CN111320256A - Preparation method of maleic anhydride liquid-phase grafted basalt fiber biological carrier - Google Patents

Preparation method of maleic anhydride liquid-phase grafted basalt fiber biological carrier Download PDF

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CN111320256A
CN111320256A CN202010134326.9A CN202010134326A CN111320256A CN 111320256 A CN111320256 A CN 111320256A CN 202010134326 A CN202010134326 A CN 202010134326A CN 111320256 A CN111320256 A CN 111320256A
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basalt fiber
basalt
maleic anhydride
liquid phase
basalt fibers
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黄娟
黄敏杰
肖君
王鸣宇
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Southeast University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • C02F3/105Characterized by the chemical composition
    • C02F3/107Inorganic materials, e.g. sand, silicates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • C02F3/2806Anaerobic processes using solid supports for microorganisms
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

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  • Inorganic Chemistry (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

The invention belongs to the technical field of sewage/wastewater treatment biomembrane carriers, relates to modification of inorganic basalt fiber carriers, and particularly relates to a method for surface modification of micron-sized inorganic basalt fiber carriers for sewage/wastewater treatment. Firstly, immersing basalt fibers pretreated by acetone into a dilute alkali solution for etching, then activating the surface groups of the basalt fibers by using a 30% hydrogen peroxide solution, immersing the basalt fibers into an ethyl acetate solution of maleic anhydride, carrying out grafting reaction by using concentrated hydrochloric acid as an initiator, and finally drying to constant weight. The basalt fiber carrier prepared by the invention has the advantages that the surface roughness is obviously improved, and meanwhile, due to the increase of oxygen-containing functional groups on the surface of the basalt fiber, the basalt fiber carrier has good hydrophilicity and biocompatibility, so that more biomass can be loaded, higher microbial activity can be maintained for a long time, and the sewage and wastewater purification effect is obviously improved. The method disclosed by the invention is simple to operate, easy to popularize and capable of being widely applied to the field of biofilm carrier fillers for sewage and wastewater treatment.

