WO2020221242A1

WO2020221242A1 - Method for preparing inorganic filler with anthraquinone compound fixed on surface thereof and use thereof

Info

Publication number: WO2020221242A1
Application number: PCT/CN2020/087440
Authority: WO
Inventors: 严滨; 叶茜; 徐苏; 曾孟祥
Original assignee: 厦门理工学院
Priority date: 2019-04-29
Filing date: 2020-04-28
Publication date: 2020-11-05
Also published as: CN110040843A; CN110040843B

Abstract

Disclosed are a method for preparing an inorganic filler with an anthraquinone compound fixed on the surface thereof and the use thereof. A chloropropyl silane coupling agent is reacted with an inorganic filler to obtain a chloropropyl group surface-modified inorganic filler, and same is then subjected to a dehydrochlorination reaction with an amino-containing anthraquinone compound under the action of an acid binding agent, so as to obtain an inorganic filler with an anthraquinone compound fixed on the surface thereof. The inorganic filler with an anthraquinone compound fixed on the surface thereof that is obtained using the preparation method can accelerate the degradation of contaminants such as dyes and nitrates, and can be reused; in addition, same has a wide source of raw materials, few reaction steps, and a low cost, and can be widely used in the treatment of wastewater containing azo dyes, nitrates, etc.

Description

Preparation method and application of anthraquinone compound fixed on surface of inorganic filler

Technical field

The invention relates to the field of water treatment engineering, in particular to a preparation method and application for fixing an anthraquinone compound on the surface of an inorganic filler.

Background technique

With the development of society and economy, the continuous growth of population and the increasing demand for industrial and agricultural products, the discharge of many heavy metals and non-biodegradable pollutants in wastewater is increasing, which seriously deteriorates water quality and ultimately affects the human body. Health and the entire natural ecosystem are causing serious harm. For example, azo dyes are the most widely used synthetic dyes in the printing and dyeing process of textiles and clothing due to their simple synthesis methods and variable structures. They are mostly used for dyeing and printing of natural and synthetic fibers. Under some special conditions, it can decompose to produce more than 20 kinds of carcinogenic aromatic amines, which can change the DNA structure of the human body through activation to cause disease and induce cancer. In the printing and dyeing process, about 10-15% of the dyes will be lost to the printing and dyeing wastewater, affecting the growth of aquatic organisms and microorganisms, causing serious harm to the receiving water body, and ultimately affecting human health, including azo dyes.

Nitrate is another chemical substance that is harmful to the human body and the environment. Ammonia nitrogen and nitrate nitrogen contained in over-applied chemical fertilizers, domestic sewage, manure, industrial sewage, etc., enter the natural environment through soil and water bodies, and are one of the main substances that cause eutrophication of water bodies. Conventional biochemical treatment processes generally can only convert ammonia nitrogen into nitrate nitrogen, and the reduction of nitrate nitrogen cannot be efficiently completed in general treatment processes because of the low denitrification efficiency.

Therefore, more and more attention is paid to the treatment of this type of wastewater, and the main treatment methods are chemical and biological methods. Biological methods have better application prospects, especially the anaerobic-aerobic process is the most effective and widely used method for treating this type of wastewater. How to increase the rate of microbial reduction of dye and nitrate has always been the focus of this type of process.

Researchers have found that redox mediators containing quinone groups can effectively accelerate the biotransformation process of azo dyes and nitrates, and increase the degradation rate. However, the redox mediator containing quinone groups has the disadvantages of low molecular weight, which is easy to lose when directly added to the water treatment system, causing secondary pollution and high continuous feeding cost. Fixing the quinone group-containing redox mediator on a physical carrier that is insoluble in water is a relatively feasible industrialized method. It has the advantage of being reusable, not easy to lose, and avoiding secondary pollution.

The Chinese authorized invention patent with the authorized announcement number CN101862680B discloses a method for preparing a porous inorganic filler to fix a quinone compound, which effectively improves the degradation rate of azo dyes. The preparation method is to plate γ-alumina on the surface of the porous inorganic filler, and then treat it with 3-aminotriethoxysilane to make the surface of the porous inorganic filler contain primary amino groups, and then pass the primary amino groups and anthracene containing sulfonyl chloride groups. The quinone compound reacts to obtain a porous inorganic filler containing quinone groups on the surface. This method has the following problems: (1) The reaction steps are long, time-consuming, the final yield is low, and the cost is high; (2) The use of anthraquinone compounds containing sulfonyl chloride groups can easily generate hydrogen chloride gas when exposed to water vapor, which is dangerous The production environment needs to be strictly controlled, resulting in inconvenience and cost increase; (3) Although porous inorganic fillers have a large specific surface area, the internal porous structure is easily blocked by the flora in practical applications and cannot play a role. Quinone-based compounds can play a role.

