阅读说明：本技术 一种改性表面带负电的新型玻璃渣过滤材料的制备方法 (Preparation method of novel glass residue filtering material with modified negatively charged surface ) 是由 赵鹏 史全滨 马骁腾 于 2018-06-01 设计创作，主要内容包括：本发明公开了一种改性表面带负电的新型玻璃渣过滤材料的制备方法,包括以下步骤：步骤S101:玻璃渣表面羟基化的预处理：a.用优级纯(GR)99.8%的乙醇反复清洗玻璃渣原料5-6次；b.将清洗好的玻璃渣原料依次放入盛有去离子水、乙醇、丙酮的烧杯中各超声10min；c.用氮气将经过超声清洗后的玻璃渣原料彻底吹干；d.将氮气吹干后的玻璃渣原料放入“食人酸”溶液(浓硫酸和双氧水的体积比为7：3),然后在95℃下水浴1-2h。本发明本发明实现了一种基于废弃玻璃资源再生利用的新型滤料,相较于石英砂传统滤料,具有节约反冲洗水、过滤效果好、滤料不易流失等优点,对水厂等使用单位降低生产成本、降低运行操作难度等具有重大意义。(The invention discloses a preparation method of a novel glass slag filtering material with a modified surface with negative electricity, which comprises the following steps: step S101, preprocessing the hydroxylation of the surface of the glass slag: a. repeatedly cleaning the glass slag raw material for 5-6 times by using 99.8% ethanol of high-grade pure (GR); b. sequentially putting the cleaned glass slag raw materials into a beaker filled with deionized water, ethanol and acetone, and performing ultrasonic treatment for 10min respectively; c. thoroughly drying the ultrasonically cleaned glass slag raw material by using nitrogen; d. and putting the glass slag raw material dried by the nitrogen into a 'human-eating acid' solution (the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 7: 3), and then carrying out water bath for 1-2h at 95 ℃. Compared with the traditional quartz sand filter material, the novel filter material based on the waste glass resource recycling has the advantages of saving backwashing water, being good in filtering effect, being not easy to lose the filter material and the like, and has great significance in reducing the production cost, the operation difficulty and the like of using units such as water plants and the like.)

1. A preparation method of a novel glass slag filtering material with a modified surface with negative electricity is characterized by comprising the following steps: the method comprises the following steps:

Step S101, preprocessing the hydroxylation of the surface of the glass slag: a. repeatedly cleaning the glass slag raw material for 5-6 times by using 99.8% ethanol of high-grade pure (GR); b. sequentially putting the cleaned glass slag raw materials into a beaker filled with deionized water, ethanol and acetone, and performing ultrasonic treatment for 10min respectively; c. thoroughly drying the ultrasonically cleaned glass slag raw material by using nitrogen; d. putting the glass slag raw material dried by nitrogen into a 'human-eating acid' solution (the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 7: 3), and then carrying out water bath for 1-2h at 95 ℃; e. washing the residual sulfuric acid on the glass slag raw material after the completion of the water bath at 95 ℃ with deionized water, and then putting the glass slag raw material into ethanol or deionized water for storage for later use;

Step S102, silane coupling on the surface of the glass slag: a. preparing a toluene solution of gamma-Methacryloxypropyltrimethoxysilane (MPS) (a silane coupling agent) (the ratio of toluene to MPS is 8ml of toluene and 8mg of MPS, and then adjusting the pH value to 3 by using acetic acid); b. immersing the hydroxylated glass slag dried by nitrogen into a prepared silane coupling agent solution, dropwise adding a catalyst solution, adjusting the dosage by self (DCC and DMAP), and standing for 24 hours; c. after the standing reaction is finished, thoroughly washing the glass sheet with ethanol, ultrasonically treating the glass sheet in a 99.8% ethanol solution of grade III pure (GR) for 3-5min, and then putting the glass sheet into ethanol for storage for later use;

Step S103, electrification functionalization of the surface of the glass slag: because the gamma-Methacryloxypropyltrimethoxysilane (MPS) has double bonds, the gamma-Methacryloxypropyltrimethoxysilane (MPS) can theoretically perform double bond polymerization with 3-sulfopropyl methacrylate potassium Salt (SPM), so that the surface of the glass slag is negatively charged; placing the glass slag and the ultrapure water connected with the silane coupling agent into a large beaker, setting the water bath temperature to 80 ℃, carrying out magnetic stirring, in the process of heating, heating to 60 ℃, respectively dropwise adding a proper amount of 3-sulfopropyl methacrylate potassium (SPM) and ammonium persulfate (initiator APS) solution (initiator and functional monomer), controlling the dropwise adding time to be about 20min, and continuously reacting for 3-5h after the dropwise adding is finished.

