitrogen contained in excessively applied fertilizers, domestic sewage, excrement, industrial sewage and the like enter the natural environment through soil, water bodies and the like, and are one of main substances for causing water body eutrophication. The conventional biochemical treatment process can only convert ammonia nitrogen into nitrate nitrogen generally, and the reduction of the nitrate nitrogen cannot be efficiently completed in the general treatment process because the denitrification efficiency is low.
Therefore, the treatment of such waste water is increasingly gaining attention, and the main treatment methods are chemical methods and biological methods. The biological method has better application prospect, especially the anaerobic-aerobic process is the most effective and widely used method for treating the wastewater, and the emphasis on how to improve the speed of reducing the dye and nitrate radical by the microorganism is always on the process.
Researchers find that the redox mediator containing the quinone group can effectively accelerate the biotransformation process of azo dyes, nitrates and the like and improve the degradation rate. The redox mediator containing quinone group has relatively low molecular weight, and may be added directly into water treating system to result in secondary pollution and high continuous feeding cost. The redox mediator containing quinone group is fixed on a physical carrier insoluble in water, so that the method is a feasible industrial method, has the advantage of repeated utilization, is not easy to lose, and avoids secondary pollution.
The invention patent of China granted under the grant publication number CN101862680B discloses a preparation method of a porous inorganic filler fixed quinone compound, which effectively improves the degradation rate of azo dyes. Plating gamma-alumina on the surface of the porous inorganic filler, treating the porous inorganic filler by using 3-amino triethoxysilane to ensure that the surface of the porous inorganic filler contains primary amino, and reacting the primary amino with an anthraquinone compound containing sulfonyl chloride groups to obtain the porous inorganic filler containing quinonyl on the surface. This method has the following problems: (1) the reaction steps are long, the time consumption is long, the final yield is low, and the cost is high; (2) the anthraquinone compound containing sulfonyl chloride group is easy to generate hydrogen chloride gas when contacting water vapor, and the danger is high, so that the production environment is strictly controlled when the anthraquinone compound is used, the operation is inconvenient and the cost is increased; (3) although the porous inorganic filler has a larger specific surface area, the internal porous structure is easily clogged by flora and cannot function in practical application, and only the quinone-based compound on the surface can function.
The redox mediator containing quinone group as electron carrier can be reduced and oxidized reversibly, so that it has the capacity of being used as electron carrier in several redox reactions to speed up the transfer of electrons from the primary electron donor to the final electron acceptor, so as to raise the speed of biological redox reaction by one to several orders of magnitude. Therefore, the electron transfer capability of the redox mediator is improved, and the redox capability of the organism can be further accelerated. The electron transfer capability of the redox mediator itself remains substantially unchanged, and one approach is to increase the electron transfer capability of the environment in which it is placed, so that it accelerates the biodegradation of azo dyes, nitrates, and the like more rapidly.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing tourmaline containing anthraquinone compounds.
Another object of the present invention is to provide tourmaline containing anthraquinone compounds
Still another object of the present invention is to provide a use of tourmaline containing anthraquinone compounds.
The technical scheme of the invention is as follows:
a method for preparing tourmaline containing anthraquinone compound comprises the following steps,
s1, stirring an organic solvent I, a chloropropyl silane coupling agent and dilute hydrochloric acid with the mass concentration of 0.1 wt% at room temperature for 0.5-2 hours, adding the mixture into tourmaline, heating to a temperature not higher than 80 ℃, reacting for 1-5 hours, cooling, filtering, washing solids with absolute ethyl alcohol for 3 times, and drying to obtain chloropropyl modified tourmaline;
s2, adding the chloropropyl modified tourmaline obtained in the step S1, an amino anthraquinone-containing compound, an organic solvent II and an acid-binding agent into a container, stirring and reacting for 1-10 hours at 10-15 ℃, heating to 55-60 ℃, stirring for 1-5 hours, filtering, washing the filtered solids with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying to obtain the tourmaline containing the anthraquinone compound.