Description

Preparation method of maleic anhydride liquid-phase grafted basalt fiber biological carrier
Field of the invention
The invention belongs to the technical field of sewage/wastewater treatment biomembrane carriers, relates to modification of inorganic basalt fiber carriers, and particularly relates to a method for surface modification of micron-sized inorganic basalt fiber carriers for sewage/wastewater treatment.
Background
The basalt fiber is a flexible inorganic fiber, has the advantages of large specific surface area, high mechanical strength, good chemical and biological stability and the like, and has the general characteristics of being used as a biological carrier. In addition, the basalt fiber has sufficient source and low price, and has independent intellectual property rights in China, thereby providing important advantages for wide application. The Chinese invention patent "a biological carrier for water purification" (CN104176822A) discloses that basalt fiber can be used as a biological membrane carrier material for water purification, and has the characteristics of easy unfolding, difficult falling, long service life, large specific surface area, high utilization efficiency of the fiber and the like. However, basalt fibers have smooth surfaces, exhibit electronegativity, and generally have poor hydrophilicity on the surfaces of commercially available basalt fibers, which all affect the initial adhesion of microorganisms and the mass transfer efficiency of biofilms. Because the basalt fiber has excellent chemical stability, the biocompatibility of the basalt fiber is improved by modification before application, so that the basalt fiber becomes an excellent biomembrane carrier.
Maleic Anhydride (MAH) is a polar compound containing multiple functional groups, contains unsaturated double bonds in a molecular structure, and is easy to generate polymerization reaction with other polymers under the action of an initiator; the acid anhydride group can also react with a functional group such as a hydroxyl group, a carboxyl group, or an amine group. The research on the independent grafting treatment of the fiber surface is not much, mainly because the basalt fiber is an inorganic substance and is difficult to directly react with a monomer, the monomer is grafted after hydrogen peroxide activation is carried out, so that the oxygen-containing functional group on the surface of the basalt fiber is increased, and the basalt fiber has better hydrophilicity and biocompatibility.
In the current researches on the surface modification technology of basalt fibers, most of the researches focus on improving the mechanical property of the basalt fibers, and few basalt fibers are used as the researches on the improvement of the hydrophilicity of the surfaces of biological carriers. In addition, at present, no report about the application of maleic anhydride to the modification of the basalt fiber carrier exists.
Disclosure of Invention
The technical problem is as follows: aiming at the defects of the prior art, the invention aims to provide a preparation method of a maleic anhydride liquid phase grafted basalt fiber biological carrier, the modified basalt fiber is obtained through the processes of pretreatment, alkali etching, activation, liquid phase grafting and the like, and the oxygen-containing functional groups on the surface of the modified basalt fiber are increased to ensure that the modified basalt fiber has good hydrophilicity and biocompatibility, so that more biomass can be loaded, and the requirement of the modified basalt fiber on waste/wastewater biological treatment carrier filler can be met.
The technical scheme is as follows: in order to solve the technical problems, the preparation method of the maleic anhydride liquid phase grafted basalt fiber biological carrier adopts the following technical scheme:
step 1, pretreatment: immersing basalt fibers into acetone, cleaning for 1-3 hours under the action of ultrasonic waves to remove impurities added on the surface in the production process, repeatedly washing the basalt fibers with distilled water for many times after taking out, and drying the basalt fibers at 105-120 ℃ for later use;
step 2, alkali etching: immersing the basalt fibers treated in the step 1 in a dilute alkali solution for etching, wherein the etching time is 1-2 h, taking out the basalt fiber bundles, washing with deionized water for many times until the pH value of the washing water is 6.5-7.5, and drying for later use;
step 3, activation: soaking the basalt fibers treated in the step 2 in a hydrogen peroxide solution for activation, wherein the soaking time is 1-3 hours, and the soaking temperature is 100-140 ℃;
step 4, liquid phase grafting: and (3) immersing the basalt fibers treated in the step (3) into an ethyl acetate solution of maleic anhydride, carrying out grafting reaction by taking concentrated hydrochloric acid as an initiator, heating in a constant-temperature water bath at 60 ℃ for 4-6 h, taking out, soaking and washing with absolute ethyl alcohol, and finally drying at 105-120 ℃ to remove surface ethyl alcohol.
Wherein:
in the step 2, the dilute alkali solution is one of NaOH and KOH, and the concentration is 0.5-2 mol/L.
The concentration mass fraction of the hydrogen peroxide solution in the step 3 is 30%.
And 4, the concentration of the ethyl acetate solution of the maleic anhydride in the step 4 is 0.1-1 mol/L.
The volume ratio of the initiator concentrated hydrochloric acid to the ethyl acetate used in the step 4 is 1: 10-1: 20.
Has the advantages that: the method for modifying the basalt fiber carrier disclosed by the invention is simple in process and convenient to operate; the prepared maleic anhydride liquid phase grafted basalt fiber carrier has the characteristics of large specific surface area of basalt fiber, good chemical and biological stability, corrosion resistance, high temperature resistance and the like, and meanwhile, the oxygen-containing functional groups on the surface are increased, so that the modified basalt fiber surface has good hydrophilicity and biocompatibility, in addition, the surface roughness of the basalt fiber is increased, the attachment of microorganisms on the surface is facilitated, the film forming amount is increased, and the sewage/wastewater treatment effect is improved;
drawings
FIG. 1 is electron microscope scanning images of basalt fiber carriers before and after modification, wherein (a) is before modification and (b) is after modification.
FIG. 2 is a diagram showing the filming effect of the modified basalt fiber carrier, wherein (a) is before modification and (b) is after modification.