2. The preparation method of the novel glass slag filtering material with the modified surface with the negative charge, according to claim 1, is characterized in that: in the step S101, the crushed flat glass slag is used as a raw material, and the glass slag raw material subjected to ultrasonic cleaning is dried by using nitrogen, so that the influence of impurities in the air on the hydroxylation of the surface of the glass slag is isolated as much as possible.

3. The preparation method of the novel glass slag filtering material with the modified surface with the negative charge, according to claim 1, is characterized in that: in the step S102, gamma-Methacryloxypropyltrimethoxysilane (MPS) is used as a silane coupling agent, and a certain amount of DCC and DMAP solution are added as catalysts to achieve silane coupling on the surface of the glass slag.

4. The preparation method of the novel glass slag filtering material with the modified surface with the negative charge, according to claim 1, is characterized in that: in the step S103, a methacrylic acid 3-sulfopropyl ester potassium Salt (SPM) is used as a functional monomer to perform double bond polymerization reaction, so that the surface of the glass slag is negatively charged, and Ammonium Persulfate (APS) is used as an initiator; in the process of temperature rise, the temperature rises to 60 ℃ and the dropping is started, and the dropping time is controlled to be about 20 min.

Technical Field

The invention relates to the field of material science and adsorption science, in particular to a preparation method of a novel glass slag filtering material with a modified surface with negative electricity.

background

Filtration is a widely used process in water treatment (purification of drinking water and wastewater treatment). In the water treatment process, filtration generally refers to a process of intercepting suspended impurities in water by a granular filter material layer such as quartz sand, so as to clarify the water. The filtration can not only remove suspended matters in water so as to reduce turbidity, but also can reduce indexes such as BOD, COD, heavy metal ion concentration, oil content, chroma and the like along with the removal of the suspended matters. In the traditional water quality filtering process, common quartz sand is generally adopted as a filtering material in a filtering pool, and then light filtering materials such as anthracite, ceramsite filtering materials and the like which are superior to the quartz sand appear. In order to improve the pollutant removal capability of the filter material, modification research on the filter material is carried out. The general development trend of the modified filter material is to research an artificial filter material with high porosity, good mechanical strength, large specific surface area, large adsorption capacity and good surface electrical property. The modified filter material is prepared by coating a layer of modifier (usually metal oxide and hydroxide) on the surface of a common filter material through chemical reaction, so as to change the physicochemical property of the surface of the original filter material and improve the dirt-intercepting capability of the filter material. Therefore, the development of a filter material capable of being recycled and regenerated is an important subject of the research on the modified filter material. In the actual use process of a common quartz sand filter tank, the problems that a quartz sand filter material has a long biological membrane, the mechanical strength is low, a large amount of washing water is consumed and the like are found, and the filter material is usually required to be cleaned and backflushed regularly to be supplemented regularly so as to keep the continuous filtering effect. After the quartz sand filter material is continuously used for a period of time, the biggest problem is the growth of a biological membrane, and the biological membrane is always closely matched with the surface of the filter material due to pores and gullies on the surface of common quartz sand, so that the backwashing strength and the backwashing time are increased, the upper layer of the filter material is lost, the backwashing water quantity is continuously increased, the production cost of a water plant is high, and the filter material with saturated adsorption is finally replaced. The invention aims at the key problem, searches, and finally uses waste glass resources to manufacture a subversive and renewable activated filter medium for cyclic utilization through electrostatic adsorption and coordination adsorption according to DLVO (compressed double-layer theory) and a grafting modification theory. The raw material glass slag of the novel filter material has the characteristics of large specific surface area and large adsorption capacity, and the surface of the glass slag is modified, so that the using effect and the service life of the glass slag can be further improved, and the influence of the growth of a biological membrane on the filter material is avoided.

