CN110066009A - A kind of tourmaline containing anthraquinone compounds, preparation method and application - Google Patents
A kind of tourmaline containing anthraquinone compounds, preparation method and application Download PDFInfo
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- CN110066009A CN110066009A CN201910357164.2A CN201910357164A CN110066009A CN 110066009 A CN110066009 A CN 110066009A CN 201910357164 A CN201910357164 A CN 201910357164A CN 110066009 A CN110066009 A CN 110066009A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to water treatment field, the specifically process field of the waste water containing pollutant, it is related to a kind of tourmaline containing anthraquinone compounds, preparation method and application.The present invention reacts chloropropyl silane coupling agent and tourmaline, obtains modified by chloropropyl by tourmaline, then with dehydrochlorination reaction under the action of acid binding agent containing aminoanthraquinone compound, obtain the tourmaline that anthraquinone compounds are contained on surface.The biological reducing process that azo dyes and nitrate can be substantially speeded up using the tourmaline that anthraquinone compounds are contained on the surface that the present invention obtains, may be reused, and raw material sources are extensive, reaction step is few, at low cost, can be widely used in the treatment of waste water.
Description
Technical field
The present invention relates to engineering of water treatment fields, and in particular to a kind of tourmaline containing anthraquinone compounds, preparation method
And application.
Background technique
As society and expanding economy, population constantly increase, requirement of the people to industrial and agricultural products is higher and higher, also gets over
Come more, therefore has synthesized a large amount of chemical substance by artificial means, thereby resulted in many containing heavy metal and difficult for biological degradation
The discharge of wastewater of pollutant enter the environment of animals and plants and human survival, finally to human health and entire nature ecology
Circle all causes to seriously endanger.For example azo dyes has become because of the features such as synthesis technology is simple, low in cost, dyeability protrudes
For fabric clothing is most widely used in dyeing and printing process, the maximum a kind of synthetic dyestuffs of dosage.Under some specific conditions,
It, which can be decomposed, generates more than 20 kinds of carcinogenic aromatic amines, changes the DNA structure of human body by activation so as to cause lesion and lures
Send out cancer.There are about the dyestuffs of 10-15% to be lost in dyeing waste water in dyeing process, the discharge meeting of these dyeing waste waters
Serious harm is generated to receiving water body, wherein just including azo dyes.
Nitrate is the another kind of chemical substance to human body and environment with larger harm.The chemical fertilizer excessively applied, life
The ammoniacal nitrogen and nitrate that sewage and excrement, trade effluent etc. contain enter natural environment via soil, water body etc., are to cause
One of main matter of water eutrophication.Ammoniacal nitrogen can only be generally changed into nitrate nitrogen, nitre state by routine biochemistry treatment process
The reduction of nitrogen can not be completed efficiently in general treatment process because denitrification efficiency is low.
Therefore, it is more taken seriously to the processing of this kind of waste water, wherein main processing method is chemical method and bioanalysis.
The application prospect of bioanalysis is more preferable, and it is also most widely used that especially anaerobic-aerobic disposal, which is the most effective of this kind of waste water of processing,
Method, how to improve micro-reduction dyestuff, the rate of nitrate anion be always this kind of technique emphasis.
Researcher has found that the redox mediators containing quinonyl can effectively accelerate the biology of azo dyes, nitrate etc.
Conversion process improves degradation rate.And the redox mediators containing quinonyl are added directly into water process since molecular weight is smaller
It is easy to run off in system and causes secondary pollution and continuous dosing disadvantage at high cost.Redox mediators containing quinonyl are fixed on
It is more feasible industrial method on physical support not soluble in water, existing the advantages of can recycling, and be not easy
It is lost, avoids the generation of secondary pollution.
