阅读说明：本技术 一种表面带电球状玻璃滤料的制备方法 (Preparation method of spherical glass filter material with charged surface ) 是由 马骁腾 赵鹏 孟玉杰 于 2019-08-30 设计创作，主要内容包括：本发明公开了一种表面带电球状玻璃滤料的制备方法,将购得的特定目数的钠钙玻璃珠原料,经预处理、硅烷偶联化、接枝改性步骤制成带有负电荷的球状玻璃滤料,根据建立指定波长下的吸光度与接枝单体物质浓度之间的校正曲线或回归方程,计算出不同反应时刻单体物质的反应量,从而控制滤料表面Zeta电位,制成不同带负电量的球状玻璃滤料。本发明制备的表面带电球状玻璃滤料具有机械强度更高、反冲洗强度更低、使用寿命更长的特点,能够提升滤池处理效率。(The invention discloses a preparation method of a spherical glass filter material with a charged surface, which is characterized in that a purchased soda-lime glass bead raw material with a specific mesh number is subjected to pretreatment, silane coupling and grafting modification to prepare the spherical glass filter material with negative charges, and the reaction amount of monomer substances at different reaction moments is calculated according to a calibration curve or a regression equation established between the absorbance at a specified wavelength and the concentration of grafted monomer substances, so that the Zeta potential on the surface of the filter material is controlled to prepare the spherical glass filter material with different negative charges. The spherical glass filter material with the charged surface prepared by the invention has the characteristics of higher mechanical strength, lower backwashing strength and longer service life, and can improve the treatment efficiency of the filter tank.)

1. A method for preparing a spherical glass filter material with a charged surface is characterized in that a purchased soda-lime glass bead raw material with a specific mesh number is subjected to pretreatment, silane coupling and grafting modification to prepare the spherical glass filter material with negative charges, and the reaction amount of monomer substances at different reaction moments is calculated according to a calibration curve or a regression equation established between the absorbance at a specified wavelength and the concentration of the grafted monomer substances, so that the Zeta potential on the surface of the filter material is controlled to prepare the spherical glass filter material with different negative charges.

2. The method for preparing the surface-charged spherical glass filter material according to claim 1, wherein the pretreatment of hydroxylation of the surface of the glass bead raw material comprises: cleaning the screened glass bead raw material with a specific mesh number for 5-6 times by using ethanol; putting the cleaned glass bead raw materials into a beaker filled with deionized water, ethanol and acetone in sequence, and carrying out ultrasonic treatment for 10 min; putting the glass bead raw material subjected to ultrasonic cleaning into a human acid solution, and then carrying out acid washing in a water bath for 2 hours; and after the water bath pickling is finished, repeatedly washing the acid liquor remained in the glass beads with deionized water, and putting the glass beads into ethanol for storage for later use.

3. The method for preparing a surface-charged spherical glass filter material according to claim 1, wherein the silane coupling of the surfaces of the glass bead raw materials: preparing a silane coupling agent, immersing the pickled glass bead raw material into a prepared silane coupling agent solution, adding a catalyst, and standing for 24 hours; after standing, thoroughly washing with ethanol, performing ultrasonic treatment in ethanol solution for 5min, and storing in ethanol solution.

4. The method for preparing the surface-charged spherical glass filter material according to claim 1, wherein the grafting modification of the surfaces of the glass bead raw materials is as follows: placing the glass bead raw material connected with the silane coupling agent and ultrapure water into a big beaker, setting the water bath temperature to 80 ℃, stirring at a constant speed by using a stirring paddle, and dropwise adding 30mL of prepared 3-sulfopropyl methacrylate potassium (SPM) and Ammonium Persulfate (APS) solution once when the temperature is raised to 80 ℃ to complete the subsequent continuous reaction.

5. The method for preparing a surface-charged spherical glass filter material according to claim 1, wherein a calibration curve or a regression equation between the absorbance at a given wavelength and the concentration of the grafted monomer material is established: preparing a group of SPM solutions with different concentrations, wherein the maximum excitation wavelength of the SPM solution is 210nm because the characteristic group of the SPM (3-sulfopropyl methacrylate sylvite) is an ester group; respectively preparing solutions with the concentration C of 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0g/L, measuring the absorbance A of the solutions at the wavelength of 210nm by a spectrophotometer, repeatedly measuring for 3-5 times, and drawing a correction curve according to the absorbance A and the concentration C of the SPM or linearly regressing to obtain a regression equation at the corresponding wavelength.