Disclosure of Invention

The invention aims to provide a preparation method of a novel glass slag filtering material with a modified surface with negative electricity, and the preparation method is used for solving the problems in the background technology.

in order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a novel glass slag filtering material with a modified surface with negative electricity comprises the following steps:

Step S101, preprocessing the hydroxylation of the surface of the glass slag: a. repeatedly cleaning the glass slag raw material for 5-6 times by using 99.8% ethanol of high-grade pure (GR); b. sequentially putting the cleaned glass slag raw materials into a beaker filled with deionized water, ethanol and acetone, and performing ultrasonic treatment for 10min respectively; c. thoroughly drying the ultrasonically cleaned glass slag raw material by using nitrogen; d. putting the glass slag raw material dried by nitrogen into a 'human-eating acid' solution (the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 7: 3), and then carrying out water bath for 1-2h at 95 ℃; e. and (3) washing the residual sulfuric acid on the glass slag raw material after the water bath at 95 ℃ is finished with deionized water, and then putting the glass slag raw material into ethanol or deionized water for storage for later use.

Step S102, silane coupling on the surface of the glass slag: a. preparing a toluene solution of gamma-Methacryloxypropyltrimethoxysilane (MPS) (a silane coupling agent) (the ratio of toluene to MPS is 8ml of toluene and 8mg of MPS, and then adjusting the pH value to 3 by using acetic acid); b. immersing the hydroxylated glass slag dried by nitrogen into a prepared silane coupling agent solution, dropwise adding a catalyst solution, adjusting the dosage by self (DCC and DMAP), and standing for 24 hours; c. and (3) thoroughly washing the glass sheet with ethanol after the standing reaction is finished, ultrasonically treating the glass sheet in a 99.8% ethanol solution of grade III pure (GR) for 3-5min after the washing is finished, and then putting the glass sheet into ethanol for storage for later use.

Step S103, electrification functionalization of the surface of the glass slag: because gamma-Methacryloxypropyltrimethoxysilane (MPS) has double bonds, the double bonds can theoretically be polymerized with 3-sulfopropyl methacrylate potassium Salt (SPM), so that the surface of the glass slag is negatively charged. Placing the glass slag and the ultrapure water connected with the silane coupling agent into a large beaker, setting the water bath temperature to 80 ℃, carrying out magnetic stirring, in the process of heating, heating to 60 ℃, respectively dropwise adding a proper amount of 3-sulfopropyl methacrylate potassium (SPM) and ammonium persulfate (initiator APS) solution (initiator and functional monomer), controlling the dropwise adding time to be about 20min, and continuously reacting for 3-5h after the dropwise adding is finished.

Further, in the step S101, the crushed flat glass slag is used as a raw material, and the glass slag raw material after ultrasonic cleaning is dried by using nitrogen, so that the influence of impurities in the air on the hydroxylation of the surface of the glass slag is isolated as much as possible.

Further, in step S102, gamma-Methacryloxypropyltrimethoxysilane (MPS) is used as a silane coupling agent, and a certain amount of DCC and DMAP solution is added as a catalyst to achieve silane coupling on the surface of the glass slag.

Further, in step S103, a double bond polymerization reaction is performed using 3-sulfopropyl methacrylate potassium Salt (SPM) as a functional monomer, so that the surface of the glass slag is negatively charged, and Ammonium Persulfate (APS) is used as an initiator. In the process of temperature rise, the temperature rises to 60 ℃ and the dropping is started, and the dropping time is controlled to be about 20 min.

Compared with the prior art, the invention has the beneficial effects that:

The preparation method can solve the problems that the upper layer filter material is lost, the backwashing water volume is continuously increased, the production cost of a water plant is high, and the filter material with saturated adsorption is finally replaced and the like because the backwashing strength and the backwashing time of the common quartz sand filter material are increased due to the growth of the biological membrane. The invention selects the glass slag filter material with rich source and low price to carry out surface hydroxylation, surface silane coupling and surface electrification functional treatment, thereby greatly improving the filtering and adsorbing effects.

Drawings

FIG. 1 is a flow chart of a preparation method of a novel glass slag filtering material with a modified negatively charged surface according to the invention;

FIG. 2 is a graph showing the comparison of Zeta potential on the surface between the unmodified raw material and the novel glass slag filter material with negatively charged modified surfaces of different types prepared in example 1 and comparative example 1 of the present invention;

FIG. 3 is a comparison graph of Zeta potential on the surface of the novel glass slag filter material with different types of modified surfaces with negative charges, which is prepared in example 2 and comparative example 2 of the present invention, with unmodified raw materials and common quartz sand filter materials.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.