China's authorization patent of invention of Authorization Notice No. CN101862680B discloses a kind of porous inorganic filling materials-fixed quinone
The preparation method of compound effectively increases the degradation rate of azo dyes.The preparation method is in porous inorganic filling materials table
Face plates gama-alumina, is then handled with 3- amino triethoxysilane, so that primary amino group is contained on porous inorganic filling materials surface,
It is reacted again by the primary amino group with the anthraquinone compounds containing sulfonic acid chloride group, obtains the porous, inorganic that quinonyl is contained on surface and fill out
Material.This method there is a problem of following: (1) reaction step is long, and time-consuming, and ultimate yield is low, at high cost；(2) use contains sulphur
The anthraquinone compounds of acid chloride groups are easy to generate hydrogen chloride gas when contacting steam, and risk is big, therefore needs when use
Strict control production environment causes inconvenient for operation and cost to improve；(3) although porous inorganic filling materials large specific surface area,
Internal porous structure is easy to be blocked by flora in practical application, cannot play a role, often the only quinone based compound, photosensitive article on surface
Object can play a role.
Contain the redox mediators of quinonyl as electron transit mediator, can be reversible being reduced and aoxidizing, therefore it has
Having can accelerate electronics to be transmitted to finally from primary electron donor in multiple redox reactions as the ability of electron carrier
Electron acceptor, so that the rate of biological oxidation-reduction, which improves one, arrives several orders of magnitude.Therefore redox is improved to be situated between
The electron transmission ability of body can more accelerate the redox ability of biology.But the electron transmission energy of redox mediators itself
Power is kept essentially constant, and a kind of method is the ability for transmitting electronics of its local environment of raising, so that it accelerates azo dye
The biodegrade of material, nitrate etc. is faster.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of preparation of tourmaline containing anthraquinone compounds is provided
Method.
It is another object of the present invention to provide a kind of tourmaline containing anthraquinone compounds
It is also an object of the present invention to provide a kind of applications of tourmaline containing anthraquinone compounds.
Technical scheme is as follows:
A kind of preparation method of the tourmaline containing anthraquinone compounds, includes the following steps,
S1, the dilute hydrochloric acid of organic solvent one, chloropropyl silane coupling agent and mass concentration 0.1wt% is stirred at room temperature
It 0.5-2 hours, is added in tourmaline, is warming up to no more than 80 DEG C, reacts 1-5 hours, cool down, filtering filters out solid use
It is washes of absolute alcohol 3 times, dry, obtain modified by chloropropyl by tourmaline；
S2, the modified by chloropropyl by tourmaline for obtaining step S1, contain aminoanthraquinone compound, organic solvent two and acid binding agent
It is added in container, is stirred to react at 10-15 DEG C 1-10 hours, be warming up to 55-60 DEG C, stir 1-5 hours, filtering filters out
Solid is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, dry, obtains the tourmaline containing anthraquinone compounds.
Preferably, the weight ratio of organic solvent one, chloropropyl silane coupling agent, dilute hydrochloric acid and tourmaline described in step S1
For 1:0.1-0.3:0.01:0.5-1.It is furthermore preferred that the organic solvent one, chloropropyl silane coupling agent, dilute hydrochloric acid and electrical
The weight ratio of stone 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 be not limited to listed above.
It is furthermore preferred that organic solvent two described in organic solvent one described in step S1 and step S2 is selected from methanol, anhydrous
One of ethyl alcohol, isopropanol, normal propyl alcohol, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, toluene and dimethylbenzene or
It is several.In further preferred scheme, organic solvent one and organic solvent two can be selected from methanol, dehydrated alcohol, isopropyl
One or more of alcohol, tetrahydrofuran, toluene and dimethylbenzene.
It is further preferred that organic solvent one is selected from one of methanol, dehydrated alcohol, isopropanol and butyl acetate or several
Kind.
It is further preferred that organic solvent two is selected from one of dehydrated alcohol, tetrahydrofuran, methyl ethyl ketone and toluene or several
Kind.
It is furthermore preferred that chloropropyl silane coupling agent described in step S1 is selected from 3- r-chloropropyl trimethoxyl silane, 3- chlorine third
One of ethyl triethoxy silicane alkane, 3- chloropropylmethyldimethoxysilane and 3- chloropropyl diethoxy silane or
It is several.In further preferred scheme, chloropropyl silane coupling agent can be selected from 3- r-chloropropyl trimethoxyl silane or 3- chlorine
Propyl-triethoxysilicane.
It is furthermore preferred that the 0.1 μm~1cm of average grain diameter of tourmaline described in step S1.In further preferred scheme,
The average grain diameter of tourmaline can be 1 μm, 3 μm, 5 μm, 10 μm, 20 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 500 μ
M, 1mm and 5mm, but be not limited to listed above.