Therefore, the quinone group-containing redox mediator is fixed on a suitable water-insoluble physical carrier by a suitable method, so that it is not easy to be lost and reused. However, there is no report of a better physical carrier and simpler Fixing method.

Summary of the invention

The purpose of the present invention is to overcome the defects of the prior art and provide a preparation method for fixing an anthraquinone compound on the surface of an inorganic filler.

Another object of the present invention is to provide an application of anthraquinone compound fixed on the surface of inorganic filler.

The technical scheme of the present invention is as follows:

A preparation method for fixing an anthraquinone compound on the surface of an inorganic filler includes the following steps:

S1. The first organic solvent, chloropropyl silane coupling agent and dilute hydrochloric acid with a mass concentration of 0.05-0.2 wt% are stirred at room temperature for 0.5-2 hours, and then added to the inorganic filler. The temperature is raised to no more than 80°C, reaction 1 -5 hours, cooling, filtering, filtering the solid, washing 3 times with absolute ethanol, and drying to obtain the chloropropyl modified inorganic filler;

S2. Add the chloropropyl modified inorganic filler, the amino-anthraquinone compound, the second organic solvent and the acid binding agent obtained in step S1 to the container, stir and react at 10-15°C for 1-10 hours, and heat up to 55- Stir for 1-5 hours at 60°C, filter, and filter the solid to wash 3 times with deionized water, then wash 3 times with absolute ethanol, and dry to obtain an inorganic filler with an anthraquinone compound fixed on the surface.

Preferably, the weight ratio of the first organic solvent, chloropropylsilane coupling agent, dilute hydrochloric acid and inorganic filler in step S1 is 0.5-2:0.05-0.2:0.005:1.

More preferably, the first organic solvent in step S1 and the second organic solvent in step S2 are selected from methanol, absolute ethanol, isopropanol, n-propanol, ethyl acetate, butyl acetate, tetrahydrofuran, and methyl ethyl ketone One or more of, toluene and xylene.

More preferably, the first organic solvent is selected from one or more of methanol, absolute ethanol, isopropanol and ethyl acetate.

More preferably, the second organic solvent is selected from one or more of absolute ethanol, tetrahydrofuran, toluene and methyl ethyl ketone.

More preferably, the chloropropyl silane coupling agent in step S1 is selected from 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxy One or more of silane and 3-chloropropylmethyldiethoxysilane.

More preferably, the inorganic filler in step S1 is selected from one or more of wollastonite, talc powder, mica powder, calcium carbonate, clay, attapulgite, montmorillonite and solid glass beads. Among them, calcium carbonate can be selected from germplasm calcium carbonate or light calcium carbonate.

The particle size of the inorganic filler is small and can have a larger specific surface area to increase the amount of anthraquinone compound fixed on the surface of the inorganic filler per unit weight, but the particle size of the inorganic filler should not be too low. It is found in the experiment that the particle size of the inorganic filler is lower than 100nm is not conducive to the degradation of azo dyes.

Preferably, the weight ratio of the chloropropyl modified inorganic filler, the amino-anthraquinone compound and the second organic solvent in step S2 is 1:0.2-0.4:3-8; in the amino-anthraquinone compound in step S2 The ratio of the number of moles of amino groups to the number of moles of the acid binding agent is 1:1.05-2.

More preferably, the amino-containing anthraquinone compound in step S2 is selected from 2-aminoanthraquinone

1-aminoanthraquinone

1-amino-2-bromo-4-hydroxyanthraquinone

1-amino-2-methylanthraquinone

1,2-Diaminoanthraquinone

1,4-Diaminoanthraquinone

2,6-Diaminoanthraquinone

1,8-Diaminoanthraquinone

1,5-Diaminoanthraquinone

And 1,5-dihydroxy-4,8-diaminoanthraquinone

One or more of them.

More preferably, the acid binding agent in step S2 is selected from triethylamine, pyridine, triethanolamine, diethanolamine, N,N-diisopropylethylamine, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide One or more of them.

An inorganic filler with an anthraquinone compound immobilized on the surface prepared by the preparation method described in any one of the above embodiments.

An inorganic filler with an anthraquinone compound immobilized on the surface prepared by the preparation method of any one of the above embodiments is used in the field of water treatment.