Detailed Description
The invention is further described below with reference to specific examples:
example 1
(1) Weighing 40g of basalt fiber, immersing the basalt fiber into 500ml of acetone solution, putting the basalt fiber into an ultrasonic cleaning instrument for cleaning for 2 hours, taking out the basalt fiber, repeatedly cleaning the basalt fiber with deionized water, and putting the basalt fiber into a 105 ℃ drying oven for drying;
(2) preparing 0.5mol/L NaOH solution, soaking basalt fibers in the NaOH solution, taking out after 2 hours, washing with deionized water for multiple times until the pH value of the washing water is 6.5-7.5, and drying for later use;
(3) preparing a hydrogen peroxide solution with the concentration of 30%, and soaking the basalt fibers obtained in the step (2) in the hydrogen peroxide solution for activation, wherein the soaking time is 2 hours, and the soaking temperature is 125 ℃;
(4) preparing an ethyl acetate solution of maleic anhydride, weighing a certain amount of maleic anhydride, and dissolving the maleic anhydride into the ethyl acetate to prepare an ethyl acetate solution of maleic anhydride with initial concentration of 0.1 mol/L;
(5) soaking the basalt fiber obtained in the step (3) in the ethyl acetate solution of maleic anhydride obtained in the step (4), carrying out grafting reaction by taking concentrated hydrochloric acid as an initiator (the volume ratio of the concentrated hydrochloric acid to the ethyl acetate is 1:20), heating in a constant-temperature water bath at 60 ℃ for 6h, taking out, soaking and washing with absolute ethyl alcohol, finally drying at 105 ℃ and removing surface ethyl alcohol to obtain the maleic anhydride liquid-phase grafted basalt fiber carrier (MBF-1).
Example 2
(1) Weighing 40g of basalt fiber, immersing the basalt fiber into 500ml of acetone solution, putting the basalt fiber into an ultrasonic cleaning instrument for cleaning for 2 hours, taking out the basalt fiber, repeatedly cleaning the basalt fiber with deionized water, and putting the basalt fiber into a 105 ℃ drying oven for drying;
(2) preparing 0.5mol/L NaOH solution, soaking basalt fibers in the NaOH solution, taking out after 2 hours, washing with deionized water for multiple times until the pH value of the washing water is 6.5-7.5, and drying for later use;
(3) preparing a hydrogen peroxide solution with the concentration of 30%, and soaking the basalt fibers obtained in the step (2) in the hydrogen peroxide solution for activation, wherein the soaking time is 2 hours, and the soaking temperature is 125 ℃;
(4) preparing an ethyl acetate solution of maleic anhydride, weighing a certain amount of maleic anhydride, and dissolving the maleic anhydride into the ethyl acetate to prepare an ethyl acetate solution of maleic anhydride with the initial concentration of 1 mol/L;
(5) soaking the basalt fiber obtained in the step (3) in the ethyl acetate solution of maleic anhydride obtained in the step (4), carrying out grafting reaction by taking concentrated hydrochloric acid as an initiator (the volume ratio of the concentrated hydrochloric acid to the ethyl acetate is 1:20), heating in a constant-temperature water bath at 60 ℃ for 6h, taking out, soaking and washing with absolute ethyl alcohol, finally drying at 105 ℃ and removing surface ethyl alcohol to obtain the maleic anhydride liquid-phase grafted basalt fiber carrier (MBF-2).
The experimental results are as follows:
1. scanning Electron Microscopy (SEM) analysis:
as shown in figure 1, the surface of the basalt fiber carrier before modification is smooth and almost contains no impurities, and the basalt fiber carrier after maleic anhydride liquid phase grafting can clearly see that the surface of the basalt fiber after modification is uneven, the surface appearance is obviously changed, the specific surface area is increased, and the attachment amount of microorganisms is increased.
2. And (3) analyzing the film forming performance:
TABLE 1 comparison of the biofilm formation effects of basalt fiber carriers before and after modification
Figure BDA0002396796480000041
As can be seen from Table 1, the surface microorganism adhesion performance of the basalt fiber carrier after maleic anhydride liquid phase grafting is obviously improved, and the film forming rate and the residual film forming rate are obviously improved compared with unmodified basalt fiber, especially the residual film forming rate. The method shows that the attachment amount of microorganisms on the surface of the modified basalt fiber carrier is increased, higher microbial activity can be maintained for a long time, the sewage/wastewater purification effect can be improved, and the MBF-2 effect is the best.
Evaluation of amount of microorganism attached:
modified and unmodified basalt fibers are made into fiber bundles, and the fiber bundles are put into a contact oxidation reaction device (5L) for a biofilm culturing experiment. The water is artificially synthesized sewage, sodium acetate is used as a carbon source, ammonium sulfate is used as a nitrogen source, and dipotassium hydrogen phosphate is used as a phosphorus source, wherein the COD (chemical oxygen demand) N and P are 100:5: 1. Inoculating sludge is taken from a sewage treatment plant (MLSS is 8000mg/L) in Jiangning development area, continuously aerating for 72h, taking out, recording a macroscopic topography of microorganisms fixed on the surface of the basalt fiber carrier, and measuring the biofilm formation rate and the residual biofilm formation rate.
1) Film forming rate: and taking out the basalt fiber carrier, and drying to constant weight.
Figure BDA0002396796480000042
Wherein: w0: the original weight (g) of basalt fiber; w1: the sum (g) of the mass of basalt fibers and microorganisms after a certain period of time of fixing the microorganisms.
2) Residual film forming rate: and taking out the basalt fiber carrier, immersing the basalt fiber carrier into a standard PBS buffer solution, putting the basalt fiber carrier and the standard PBS buffer solution into an ultrasonic oscillator at room temperature, oscillating the basalt fiber carrier and the standard PBS buffer solution for 20min at the power of 30w, slowly washing the basalt fiber carrier by using distilled water, and drying the basalt fiber carrier to constant weight.
Figure BDA0002396796480000051
Wherein: w2: (g) mass sum of basalt fiber and microorganism after ultrasonic oscillation.
Further, the standard PBS buffer described in 2) was 8.5g/L sodium chloride, 2.28.5g/L disodium hydrogenphosphate, 0.48.5g/L sodium dihydrogenphosphate, and pH 7.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (5)