Preferably, modified by chloropropyl by tourmaline described in step S2, the weight containing aminoanthraquinone compound and organic solvent two
Amount is than being 1:0.1-0.3:3-8；Middle amino molal quantity and the acid binding agent described in step S2 containing aminoanthraquinone compound
Mole ratio is 1:1.05-1.5.The effect of acid binding agent is the hydrogen chloride for absorbing chloropropyl and amino reaction generation, promotes reaction
Progress, therefore the mole of acid binding agent will be more than the mole of the hydrogen chloride generated, but acid binding agent is excessively excessive, a side
Face is the waste for causing raw material, on the other hand also will increase the difficulty of post-processing.
It is furthermore preferred that being selected from 1- AMINO 2 BROMO 4 HYDROXY ANTHRAQUINONE containing aminoanthraquinone compound described in step S21- amino-2-methyl anthraquinone2- amino anthraquinones1- amino anthraquinones1,2- diamino-anthraquinone1,4- diamino-anthraquinone2,6- diamino-anthraquinone1,8- diamino-anthraquinone1,5- diamino-anthraquinoneWith 1,5- dihydroxy -4,8- diamino-anthraquinoneOne or more of.?
It is described to be selected from 1- AMINO 2 BROMO 4 HYDROXY ANTHRAQUINONE, 1- amino -2- first containing aminoanthraquinone compound in further preferred scheme
One or more of base anthraquinone, 2- amino anthraquinones and 1- amino anthraquinones.
It is furthermore preferred that acid binding agent described in step S2 is selected from triethylamine, pyridine, triethanolamine, diethanol amine, N, N- bis-
One or more of wopropyl ethyl amine, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.It is furthermore preferred that described tie up acid
Agent is selected from triethylamine, pyridine and N, one or more of N- diisopropylethylamine.
The tourmaline containing anthraquinone compounds that preparation method described in a kind of any of the above-described embodiment is prepared.
The tourmaline containing anthraquinone compounds that preparation method described in a kind of any of the above-described embodiment is prepared is in water
The application of process field.
Tourmaline is also Tourmaline, is the compound that a kind of borate, silicate and Determination of multiple metal elements are composed, tool
There are pyroelectricity and piezoelectricity.When variation of the tourmaline by temperature, the both ends of crystal can be respectively provided with positive and negative different electricity
Lotus, this is the unique pyroelectricity of tourmaline.When the both ends of tourmaline are under pressure, showing with different charges can also be presented
As.The present invention utilizes the pyroelectricity and piezoelectricity of tourmaline, its surface is used modified applied to water process containing anthraquinone compounds
When, with the variation of water temperature and/or due to the pressure to tourmaline that water body flow generates, lead to the both ends of tourmaline
Positive and negative charge is generated, the positive and negative charge of generation improves the electric conductivity of its surrounding water, therefore anthraquinone compounds work can be improved
It is acted on for the accelerated degradation of redox mediators azo dyes, nitrate.
The present invention utilizes the chloropropyl containing amino group and modified by chloropropyl by tourmaline surface on aminoanthraquinone compound
Dehydrochlorination reaction between group promotes the progress of reaction using acid binding agent absorbing hydrogen chloride, so that tourmaline passes through chemistry
Key has the characteristics that stability is good in surface grafting anthraquinone compounds.
The beneficial effects of the present invention are:
(1) present invention uses cheap tourmaline as physical support, from a wealth of sources, at low cost；
(2) reaction step of the invention is few, reaction process is simple, at low cost；
(3) present invention generates the raw material of toxic and harmful gas without the contact of easy and moisture；
(4) tourmaline of surface grafting anthraquinone compounds that the present invention obtains can obvious speedup azo dyes and nitrate
Biodegradation rate, and after simply handling, it can continue to use.
(5) present invention utilizes the pyroelectricity and piezoelectricity of tourmaline, produces in variation of ambient temperature and/or to tourmaline both ends
In the case where raw pressure, so that the tourmaline containing anthraquinone compounds more quickly promotes the drop of azo dyes, nitrate etc.
Solution.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
If not specified, the number in following embodiments is all parts by weight.