The invention utilizes the dehydrochlorination reaction between the amino group and the chloropropyl group on the amino-containing anthraquinone compound, and uses an acid binding agent to absorb hydrogen chloride, which promotes the dehydrochlorination reaction between the amino group and the chloropropyl group, and the surface of the inorganic filler passes Anthraquinone compounds with more chemical bonds fixed have the characteristics of good stability.

The beneficial effects of the present invention are:

(1) In the present invention, inexpensive inorganic fillers are used as physical carriers, which have a wide range of sources, low cost, and are insoluble in water;

(2) The present invention has fewer reaction steps, simple reaction process, low cost and convenient post-processing;

(3) The present invention does not need to use raw materials that are easy to contact with moisture to produce toxic and harmful gases, which improves operability and reduces harm to operators and the environment;

(4) The inorganic filler with anthraquinone compound immobilized on the surface obtained by the present invention can significantly increase the degradation rate of azo dyes and nitrates, and can be used continuously after simple treatment.

Detailed ways

The technical solutions of the present invention will be further illustrated and described below through specific embodiments.

Unless otherwise specified, the parts in the following embodiments are all parts by weight.

Example 1

Stir 50 parts of absolute ethanol, 6 parts of chloropropyltriethoxysilane and 0.5 parts of dilute hydrochloric acid with a mass concentration of 0.05wt% at room temperature for 0.5 hours, add them to 100 parts of 800 mesh heavy calcium carbonate, and heat to 60 The temperature was stirred and reacted for 2 hours, the temperature was lowered, and the filter was filtered. The filtered solid was washed 3 times with absolute ethanol and dried to obtain chloropropyl modified heavy calcium carbonate.

Place the container in a water bath at 12°C, add 100 parts of chloropropyl modified heavy calcium carbonate, 22 parts of 2-aminoanthraquinone, 400 parts of tetrahydrofuran and 11 parts of triethylamine in sequence, stir and react for 5 hours, and heat up to 55°C , Stirred for 3 hours, filtered, the filtered solid was washed with deionized water 3 times, then washed with absolute ethanol 3 times, and dried to obtain heavy calcium carbonate with anthraquinone compound fixed on the surface. FT-IR analysis shows that the product has a strong and sharp absorption peak at 1667cm ^-1 , which is the characteristic absorption peak of the carbonyl group on the anthraquinone molecular structure, and a moderately sharp absorption peak at 1597cm ^-1 , which is the hydrocarbon on the benzene ring. The characteristic absorption peak indicates that the anthraquinone compound is fixed on the surface of heavy calcium carbonate. The elemental analysis method was used to determine the N element content of heavy calcium carbonate before and after fixation, and the content of fixed anthraquinone compound on the surface of heavy calcium carbonate was 1.67 mmol/g by calculation.

Example 2

100 parts of absolute ethanol, 10 parts of chloropropyltrimethoxysilane and 0.5 parts of dilute hydrochloric acid with a mass concentration of 0.1% by weight were stirred at room temperature for 0.5 hours, added to 100 parts of solid glass microspheres with an average particle size of 30μm, and heated The temperature was raised to 45° C., the reaction was stirred for 4 hours, the temperature was lowered, and the filter was filtered. The filtered solid was washed 3 times with absolute ethanol and dried to obtain chloropropyl modified solid glass microspheres 1.

Place the container in a water bath at 15°C, add 100 parts of chloropropyl modified solid glass microspheres 1, 30 parts of 1-aminoanthraquinone, 400 parts of toluene and 18 parts of triethylamine in sequence, stir and react for 7 hours, and heat up to 60 After stirring for 2 hours at ℃, filtering, the filtered solid was washed 3 times with deionized water, then washed 3 times with absolute ethanol, and dried to obtain solid glass microspheres 1 with anthraquinone compound fixed on the surface. FT-IR analysis shows that the product has a strong and sharp absorption peak at 1667cm ^-1 , which is the characteristic absorption peak of the carbonyl group on the anthraquinone molecular structure, and a moderately sharp absorption peak at 1599cm ^-1 , which is the hydrocarbon on the benzene ring. The characteristic absorption peak indicates that the anthraquinone compound is fixed on the surface of the solid glass microsphere. The elemental analysis method was used to determine the N element content of the solid glass microspheres before and after the fixation. The content of the fixed anthraquinone compound on the surface of the solid glass microspheres was calculated to be 1.39 mmol/g.