Preferably, the weight ratio of the organic solvent I, the chloropropyl silane coupling agent, the dilute hydrochloric acid and the tourmaline in the step S1 is 1:0.1-0.3:0.01: 0.5-1. More preferably, the weight ratio of the organic solvent I, the chloropropyl silane coupling agent, the dilute hydrochloric acid and the tourmaline can be 1:0.1:0.01:0.5, 1:0.15:0.01:0.5, 1:0.2:0.01:0.5, 1:0.25:0.01:0.5, 1:0.3:0.01:0.5, 1:0.1:0.01:1, 1:0.15:0.01:1, 1:0.2:0.01:1, 1:0.25:0.01:1, 1:0.3:0.01:1, but is not limited to the above list.
More preferably, the organic solvent I in step S1 and the organic solvent II in step S2 are selected from one or more of methanol, absolute ethanol, isopropanol, n-propanol, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, toluene and xylene. In a further preferred scheme, the organic solvent I and the organic solvent II can be selected from one or more of methanol, absolute ethyl alcohol, isopropanol, tetrahydrofuran, toluene and xylene.
Further preferably, the organic solvent one is one or more selected from methanol, absolute ethanol, isopropanol and butyl acetate.
Further preferably, the organic solvent II is one or more selected from absolute ethyl alcohol, tetrahydrofuran, methyl ethyl ketone and toluene.
More preferably, the chloropropyl silane coupling agent in step S1 is one or more selected from the group consisting of 3-chloropropyl trimethoxy silane, 3-chloropropyl triethoxy silane, 3-chloropropyl methyl dimethoxy silane and 3-chloropropyl methyl diethoxy silane. In a further preferred embodiment, the chloropropyl silane coupling agent may be selected from 3-chloropropyltrimethoxysilane or 3-chloropropyltriethoxysilane.
More preferably, the tourmaline has an average particle size of 0.1 μm to 1cm in step S1. In a further preferred embodiment, the average particle diameter of tourmaline may be 1 μm, 3 μm, 5 μm, 10 μm, 20 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 500 μm, 1mm and 5mm, but is not limited to the above.
Preferably, the weight ratio of the chloropropyl modified tourmaline, the amino anthraquinone-containing compound and the organic solvent II in the step S2 is 1:0.1-0.3: 3-8; the molar ratio of the amino group of the amino anthraquinone-containing compound to the acid scavenger in the step S2 is 1: 1.05-1.5. The acid-binding agent is used for absorbing hydrogen chloride generated by the reaction of chloropropyl and amino and promoting the reaction, so the molar weight of the acid-binding agent is more than that of the generated hydrogen chloride, but the excessive acid-binding agent causes the waste of raw materials on one hand and increases the difficulty of post-treatment on the other hand.
More preferably, the amino anthraquinone-containing compound of step S2 is selected from 1-amino-2-bromo-4-hydroxyanthraquinones1-amino-2-methylanthraquinone2-aminoanthraquinones1-aminoanthraquinones1, 2-diaminoanthraquinones1, 4-diaminoanthraquinones2, 6-diaminoanthraquinone1, 8-diaminoanthraquinones1, 5-diaminoanthraquinonesAnd 1, 5-dihydroxy-4, 8-diaminoanthraquinoneOne or more of them. In a further preferred embodiment, the amino anthraquinone-containing compound is selected from one or more of 1-amino-2-bromo-4-hydroxyanthraquinone, 1-amino-2-methylanthraquinone, 2-aminoanthraquinone and 1-aminoanthraquinone.
More preferably, in step S2, the acid-binding agent is selected from one or more of triethylamine, pyridine, triethanolamine, diethanolamine, N-diisopropylethylamine, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. More preferably, the acid-binding agent is one or more selected from triethylamine, pyridine and N, N-diisopropylethylamine.
Tourmaline containing anthraquinone compound prepared by the preparation method of any one of the above embodiments.
The application of the tourmaline containing anthraquinone compounds prepared by the preparation method of any one of the above embodiments in the field of water treatment.