Technical Field

The invention belongs to the field of preparation of environment-friendly materials and treatment of drinking water, and particularly relates to a preparation method of a spherical glass filter material with an electrified surface.

Background

The filter tank is used as the final pass of the water source purification treatment process of a water plant, mainly blocks floating matters, impurities and the like remained in water through a granular filter material layer, effectively filters organic matters and bacteria in the water, and the quality of the treatment effect can directly influence the quality of the water leaving a factory. Under the current large background that the water quality is increasingly serious and the water quality standard is increasingly improved, the operational reliability of the filter tank directly influences the safety, stability and high efficiency of the operation of a water plant, so the selection of the filter material is very important.

Generally, the filter material adopted by the filter tank of the water plant is mainly common quartz sand, and in addition, anthracite, ceramsite filter material and the like are adopted. In the actual use process of the traditional quartz sand filter material, the problems that the quartz sand has a long biological membrane, the mechanical strength is low, a large amount of washing water is consumed and the like are found. Because the surface of the common quartz sand has pores and gullies, the biological membrane is often tightly fit with the surface of the filter material, so that the backwashing strength and time are increased, the upper-layer filter material is lost, the backwashing water amount is continuously increased, and finally the filter material with saturated adsorption is replaced.

Aiming at the problem of low biological membrane growth and washing efficiency in the actual operation of the filter tank of the water plant at present, the preparation of the spherical glass filter material with the charged surface, which has high mechanical strength, low back washing strength and long service life, has important significance.

Disclosure of Invention

Aiming at the current situation that the filter material which can overcome the growth of a biological membrane and greatly improve the mechanical strength and the service life is lacked in the prior art, the preparation method of the spherical glass filter material with the charged surface is provided, the prepared spherical glass filter material with the charged surface has the characteristics of higher mechanical strength, lower back washing strength and longer service life, and the treatment efficiency of the filter tank can be improved.

The purpose of the invention is realized by the following technical scheme.

The invention relates to a preparation method of a spherical glass filter material with charged surface, which comprises the steps of pretreating, silane coupling and graft modification of purchased soda-lime glass bead raw materials with specific meshes to prepare the spherical glass filter material with negative charges, and calculating the reaction amount of monomer substances at different reaction moments according to a calibration curve or a regression equation established between the absorbance at a specified wavelength and the concentration of the grafted monomer substances, so as to control the Zeta potential on the surface of the filter material and prepare the spherical glass filter materials with different negative charges.

The pretreatment of hydroxylation of the surface of the glass bead raw material comprises the following steps: cleaning the screened glass bead raw material with a specific mesh number for 5-6 times by using ethanol; putting the cleaned glass bead raw materials into a beaker filled with deionized water, ethanol and acetone in sequence, and carrying out ultrasonic treatment for 10 min; putting the glass bead raw material subjected to ultrasonic cleaning into a human acid solution, and then carrying out acid washing in a water bath for 2 hours; and after the water bath pickling is finished, repeatedly washing the acid liquor remained in the glass beads with deionized water, and putting the glass beads into ethanol for storage for later use.

Silane coupling on the surface of the glass bead raw material: preparing a silane coupling agent, immersing the pickled glass bead raw material into a prepared silane coupling agent solution, adding a catalyst, and standing for 24 hours; after standing, thoroughly washing with ethanol, performing ultrasonic treatment in ethanol solution for 5min, and storing in ethanol solution.

Grafting modification of the surface of the glass bead raw material: placing the glass bead raw material connected with the silane coupling agent and ultrapure water into a big beaker, setting the water bath temperature to 80 ℃, stirring at a constant speed by using a stirring paddle, and dropwise adding 30mL of prepared 3-sulfopropyl methacrylate potassium (SPM) and Ammonium Persulfate (APS) solution once when the temperature is raised to 80 ℃ to complete the subsequent continuous reaction.

Establishing a calibration curve or regression equation between the absorbance at the specified wavelength and the concentration of the grafting monomer material: preparing a group of SPM solutions with different concentrations, wherein the maximum excitation wavelength of the SPM solution is 210nm because the characteristic group of the SPM (3-sulfopropyl methacrylate sylvite) is an ester group; respectively preparing solutions with the concentration C of 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0g/L, measuring the absorbance A of the solutions at the wavelength of 210nm by a spectrophotometer, repeatedly measuring for 3-5 times, and drawing a correction curve according to the absorbance A and the concentration C of the SPM or linearly regressing to obtain a regression equation at the corresponding wavelength.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

The preparation method of the spherical glass filter material with the charged surface realizes the accurate control of the negative charge amount on the surface and the grain diameter of the filter material. Compared with the traditional quartz sand filter material, the filter material has fewer pores and gullies on the surface, and due to the electronegativity of the surface, according to the DLVO theory, the filter material can effectively solve the problem of biofilm growth in the use process, improves the service life of the filter material, reduces the backwashing strength and the backwashing water quantity, reduces the production cost of a water plant, and has economic value and environmental protection significance.

drawings

FIG. 1 is a calibration curve of absorbance A and concentration C at a wavelength of 210 nm.