Example 3

Place the container in a water bath at 13°C, and add 100 parts of chloropropyl modified solid glass microspheres 1, 30 parts of 1,5-diaminoanthraquinone, 500 parts of toluene and 30 parts of triethylamine obtained in Example 2 in sequence , Stir the reaction for 7 hours, warm to 60°C, stir for 2 hours, filter, filter out the solid, wash 3 times with deionized water, then wash 3 times with absolute ethanol, and dry to obtain a solid glass microsphere with anthraquinone compound fixed on the surface Ball 2. The elemental analysis method was used to determine the N element content of the solid glass microspheres before and after the fixation. The content of the fixed anthraquinone compound on the surface of the solid glass microspheres was calculated to be 1.22 mmol/g.

Example 4

100 parts of absolute ethanol, 15 parts of chloropropyltrimethoxysilane and 0.5 parts of dilute hydrochloric acid with a mass concentration of 0.1% by weight were stirred at room temperature for 1 hour, then added to 100 parts of solid glass microspheres with an average particle size of 120μm, and heated The temperature was raised to 65° C., the reaction was stirred for 5 hours, the temperature was lowered, and the filter was filtered. The filtered solid was washed 3 times with absolute ethanol and dried to obtain chloropropyl-modified solid glass microspheres 2.

Place the container in a water bath at 12°C, add 100 parts of chloropropyl modified solid glass microspheres 2, 30 parts of 1-aminoanthraquinone, 600 parts of toluene and 18 parts of triethylamine in sequence, stir and react for 7 hours, and heat up to 60 After stirring for 2 hours, filtering, the filtered solid was washed 3 times with deionized water, then washed 3 times with absolute ethanol, and dried to obtain solid glass microspheres 3 with an anthraquinone compound fixed on the surface. The elemental analysis method was used to determine the N element content of the solid glass microspheres before and after the fixation. The content of the fixed anthraquinone compound on the surface of the solid glass microspheres was calculated to be 1.05 mmol/g.

Example 5

200 parts of isopropanol, 18 parts of chloropropyltriethoxysilane and 0.5 parts of dilute hydrochloric acid with a mass concentration of 0.1% by weight were stirred at room temperature for 1 hour, added to 100 parts of 1000 mesh talc, and heated to 60°C, The reaction was stirred for 4 hours, cooled, filtered, and the filtered solid was washed 3 times with absolute ethanol, and dried to obtain chloropropyl modified talc.

Place the container in a water bath at 10°C, add 100 parts of chloropropyl modified talc, 35 parts of 1-amino-2-methylanthraquinone, 500 parts of tetrahydrofuran and 18 parts of pyridine in sequence, stir and react for 6 hours, and heat up to 55 Stir at temperature for 3 hours, filter, filter the solid, wash with deionized water 3 times, then wash 3 times with absolute ethanol, and dry to obtain talc powder with anthraquinone compound fixed on the surface. The elemental analysis method was used to determine the N content of the talc before and after the fixation, and the content of the fixed anthraquinone compound on the surface of the talc was 1.81 mmol/g by calculation.

test

Test of acceleration effect on degradation of azo dyes: 2g of blank inorganic filler and 2g of inorganic filler with fixed anthraquinone compound on the surface of Examples 1-5 were washed with physiological saline three times, and then added to 200ml of azo containing logarithmic growth phase. Dye-degrading strain GYZ (staphylococcus sp.) was tested for decolorization in 120 mg/L acid red B, and the concentration of acid red B changed over time. The results are shown in Table 1.

Test for accelerating effect of nitrate degradation: Wash 2g of blank inorganic filler and 2g of inorganic filler with fixed anthraquinone compound on the surface of Examples 1-5 with physiological saline for 3 times, and then add them to 200ml of logarithmic growth phase denitrifying microorganisms. Test in 150mg/L nitrate wastewater to determine the change of nitrate concentration over time. The results are shown in Table 2.

Stability test: Wash 2g of the inorganic fillers with fixed anthraquinone compounds on the surface of Examples 1-5 with physiological saline for 3 times, and then add them to 200ml containing logarithmic growth phase azo dye degradation strain GYZ (staphylococcus sp.) A decolorization test was performed in 120 mg/L of Acid Red B, and the concentration of Acid Red B after 8 hours was measured. After the test, the inorganic filler on which the anthraquinone compound is fixed on the surface is washed and dried with water and absolute ethanol, and then subjected to the decolorization test with Acid Red B for 8 hours according to the above method, and the test is repeated 12 times. The results are shown in Table 3.

Table 1 Accelerated Test Results of Acid Red B Degradation

It can be seen from Table 1 that the inorganic filler with fixed anthraquinone compound on the surface of the present invention has a significant effect of promoting the degradation of azo dyes, and the higher the content of anthraquinone compound fixed on the surface of the inorganic filler, the more obvious the degradation of azo dyes.