Embodiment 1
The dilute hydrochloric acid of 100 parts of dehydrated alcohols, 10 parts of chloropropyl triethoxysilanes and 1 part of mass concentration 0.1wt% is existed
It stirs 0.5 hour at room temperature, is added in 50 parts of 3 μm of tourmaline, is warming up to 60 DEG C, be stirred to react 2 hours, cool down, filtering,
It filters out solid washes of absolute alcohol 3 times, it is dry, obtain modified by chloropropyl by tourmaline 1.
Container is placed in 10 DEG C of water-bath, sequentially add 100 parts of modified by chloropropyl by tourmaline, 1,21 part of 2- amino anthraquinones,
350 parts of tetrahydrofurans and 11.3 parts of triethylamines, are stirred to react 5 hours, are warming up to 55 DEG C, stir 3 hours, and filtering filters out solid
It is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, it is dry, it obtains to surface and is fixed with the tourmaline of anthraquinone compounds
1.FT-IR analysis, product is in 1668cm-1There is strong sharp absorption peak in place, is the characteristic absorption of carbonyl on anthraquinone ring
Peak, in 1598cm-1There is the sharp absorption peak of moderate strength, is the hydrocarbon characteristic absorption peak on phenyl ring, shows anthraquinone chemical combination
Object is fixed on the surface of tourmaline.The N element content that fixed front and back tourmaline is measured using elemental analysis method, passes through calculating
The anthraquinone compounds content for obtaining 1 surface of tourmaline is 2.03mmol/g.
Embodiment 2
By the dilute hydrochloric acid of 100 parts of methanol, 15 parts of r-chloropropyl trimethoxyl silanes and 1 part of mass concentration 0.1wt% in room temperature
Lower stirring 0.5 hour, is added in 100 parts of 10 μm of tourmaline, is warming up to 50 DEG C, be stirred to react 3 hours, cools down, and filters, filter
Solid is dry with washes of absolute alcohol 3 times out, obtains modified by chloropropyl by tourmaline 2.
Container is placed in 14 DEG C of water-bath, sequentially add 100 parts of modified by chloropropyl by tourmaline, 2,12 parts of 1- amino anthraquinones,
500 parts of tetrahydrofurans and 8.1 parts of triethylamines, are stirred to react 8 hours, are warming up to 55 DEG C, stir 5 hours, and filtering filters out solid
It is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, it is dry, it obtains to surface and is fixed with the tourmaline of anthraquinone compounds
2.The N element content that fixed front and back tourmaline is measured using elemental analysis method, is obtained by calculation the anthracene on 2 surface of tourmaline
Naphtoquinone compounds content is 1.77mmol/g.
Embodiment 3
Container is placed in 14 DEG C of water-bath, sequentially adds 100 parts of modified by chloropropyl by tourmaline, 2,12 parts of 2,6- diamino
Anthraquinone, 500 parts of tetrahydrofurans and 13 parts of triethylamines, are stirred to react 6 hours, are warming up to 55 DEG C, stir 5 hours, and filtering filters out
Solid is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, dry, is obtained to surface and is fixed with the electricity of anthraquinone compounds
Gas stone 3.The N element content that fixed front and back tourmaline is measured using elemental analysis method, is obtained by calculation 2 surface of tourmaline
Anthraquinone compounds content be 1.62mmol/g.
Embodiment 4
By the dilute hydrochloric acid of 100 parts of methanol, 20 parts of r-chloropropyl trimethoxyl silanes and 1 part of mass concentration 0.1wt% in room temperature
Lower stirring 0.5 hour, is added in 100 parts of 100 μm of tourmaline, is warming up to 50 DEG C, be stirred to react 3 hours, cools down, filtering,
It filters out solid washes of absolute alcohol 3 times, it is dry, obtain modified by chloropropyl by tourmaline 4.
Container is placed in 12 DEG C of water-bath, sequentially add 100 parts of modified by chloropropyl by tourmaline, 4,21 parts of 1- amino anthraquinones,
400 parts of tetrahydrofurans and 11.8 parts of triethylamines, are stirred to react 5 hours, are warming up to 60 DEG C, stir 5 hours, and filtering filters out solid
It is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, it is dry, it obtains to surface and is fixed with the tourmaline of anthraquinone compounds
4.The N element content that fixed front and back tourmaline is measured using elemental analysis method, is obtained by calculation the anthracene on 4 surface of tourmaline
Naphtoquinone compounds content is 1.45mmol/g.