Tourmaline, also called tourmaline, is a compound formed by combining borate, silicate and various metal elements, and has pyroelectricity and piezoelectricity. When the tourmaline is subjected to temperature change, two ends of the crystal respectively carry different positive and negative charges, which is the unique pyroelectricity of the tourmaline. When the two ends of the tourmaline are pressed, the phenomenon of carrying different charges can be presented. According to the invention, the pyroelectricity and the piezoelectricity of the tourmaline are utilized, the anthraquinone-containing compound is used for modifying the surface of the tourmaline and then the modified anthraquinone-containing compound is applied to water treatment, positive and negative charges are generated at two ends of the tourmaline along with the change of the temperature of a water body and/or the pressure on the tourmaline generated by the flow of the water body, and the generated positive and negative charges improve the conductivity of the surrounding water body, so that the accelerated degradation effect of the anthraquinone compound as an oxidation reduction mediator on azo dyes and nitrates can be improved.
According to the invention, dehydrochlorination reaction between an amino group on the amino anthraquinone-containing compound and a chloropropyl group on the surface of the chloropropyl modified tourmaline is utilized, and an acid-binding agent is used for absorbing hydrogen chloride to promote the reaction, so that the tourmaline is grafted with the anthraquinone compound on the surface through a chemical bond, and the tourmaline has the characteristic of good stability.
The invention has the beneficial effects that:
(1) the invention adopts the tourmaline with low price as the physical carrier, has wide source and low cost;
(2) the method has the advantages of few reaction steps, simple reaction process and low cost;
(3) the invention does not need to adopt raw materials which are easy to contact with moisture to generate toxic and harmful gases;
(4) the tourmaline with the anthraquinone compound grafted on the surface can obviously increase the biodegradation rate of azo dyes and nitrates, and can be continuously used after simple treatment.
(5) The invention utilizes the pyroelectricity and the piezoelectricity of the tourmaline, so that the tourmaline containing anthraquinone compounds can more rapidly promote the degradation of azo dyes, nitrates and the like under the condition of environmental temperature change and/or pressure generated at two ends of the tourmaline.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Unless otherwise specified, the parts in the following embodiments are parts by weight.
Example 1
Stirring 100 parts of absolute ethyl alcohol, 10 parts of chloropropyl triethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1 wt% at room temperature for 0.5 hour, adding into 50 parts of tourmaline with the particle size of 3 mu m, heating to 60 ℃, stirring for reaction for 2 hours, cooling, filtering, washing the filtered solids with absolute ethyl alcohol for 3 times, and drying to obtain chloropropyl modified tourmaline 1.
Placing a container in a water bath at 10 ℃, sequentially adding 100 parts of chloropropyl modified tourmaline 1, 21 parts of 2-aminoanthraquinone, 350 parts of tetrahydrofuran and 11.3 parts of triethylamine, stirring for reaction for 5 hours, heating to 55 ℃, stirring for 3 hours, filtering, washing a solid with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying to obtain the tourmaline 1 with an anthraquinone compound fixed on the surface. FT-IR analysis showed the product to be 1668cm-1The absorption peak is a sharp absorption peak of carbonyl group on anthraquinone structure and is 1598cm-1A sharp absorption peak with medium intensity is shown, which is the characteristic absorption peak of the hydrocarbon on the benzene ring, and the anthraquinone compound is shown to be fixed on the surface of the tourmaline. The content of N element of tourmaline before and after fixation is determined by element analysis method, and the content of anthraquinone compound on the surface of tourmaline 1 is 2.03mmol/g by calculation.
Example 2
100 parts of methanol, 15 parts of chloropropyl trimethoxyl silane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1 wt% are stirred for 0.5 hour at room temperature, added into 100 parts of 10 mu m tourmaline, heated to 50 ℃, stirred for reaction for 3 hours, cooled, filtered, the solid is filtered out, washed for 3 times by absolute ethyl alcohol, and dried to obtain chloropropyl modified tourmaline 2.
Placing the container in a water bath at 14 ℃, sequentially adding 100 parts of chloropropyl modified tourmaline 2, 12 parts of 1-aminoanthraquinone, 500 parts of tetrahydrofuran and 8.1 parts of triethylamine, stirring for reacting for 8 hours, heating to 55 ℃, stirring for 5 hours, filtering, washing the filtered solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying to obtain the tourmaline 2 with the anthraquinone compound fixed on the surface. The content of N element in tourmaline before and after fixation is determined by element analysis method, and anthraquinone compound content on tourmaline 2 surface is 1.77 mmol/g.