Table 2 Accelerated test results of nitrate degradation

It can be seen from Table 2 that the inorganic filler with anthraquinone compound immobilized on the surface of the present invention has a significant effect of promoting the degradation of nitrate, and the higher the content of the anthraquinone compound immobilized on the surface of the inorganic filler, the more obvious the acceleration effect on the degradation of nitrate.

Table 3 Degradation stability test results of Acid Red B

It can be seen from Table 3 that the inorganic filler with fixed anthraquinone compound on the surface obtained in the present invention has a better acceleration effect after it can be used repeatedly for 12 times in accelerating the biodegradation of azo dyes.

In summary, the inorganic filler with surface immobilized anthraquinone compound obtained in the present invention has a good acceleration effect on the biodegradation of azo dyes and nitrates, and has good stability and can be used repeatedly. Can be widely used in wastewater.

The above has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments are only preferred embodiments of the present invention. The scope of implementation of the present invention cannot be limited accordingly, that is, it is made in accordance with the patent scope of the present invention and the contents of the specification. The equivalent changes and modifications of should still fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

A preparation method for fixing an anthraquinone compound on the surface of an inorganic filler, characterized in that it comprises the following steps:

S1. The first organic solvent, chloropropyl silane coupling agent and dilute hydrochloric acid with a mass concentration of 0.05-0.2 wt% are stirred at room temperature for 0.5-2 hours, and then added to the inorganic filler. The temperature is raised to no more than 80°C, reaction 1 -5 hours, cooling, filtering, filtering the solid, washing 3 times with absolute ethanol, and drying to obtain the chloropropyl modified inorganic filler;

S2. Add the chloropropyl modified inorganic filler, the amino-anthraquinone compound, the second organic solvent and the acid binding agent obtained in step S1 to the container, stir and react at 10-15°C for 1-10 hours, and heat up to 55- Stir for 1-5 hours at 60°C, filter, and filter the solid to wash 3 times with deionized water, then wash 3 times with absolute ethanol, and dry to obtain an inorganic filler with an anthraquinone compound fixed on the surface.
The preparation method according to claim 1, wherein the weight ratio of the first organic solvent, chloropropyl silane coupling agent, dilute hydrochloric acid and inorganic filler in step S1 is 0.5-2:0.05-0.2:0.005 :1.
The preparation method according to claim 1 or 2, wherein the first organic solvent in step S1 and the second organic solvent in step S2 are selected from methanol, absolute ethanol, isopropanol, and n-propanol One or more of, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, toluene and xylene.
The preparation method according to claim 1 or 2, wherein the chloropropyl silane coupling agent in step S1 is selected from the group consisting of 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane , One or more of 3-chloropropylmethyldimethoxysilane and 3-chloropropylmethyldiethoxysilane.
The preparation method according to claim 1 or 2, wherein the inorganic filler in step S1 is selected from wollastonite, talc, mica powder, calcium carbonate, clay, attapulgite, montmorillonite and solid glass One or more of microbeads.
The preparation method according to claim 1, wherein the weight ratio of the chloropropyl modified inorganic filler, the amino-containing anthraquinone compound and the second organic solvent in step S2 is 1:0.1-0.3:3-8; In step S2, the ratio of the number of moles of amino groups in the amino-containing anthraquinone compound to the number of moles of the acid binding agent is 1:1.05-2.
The preparation method according to claim 1 or 6, wherein the amino-containing anthraquinone compound in step S2 is selected from 2-aminoanthraquinone
1-aminoanthraquinone
1-amino-2-bromo-4-hydroxyanthraquinone
1-amino-2-methylanthraquinone
1,2-Diaminoanthraquinone
1,4-Diaminoanthraquinone
2,6-Diaminoanthraquinone
1,8-Diaminoanthraquinone
1,5-Diaminoanthraquinone
And 1,5-dihydroxy-4,8-diaminoanthraquinone
One or more of them.
The preparation method according to claim 1 or 6, wherein the acid binding agent in step S2 is selected from triethylamine, pyridine, triethanolamine, diethanolamine, N,N-diisopropylethylamine, carbonic acid One or more of sodium, potassium carbonate, sodium hydroxide and potassium hydroxide.
An inorganic filler with an anthraquinone compound fixed on the surface prepared by the preparation method of any one of claims 1-8.
An application of an inorganic filler with an anthraquinone compound fixed on the surface prepared by the preparation method of any one of claims 1-8 in the field of water treatment.