Embodiment 5
Container is placed in 12 DEG C of water-bath, sequentially adds 100 parts of modified by chloropropyl by tourmaline, 4,20 parts of 2,6- diamino
Anthraquinone, 500 parts of tetrahydrofurans and 14.6 parts of pyridines, are stirred to react 5 hours, are warming up to 60 DEG C, stir 5 hours, and filtering filters out
Solid is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, dry, is obtained to surface and is fixed with the electricity of anthraquinone compounds
Gas stone 5.The N element content that fixed front and back tourmaline is measured using elemental analysis method, is obtained by calculation 5 surface of tourmaline
Anthraquinone compounds content be 1.38mmol/g.
Embodiment 6
By the dilute hydrochloric acid of 100 parts of isopropanols, 30 parts of r-chloropropyl trimethoxyl silanes and 1 part of mass concentration 0.1wt% in room
It temperature lower stirring 1 hour, is added in 100 parts of 500 μm of tourmaline, is warming up to 70 DEG C, be stirred to react 2 hours, cool down, filtering,
It filters out solid washes of absolute alcohol 3 times, it is dry, obtain modified by chloropropyl by tourmaline 5.
Container is placed in 12 DEG C of water-bath, sequentially adds 100 parts of modified by chloropropyl by tourmaline, 5,28 parts of 1- amino -2- bromines
- 4- hydroxy-anthraquione, 500 parts of toluene and 9.7 parts of pyridines, are stirred to react 10 hours, are warming up to 55 DEG C, stir 4 hours, filter, filter
Solid is cleaned 3 times with deionized water out, then with washes of absolute alcohol 3 times, dry, is obtained to surface and is fixed with anthraquinone compounds
Tourmaline 6.The N element content that fixed front and back tourmaline is measured using elemental analysis method, is obtained by calculation 6 table of tourmaline
The anthraquinone compounds content in face is 1.14mmol/g.
Comparative example 1
By the dilute hydrochloric acid of 100 parts of methanol, 15 parts of r-chloropropyl trimethoxyl silanes and 1 part of mass concentration 0.1wt% in room temperature
Lower stirring 0.5 hour, is added in 100 parts of 10 μm of talcum powder, is warming up to 50 DEG C, be stirred to react 3 hours, cools down, and filters, filter
Solid is dry with washes of absolute alcohol 3 times out, obtains modified by chloropropyl by talcum powder.
Container is placed in 14 DEG C of water-bath, sequentially add 100 parts of modified by chloropropyl by talcum powder, 12 parts of 1- amino anthraquinones,
350 parts of tetrahydrofurans and 8.1 parts of triethylamines, are stirred to react 8 hours, are warming up to 55 DEG C, stir 5 hours, and filtering filters out solid
It is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, it is dry, it obtains to surface and is fixed with the talcum powder of anthraquinone compounds.
The N element content that fixed front and back talcum powder is measured using elemental analysis method, is obtained by calculation the anthraquinone on talcum powder surface
Conjunction object content is 1.70mmol/g.
Comparative example 2
By the dilute hydrochloric acid of 100 parts of methanol, 20 parts of r-chloropropyl trimethoxyl silanes and 1 part of mass concentration 0.1wt% in room temperature
Lower stirring 0.5 hour, is added to 100 parts of 100 μm of powdered whitings, is warming up to 50 DEG C, be stirred to react 3 hours, cools down, mistake
Filter, filters out solid washes of absolute alcohol 3 times, dry, obtains modified by chloropropyl by powdered whiting.
Container is placed in 12 DEG C of water-bath, sequentially adds 100 parts of modified by chloropropyl by powdered whitings, 21 parts of 1- amino anthracenes
Quinone, 400 parts of tetrahydrofurans and 11.8 parts of triethylamines, are stirred to react 5 hours, are warming up to 60 DEG C, stir 5 hours, and filtering filters out
Solid is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, dry, is obtained to surface and is fixed with the weight of anthraquinone compounds
Matter calcium carbonate.The N element content that fixed front and back powdered whiting is measured using elemental analysis method, is obtained by calculation heavy
The anthraquinone compounds content of calcium carbonate surface is 1.48mmol/g.