Example 3
Placing the container in a water bath at 14 ℃, sequentially adding 100 parts of chloropropyl modified tourmaline 2, 12 parts of 2, 6-diaminoanthraquinone, 500 parts of tetrahydrofuran and 13 parts of triethylamine, stirring for reacting for 6 hours, heating to 55 ℃, stirring for 5 hours, filtering, washing the filtered solids with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying to obtain the tourmaline 3 with the anthraquinone compound fixed on the surface. The content of N element in the tourmaline before and after fixation is determined by element analysis method, and the content of anthraquinone compound on the surface of tourmaline 2 is 1.62mmol/g by calculation.
Example 4
100 parts of methanol, 20 parts of chloropropyl trimethoxyl silane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1 wt% are stirred for 0.5 hour at room temperature, added into 100 mu m tourmaline, heated to 50 ℃, stirred for reaction for 3 hours, cooled, filtered, the solid is filtered out, washed for 3 times by absolute ethyl alcohol and dried, and the chloropropyl modified tourmaline 4 is obtained.
Placing the container in a water bath at 12 ℃, sequentially adding 100 parts of chloropropyl modified tourmaline 4, 21 parts of 1-aminoanthraquinone, 400 parts of tetrahydrofuran and 11.8 parts of triethylamine, stirring for reaction for 5 hours, heating to 60 ℃, stirring for 5 hours, filtering, washing the filtered solids with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying to obtain tourmaline 4 with anthraquinone compounds fixed on the surface. The content of N element in tourmaline before and after fixation is determined by element analysis method, and the content of anthraquinone compound on tourmaline 4 surface is 1.45mmol/g by calculation.
Example 5
Placing the container in a water bath at 12 ℃, sequentially adding 100 parts of chloropropyl modified tourmaline 4, 20 parts of 2, 6-diamino anthraquinone, 500 parts of tetrahydrofuran and 14.6 parts of pyridine, stirring for reaction for 5 hours, heating to 60 ℃, stirring for 5 hours, filtering, washing the filtered solids with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying to obtain tourmaline 5 with anthraquinone compounds fixed on the surface. The content of N element in the tourmaline before and after fixation is determined by element analysis method, and the content of anthraquinone compound on the surface of tourmaline 5 is 1.38mmol/g by calculation.
Example 6
100 parts of isopropanol, 30 parts of chloropropyl trimethoxyl silane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1 wt% are stirred for 1 hour at room temperature, added into 100 parts of 500 mu m tourmaline, heated to 70 ℃, stirred for reaction for 2 hours, cooled, filtered, the solid is filtered out, washed for 3 times by absolute ethyl alcohol, and dried to obtain chloropropyl modified tourmaline 5.
Placing the container in a water bath at 12 ℃, sequentially adding 100 parts of chloropropyl modified tourmaline 5, 28 parts of 1-amino-2-bromo-4-hydroxyanthraquinone, 500 parts of toluene and 9.7 parts of pyridine, stirring for reaction for 10 hours, heating to 55 ℃, stirring for 4 hours, filtering, washing the filtered solids with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying to obtain tourmaline 6 with the anthraquinone compound fixed on the surface. The content of N element in tourmaline before and after fixation is determined by element analysis method, and the content of anthraquinone compound on the surface of tourmaline 6 is 1.14 mmol/g.
Comparative example 1
Stirring 100 parts of methanol, 15 parts of chloropropyl trimethoxyl silane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1 wt% at room temperature for 0.5 hour, adding into 100 parts of 10-micron talcum powder, heating to 50 ℃, stirring for reaction for 3 hours, cooling, filtering, washing solids with absolute ethyl alcohol for 3 times, and drying to obtain the chloropropyl modified talcum powder.