1. The preparation method of the maleic anhydride liquid phase grafted basalt fiber biological carrier is characterized by comprising the following steps:
step 1, pretreatment: immersing basalt fibers into acetone, cleaning for 1-3 hours under the action of ultrasonic waves to remove impurities added on the surface in the production process, repeatedly washing the basalt fibers with distilled water for many times after taking out, and drying the basalt fibers at 105-120 ℃ for later use;
step 2, alkali etching: immersing the basalt fibers treated in the step 1 in a dilute alkali solution for etching, wherein the etching time is 1-2 h, taking out the basalt fiber bundles, washing with deionized water for many times until the pH value of the washing water is 6.5-7.5, and drying for later use;
step 3, activation: soaking the basalt fibers treated in the step 2 in a hydrogen peroxide solution for activation, wherein the soaking time is 1-3 hours, and the soaking temperature is 100-140 ℃;
step 4, liquid phase grafting: and (3) immersing the basalt fibers treated in the step (3) into an ethyl acetate solution of maleic anhydride, carrying out grafting reaction by taking concentrated hydrochloric acid as an initiator, heating in a constant-temperature water bath at 60 ℃ for 4-6 h, taking out, soaking and washing with absolute ethyl alcohol, and finally drying at 105-120 ℃ to remove surface ethyl alcohol.
2. The method for preparing the maleic anhydride liquid phase grafted basalt fiber bio-carrier according to claim 1, wherein the method comprises the following steps: in the step 2, the dilute alkali solution is one of NaOH and KOH, and the concentration is 0.5-2 mol/L.
3. The method for preparing the maleic anhydride liquid phase grafted basalt fiber bio-carrier according to claim 1, wherein the method comprises the following steps: the concentration mass fraction of the hydrogen peroxide solution in the step 3 is 30%.
4. The method for preparing the maleic anhydride liquid phase grafted basalt fiber bio-carrier according to claim 1, wherein the method comprises the following steps: and 4, the concentration of the ethyl acetate solution of the maleic anhydride in the step 4 is 0.1-1 mol/L.
5. The method for preparing the maleic anhydride liquid phase grafted basalt fiber bio-carrier according to claim 1, wherein the method comprises the following steps: the volume ratio of the initiator concentrated hydrochloric acid to the ethyl acetate used in the step 4 is 1: 10-1: 20.
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CN111717983A (en) * 2020-07-06 2020-09-29 苏州汇博龙环保科技有限公司 Process and equipment for modifying wastewater filler material and process for treating wastewater
CN114368887A (en) * 2021-12-29 2022-04-19 图方便(苏州)环保科技有限公司 Sludge treatment device capable of promoting microbial fermentation and application thereof
CN114525074A (en) * 2022-01-25 2022-05-24 广东华达轩建筑工程有限公司 Decorative interior wall coating and preparation method thereof
CN115057526A (en) * 2022-07-06 2022-09-16 江苏大学 Preparation method and application of modified basalt fiber biological filler
CN116495870A (en) * 2023-06-28 2023-07-28 江苏省环境工程技术有限公司 Preparation method of magnesium modified basalt fiber filler suitable for sewage and wastewater treatment

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Publication number Priority date Publication date Assignee Title
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CN114525074A (en) * 2022-01-25 2022-05-24 广东华达轩建筑工程有限公司 Decorative interior wall coating and preparation method thereof
CN115057526A (en) * 2022-07-06 2022-09-16 江苏大学 Preparation method and application of modified basalt fiber biological filler
CN116495870A (en) * 2023-06-28 2023-07-28 江苏省环境工程技术有限公司 Preparation method of magnesium modified basalt fiber filler suitable for sewage and wastewater treatment

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Application publication date: 20200623