Test
Degradation of Azo Dyes acceleration effect test: respectively by 2g blank tourmaline, 2g embodiment 1-6 and 2g comparative example 1-2
The product of middle surface grafting anthraquinone compounds is added to azo of the 200ml containing logarithmic growth phase with after normal saline flushing 3 times
In the Acid Red B of the 120mg/L of dye degradation strain GYZ (staphylococcus sp.) under the speed of agitator of 10rpm into
Row decoloration test, measurement Acid Red B concentration change with time.The results are shown in Table 1.
Nitrate degradation acceleration effect test: respectively will be in 2g blank tourmaline, 2g embodiment 1-6 and 2g comparative example 1-2
It is micro- to be added to 200ml denitrification containing logarithmic growth phase with after normal saline flushing 3 times for the product of surface grafting anthraquinone compounds
It is tested under the speed of agitator of 10rpm in the nitrate wastewater of the 150mg/L of biology, measurement nitrate concentration is at any time
Variation.The results are shown in Table 2.
Stability test: the tourmaline of surface grafting anthraquinone compounds in 2g embodiment 1-6 is rushed with physiological saline respectively
After washing 3 times, it is added to Degradation of Azo Dyes bacterial strain GYZ (staphylococcus sp.) of the 200ml containing logarithmic growth phase
Decoloration test is carried out in the Acid Red B of 120mg/L, the concentration of Acid Red B after measurement 8 hours.Test rear surface is grafted anthraquinone
It is small that with Acid Red B decoloration test 8 is carried out according to the above method again after the tourmaline of compound clear water and washes of absolute alcohol are dry
When, it tests 12 times repeatedly.Wherein, the test process of embodiment 1-3 is carried out under the speed of agitator of 10rpm, is implemented
Example 4-6 test process be again 25-30 DEG C to be carried out under the temperature change of 1 DEG C/min, the results are shown in Table 3.
1 Acid Red B of table degradation accelerated test result
As shown in Table 1, the tourmaline of surface grafting anthraquinone compounds of the invention has significant promotion Acid Red B azo
The effect of dyestuff degradation, and with the increase of anthraquinone compounds content, faster to the degradation of Acid Red B.Comparative example 4
With the test of comparative example 1, the content of the anthraquinone compounds of tourmaline surface grafting is significantly lower than comparative example 1 in embodiment 4, but
It is similar to the degradation effect of Acid Red B dyestuff.The test of comparative example 6 and comparative example 2 has same result.Cause
This, can be degraded azo dyes faster using the tourmaline of the invention containing anthraquinone compounds.
2 nitrate of table degradation accelerated test result
As shown in Table 2, the tourmaline of surface grafting anthraquinone compounds of the invention has significant promotion nitrate degradation
Effect, and with the increase of anthraquinone compounds content, faster to the degradation of nitrate.Comparative example 4 and comparative example 1
Test, the content of the anthraquinone compounds of tourmaline surface grafting is significantly lower than comparative example 1 in embodiment 4, but to nitrate
Degradation effect it is similar.The test of comparative example 6 and comparative example 2 has same result.Therefore, using of the invention
Tourmaline containing anthraquinone compounds can degrade nitrate faster.
3 Acid Red B stability to degradation measurement result of table
As shown in Table 3, the tourmaline for the surface grafting anthraquinone compounds that the present invention obtains is promoting azo dyes and nitric acid
Also there is preferable effect after Reusability 12 times in salt biodegrade.
In conclusion the life of the tourmaline azo dyes and nitrate for the surface grafting anthraquinone compounds that the present invention obtains
Object degradation has preferable facilitation, and stability is good, can Reusability, can be widely applied in water process.
The basic principles, principal features and advantages of the present invention have been shown and described in the above.Those skilled in the art answer
The present invention is not limited to the above embodiments for the understanding, and above-described embodiment is only presently preferred embodiments of the present invention, Bu Nengyi
This is limited the scope of implementation of the present invention, i.e. equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification, all
Should still it belong in the range of the present invention covers.The claimed scope of the invention is defined by appended claims and its equivalent.