Placing the container in a water bath at 14 ℃, sequentially adding 100 parts of chloropropyl modified talcum powder, 12 parts of 1-aminoanthraquinone, 350 parts of tetrahydrofuran and 8.1 parts of triethylamine, stirring for reacting for 8 hours, heating to 55 ℃, stirring for 5 hours, filtering, washing filtered solids with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying to obtain the talcum powder with anthraquinone compounds fixed on the surface. The content of the N element in the talcum powder before and after fixation is measured by adopting an element analysis method, and the content of the anthraquinone compound on the surface of the talcum powder is 1.70mmol/g through calculation.
Comparative example 2
Stirring 100 parts of methanol, 20 parts of chloropropyltrimethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1 wt% at room temperature for 0.5 hour, adding 100 parts of heavy calcium carbonate with the particle size of 100 microns, heating to 50 ℃, stirring for reaction for 3 hours, cooling, filtering, washing solids with absolute ethyl alcohol for 3 times, and drying to obtain the chloropropyl modified heavy calcium carbonate.
Placing the container in a water bath at 12 ℃, sequentially adding 100 parts of chloropropyl modified heavy calcium carbonate, 21 parts of 1-aminoanthraquinone, 400 parts of tetrahydrofuran and 11.8 parts of triethylamine, stirring for reaction for 5 hours, heating to 60 ℃, stirring for 5 hours, filtering, washing the filtered solids with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying to obtain the heavy calcium carbonate with the anthraquinone compound fixed on the surface. The content of N element in the heavy calcium carbonate before and after fixation is determined by adopting an element analysis method, and the content of anthraquinone compound on the surface of the heavy calcium carbonate is 1.48mmol/g through calculation.
Testing
And (3) testing the degradation acceleration effect of the azo dye: after washing 2g of blank tourmaline, 2g of the products of examples 1 to 6 and 2g of comparative examples 1 to 2, respectively, with physiological saline for 3 times, they were added to 200ml of 120mg/L acid Red B containing azo dye-degrading strain GYZ (staphylococus sp.) in logarithmic growth phase at a stirring rotation speed of 10rpm to perform a discoloration test, and the change of the acid Red B concentration with time was measured. The results are shown in Table 1.
Nitrate degradation acceleration effect test: 2g of blank tourmaline, 2g of the products of examples 1 to 6 and 2g of comparative examples 1 to 2, to which anthraquinone compounds were surface-grafted, were washed with physiological saline for 3 times, respectively, and then added to 200ml of nitrate waste water containing denitrifying microorganisms in logarithmic growth phase at a concentration of 150mg/L with stirring at 10rpm to conduct a test, and the change in nitrate concentration with time was measured. The results are shown in Table 2.
And (3) stability testing: 2g of tourmaline, to which the anthraquinone compounds were surface-grafted in examples 1 to 6, was washed with physiological saline for 3 times, respectively, and then added to 200ml of 120mg/L acid Red B containing an azo dye degrading strain GYZ (staphylococcus sp.) in the logarithmic phase for decolorization test, and the concentration of acid Red B after 8 hours was measured. Washing tourmaline with anthraquinone compound grafted on surface, drying, decolorizing with acid red B for 8 hr, and repeating the above steps for 12 times. Wherein the test procedures of examples 1-3 were conducted at a stirring speed of 10rpm, and the test procedures of examples 4-6 were conducted at a temperature change of 1 deg.C/min at 25-30 deg.C, and the results are shown in Table 3.
TABLE 1 acid Red B degradation acceleration test results
As can be seen from table 1, the tourmaline with the anthraquinone compound grafted on the surface thereof according to the present invention has a significant effect of promoting the degradation of azo dyes of acid red B, and the degradation of acid red B is faster as the content of the anthraquinone compound increases. Comparing the test of example 4 and comparative example 1, the content of anthraquinone compound surface-grafted to tourmaline in example 4 was significantly lower than that of comparative example 1, but the degradation effect on acid red B dye was almost the same. The tests of comparative example 6 and comparative example 2 gave the same results. Therefore, the use of the tourmaline containing anthraquinone compounds according to the present invention can degrade azo dyes more rapidly.