Detailed Description

The invention is further described below with reference to the accompanying drawings.

The invention relates to a preparation method of a spherical glass filter material with charged surface, which comprises the steps of pretreating, silane coupling, grafting modification and the like of purchased soda-lime glass bead raw materials with specific meshes to prepare the spherical glass filter material with negative charges, and calculating the reaction amount of monomer substances at different reaction moments according to a calibration curve or a regression equation established between the absorbance at a specified wavelength and the concentration of the grafted monomer substances, so as to control the Zeta potential on the surface of the filter material and prepare the spherical glass filter materials with different negative charges.

Wherein, the pretreatment of hydroxylation of the surface of the glass bead raw material: washing the glass bead raw material with a specific screened mesh number with ethanol for about 5-6 times; putting the cleaned glass bead raw materials into a beaker filled with deionized water, ethanol and acetone in sequence, and carrying out ultrasonic treatment for 10 min; putting the glass bead raw material subjected to ultrasonic cleaning into a human acid solution, and then carrying out acid washing in water bath (at 95 ℃) for 2 hours; and after the water bath pickling is finished, repeatedly washing the acid liquor remained in the glass beads with deionized water, and putting the glass beads into ethanol for storage for later use. The main purpose of this step is to clean the surface of the filter material from organic impurities. Wherein the 'edible acid' solution consists of concentrated sulfuric acid and hydrogen peroxide, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 7: 3.

Wherein, silane coupling on the surface of the glass bead raw material: preparing a silane coupling agent, immersing the acid-washed glass bead raw material into the prepared silane coupling agent solution, adding catalysts DCC (N, N' -methyltetra-cyclohexyldicyclohexylamine) and DMAP (N, N-dimethyl-4-pyridylamine), and standing for 24 hours. After standing, thoroughly washing with ethanol, performing ultrasonic treatment in ethanol solution for 5min, and storing in ethanol solution. Wherein the silane coupling agent is a toluene solution of gamma-Methacryloxypropyltrimethoxysilane (MPS). MPS (gamma-methacryloxypropyltrimethoxysilane) is a silane coupling agent with good stability, forms a Si-O-Si bond through hydrolysis, thereby fixing one end of the silane coupling agent on glass, exposing an active organic functional group with a double bond at the other end on the surface, realizing grafting of various functional monomer substances, and being the basis of surface functionalization of filter materials.

Wherein, the grafting modification of the surface of the glass bead raw material: placing the glass bead raw material connected with the silane coupling agent and ultrapure water into a big beaker, setting the water bath temperature to 80 ℃, stirring at a constant speed by using a stirring paddle, and dropwise adding 30mL of prepared 3-sulfopropyl methacrylate potassium (SPM) and Ammonium Persulfate (APS) solution once when the temperature is raised to 80 ℃ to complete the subsequent continuous reaction. After silane coupling, the double bond at one end of MPS can theoretically undergo a double bond polymerization reaction with 3-sulfopropyl methacrylate potassium (SPM), thereby negatively charging the surface of the glass bead raw material.

Wherein, a calibration curve or regression equation between the absorbance at a specified wavelength and the concentration of the grafting monomer material is established: a group of SPM solutions with different concentrations is prepared, and the maximum excitation wavelength of the SPM solution is 210nm because the characteristic group of the SPM (3-sulfopropyl methacrylate potassium salt) is an ester group. Respectively preparing solutions with the concentration C of 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0g/L, measuring the absorbance A of the solutions at the wavelength of 210nm by a spectrophotometer, repeatedly measuring for 3-5 times, and drawing a correction curve according to the absorbance A and the concentration C of the SPM or linearly regressing to obtain a regression equation at the corresponding wavelength. The absorbance A of the reaction solution can be sampled and measured at any time during the reaction, the concentration C of the monomer SPM in the reaction solution is correspondingly obtained, whether the reaction is complete or not and the reaction amount of the monomer are determined, so that the Zeta potential on the surface of the filter material is controlled, and the spherical glass filter materials with different negative amounts are manufactured.