Claims (10)
1. a kind of preparation method of the tourmaline containing anthraquinone compounds, it is characterised in that: include the following steps,
S1,0.5- is stirred at room temperature in the dilute hydrochloric acid of organic solvent one, chloropropyl silane coupling agent and mass concentration 0.1wt%
It 2 hours, is added in tourmaline, is warming up to no more than 80 DEG C, reacts 1-5 hours, cool down, filtering filters out solid with anhydrous second
Alcohol cleans 3 times, dry, obtains modified by chloropropyl by tourmaline；
S2, the modified by chloropropyl by tourmaline for obtaining step S1 are added containing aminoanthraquinone compound, organic solvent two and acid binding agent
It into container, is stirred to react at 10-15 DEG C 1-10 hours, is warming up to 55-60 DEG C, stirred 1-5 hours, filtering filters out solid
It is cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times, it is dry, obtain the tourmaline containing anthraquinone compounds.
2. preparation method according to claim 1, it is characterised in that: organic solvent one described in step S1, chloropropyl silicon
The weight ratio of alkane coupling agent, dilute hydrochloric acid and tourmaline is 1:0.1-0.3:0.01:0.5-1.
3. preparation method according to claim 1 or 2, it is characterised in that: organic solvent one and step described in step S1
Organic solvent two described in S2 be selected from methanol, dehydrated alcohol, isopropanol, normal propyl alcohol, ethyl acetate, butyl acetate, tetrahydrofuran,
One or more of methyl ethyl ketone, toluene and dimethylbenzene.
4. preparation method according to claim 1 or 2, it is characterised in that: chloropropyl silane coupling agent described in step S1
Selected from 3- r-chloropropyl trimethoxyl silane, 3- chloropropyl triethoxysilane, 3- chloropropylmethyldimethoxysilane and 3- chlorine
One or more of hydroxypropyl methyl diethoxy silane.
5. preparation method according to claim 1 or 2, it is characterised in that: the average grain diameter of tourmaline described in step S1
0.1 μm~1cm.
6. preparation method according to claim 1, it is characterised in that: modified by chloropropyl by tourmaline described in step S2 contains
The weight ratio of aminoanthraquinone compound and organic solvent two is 1:0.1-0.3:3-8；Chemical combination containing amino anthraquinones described in step S2
The middle amino molal quantity of object and the mole ratio of the acid binding agent are 1:1.05-1.5.
7. preparation method according to claim 1 or 6, it is characterised in that: contain aminoanthraquinone compound described in step S2
Selected from 1- AMINO 2 BROMO 4 HYDROXY ANTHRAQUINONE1- amino-2-methyl anthraquinone2- amino anthraquinones1- amino anthraquinones1,2-
Diamino-anthraquinone1,4- diamino-anthraquinone2,6- diamino-anthraquinone1,8- diamino-anthraquinone1,5- diamino-anthraquinoneWith 1,5- dihydroxy -4,8- diamino-anthraquinoneOne or more of.
8. preparation method according to claim 1 or 6, it is characterised in that: acid binding agent described in step S2 be selected from triethylamine,
Pyridine, triethanolamine, diethanol amine, N, in N- diisopropylethylamine, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide
It is one or more of.
9. a kind of tourmaline containing anthraquinone compounds that the described in any item preparation methods of claim 1-8 are prepared.
10. a kind of tourmaline containing anthraquinone compounds that the described in any item preparation methods of claim 1-8 are prepared is in water
The application of process field.
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| WO2020221240A1 (en) * | 2019-04-29 | 2020-11-05 | 厦门理工学院 | Method for preparing tourmaline containing anthraquinone compound by means of thiol-ene click chemistry and application thereof |
| WO2020221242A1 (en) * | 2019-04-29 | 2020-11-05 | 厦门理工学院 | Method for preparing inorganic filler with anthraquinone compound fixed on surface thereof and use thereof |
| WO2020221244A1 (en) * | 2019-04-29 | 2020-11-05 | 厦门理工学院 | Anthraquinone compound-containing tourmaline, preparation method and application thereof |
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