TABLE 2 nitrate degradation acceleration test results
As can be seen from table 2, the tourmaline surface-grafted with anthraquinone compounds according to the present invention has a significant effect of promoting the degradation of nitrate, and the degradation of nitrate is faster as the content of anthraquinone compounds increases. Comparing the test of example 4 and comparative example 1, the content of anthraquinone compound surface-grafted to tourmaline in example 4 was significantly lower than that of comparative example 1, but the effect of degradation of nitrate was almost the same. The tests of comparative example 6 and comparative example 2 gave the same results. Therefore, nitrate can be more rapidly degraded using the tourmaline containing anthraquinone compounds according to the present invention.
TABLE 3 degradation stability determination results for acid Red B
As can be seen from Table 3, the tourmaline with the anthraquinone compound grafted on the surface obtained by the present invention has a good effect after repeated use for 12 times in promoting the biodegradation of azo dyes and nitrates.
In conclusion, the tourmaline with the anthraquinone compound grafted on the surface has a good promotion effect on the biodegradation of azo dyes and nitrates, is good in stability, can be repeatedly used, and can be widely applied to water treatment.
The foregoing has shown and described the fundamental principles, major features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for preparing tourmaline containing anthraquinone compound is characterized in that: comprises the following steps of (a) carrying out,
s1, stirring an organic solvent I, a chloropropyl silane coupling agent and dilute hydrochloric acid with the mass concentration of 0.1 wt% at room temperature for 0.5-2 hours, adding the mixture into tourmaline, heating to a temperature not higher than 80 ℃, reacting for 1-5 hours, cooling, filtering, washing solids with absolute ethyl alcohol for 3 times, and drying to obtain chloropropyl modified tourmaline;
s2, adding the chloropropyl modified tourmaline obtained in the step S1, an amino anthraquinone-containing compound, an organic solvent II and an acid-binding agent into a container, stirring and reacting for 1-10 hours at 10-15 ℃, heating to 55-60 ℃, stirring for 1-5 hours, filtering, washing the filtered solids with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying to obtain the tourmaline containing the anthraquinone compound.
2. The method of claim 1, wherein: in the step S1, the weight ratio of the organic solvent I, the chloropropyl silane coupling agent, the dilute hydrochloric acid and the tourmaline is 1:0.1-0.3:0.01: 0.5-1.
3. The production method according to claim 1 or 2, characterized in that: the organic solvent I in the step S1 and the organic solvent II in the step S2 are selected from one or more of methanol, absolute ethyl alcohol, isopropanol, n-propanol, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, toluene and xylene.
4. The production method according to claim 1 or 2, characterized in that: in the step S1, the chloropropyl silane coupling agent is one or more selected from 3-chloropropyl trimethoxy silane, 3-chloropropyl triethoxy silane, 3-chloropropyl methyl dimethoxy silane and 3-chloropropyl methyl diethoxy silane.
5. The production method according to claim 1 or 2, characterized in that: the average grain diameter of the tourmaline in the step S1 is 0.1 μm-1 cm.
6. The method of claim 1, wherein: in the step S2, the weight ratio of the chloropropyl modified tourmaline, the amino anthraquinone-containing compound and the organic solvent II is 1:0.1-0.3: 3-8; the molar ratio of the amino group of the amino anthraquinone-containing compound to the acid-binding agent in the step S2 is 1: 1.05-1.5.
7. The production method according to claim 1 or 6, characterized in that: the amino anthraquinone-containing compound in step S2 is selected from 1-amino-2-bromo-4-hydroxyanthraquinone1-amino-2-methylanthraquinone2-aminoanthraquinones1-aminoanthraquinones1, 2-diaminoanthraquinones1, 4-diaminoanthraquinones2, 6-diaminoanthraquinone1, 8-diaminoanthraquinones1, 5-diaminoanthraquinonesAnd 1, 5-dihydroxy-4, 8-diaminoanthraquinoneOne or more of them.
8. The production method according to claim 1 or 6, characterized in that: in the step S2, the acid-binding agent is one or more selected from triethylamine, pyridine, triethanolamine, diethanolamine, N-diisopropylethylamine, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.
9. A tourmaline containing anthraquinone compounds prepared by the preparation method of any one of claims 1 to 8.
10. Use of tourmaline containing anthraquinone compounds prepared by the preparation method of any one of claims 1 to 8 in the field of water treatment.
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