阅读说明：本技术 一种有机高分子填料表面改性方法 (Organic polymer filler surface modification method ) 是由 孙祝秋 席劲瑛 于 2019-11-08 设计创作，主要内容包括：本发明公开了一种有机高分子填料表面改性方法,首先利用酸性氧化剂对有机高分子填料表面进行均匀腐蚀,然后利用阳离子负载液和水性环氧树脂浸泡,使其表面附着阳离子,清洗烘干后得到改性有机高分子填料。还可以在超声波环境中进行化学腐蚀,从而达到更优的效果。通常选用疏水性有机高分子填料。本发明具有成本低廉,改性简单,可操作性强等优点。(The invention discloses a surface modification method of an organic polymer filler, which comprises the steps of firstly, uniformly corroding the surface of the organic polymer filler by using an acidic oxidant, then soaking the surface of the organic polymer filler by using a cation negative carrier liquid and aqueous epoxy resin to attach cations to the surface of the organic polymer filler, and cleaning and drying the organic polymer filler to obtain the modified organic polymer filler. Chemical corrosion can be carried out in an ultrasonic environment, so that a better effect is achieved. Hydrophobic organic polymeric fillers are generally selected. The invention has the advantages of low cost, simple modification, strong operability and the like.)

1. A method for modifying the surface of an organic polymer filler, the method comprising:

measuring a proper amount of water, weighing a proper amount of potassium permanganate according to the ratio of (10-25) g of potassium permanganate to L of water, measuring a proper amount of concentrated sulfuric acid according to the ratio of 1mL of concentrated sulfuric acid to g of potassium permanganate, and uniformly mixing the potassium permanganate, the concentrated sulfuric acid and the proper amount of water to serve as an acidic oxidant;

weighing a proper amount of water, weighing a proper amount of cationic polyacrylamide and ferric chloride according to the mass ratio of the cationic polyacrylamide to the ferric chloride to the water of (3-10): 20-30): 2000, and uniformly mixing the cationic polyacrylamide and the ferric chloride with the water to form a cationic negative carrier liquid taking the cationic polyacrylamide and the ferric chloride as the cationic negative carrier liquid;

soaking the organic polymer filler in the acidic oxidant for more than 10 minutes, and then taking out the chemically corroded organic polymer filler for cleaning to obtain a chemically modified organic polymer filler with a uniform and rough surface;

soaking the chemically modified organic polymer filler in a soaking pool filled with the cation negative carrier liquid, wherein the cation negative carrier liquid is used as a soaking liquid; adding a proper amount of waterborne epoxy resin into a soaking pool, uniformly stirring the waterborne epoxy resin, the chemically modified organic polymer filler and the cation loading liquid, adding a proper amount of curing agent into the soaking pool, stirring and soaking for 2 hours to ensure that the cation loading agent is attached to the surface of the chemically modified organic polymer filler to form the cation loaded organic polymer filler;

drying the cation-loaded organic polymer filler to obtain an organic polymer filler with a surface stably loaded with cations;

and cleaning the organic polymer filler with the surface stably loaded with cations by using water and drying to obtain the surface modified organic polymer filler.

2. The method of claim 1, further comprising:

and soaking the organic polymer filler in the acidic oxidant, placing the organic polymer filler in an ultrasonic environment for more than 10 minutes, and then taking out the organic polymer filler subjected to chemical corrosion for cleaning.

3. The method for modifying the surface of an organic polymer filler according to claim 1 or 2, wherein the cleaning process of the chemically etched organic polymer filler comprises:

cleaning the organic polymer filler subjected to chemical corrosion by using a hydrochloric acid solution, and soaking the organic polymer filler in a phosphate buffer solution to enable the organic polymer filler to be acid-base neutral, so as to obtain a chemically modified organic polymer filler with a uniform and rough surface;

the hydrochloric acid solution is 5% -10% hydrochloric acid solution; the phosphate buffer solution is neutral phosphate buffer solution.

4. The method for modifying the surface of the organic polymer filler according to claim 1, wherein the soaking solution is added to the aqueous epoxy resin according to the volume ratio of the aqueous epoxy resin to the cationic negative carrier liquid of 1 (50-100).

5. The method for modifying the surface of an organic polymer filler according to claim 1, wherein the curing agent is an aliphatic polyamine curing agent, and the curing agent is added in an amount corresponding to half the volume of the aqueous epoxy resin.

6. The method for modifying the surface of an organic polymer filler according to claim 1, wherein the organic polymer filler is selected from a polyurethane filler, a polyethylene filler, or a polyvinyl chloride filler.

Technical Field

The invention relates to a surface modification method of an organic polymer filler, in particular to a surface modification method of an organic polymer filler for promoting biofilm formation, and belongs to the technical field of environmental treatment.

Background

With the development of the social industry and the increase of the traditional fossil fuel consumption, a large amount of pollutants are generated and discharged into the natural environment, the damage of the pollutants to public health is more and more serious, and the environmental pollution treatment becomes a global cause for ensuring the living standard of human beings and the sustainable development of society. At present, a plurality of technologies and processes for treating pollutants in various forms exist, wherein the biomembrane treatment method is gradually concerned due to the advantages of high cost performance, low secondary pollution, stable operation, simple operation and the like. The biofilm reactors which are widely applied at present comprise a biofilter used for wastewater treatment, a biological rotating disk, a biological contact oxidation device, a biological fluidized bed and the like, and a biofilter tower and a biological trickling filter tower used for waste gas treatment.

The filler is used as a main component in the biofilm reactor, not only provides a growth environment for microorganisms, but also has important influence on mass transfer among gas phase, liquid phase and biofilm phase in the reactor. Therefore, the physical and chemical properties of the filler in the biofilm reactor have great significance on the formation of the biofilm, and the formation of the biofilm directly influences the operation performance of the biofilm reactor. The currently applied biomembrane fillers are more in variety, and the organic polymer fillers have the advantages of easy acquisition, low cost, long service time, high rebound rate and the like compared with other fillers, and are widely applied to the process of treating pollutants by using the fillers as the fillers. However, the smooth surface of the organic polymer filler and the hydrophobic oxide film on the surface often cause the problems of difficult attachment, slow formation, poor quality and the like of the biofilm, thereby causing the extension of the starting time of the biofilm reactor and the reduction of the running performance of the biofilm reactor.

Disclosure of Invention

The invention aims to provide a surface modification method of an organic polymer filler, which is characterized in that the surface of the filler is rough through chemical corrosion and is further subjected to physical modification so that cations are loaded on the surface of the filler to achieve surface modification, so that a biological membrane is easily attached to the surface of the organic polymer filler, the formation of the biological membrane is promoted, and the aim of quickly starting the biological membrane reactor can be fulfilled.

The invention is realized by the following technical scheme:

a method for modifying the surface of an organic polymer filler comprises the following steps:

measuring a proper amount of water, weighing a proper amount of potassium permanganate according to the ratio of (10-25) g of potassium permanganate to L of water, measuring a proper amount of concentrated sulfuric acid according to the ratio of 1mL of concentrated sulfuric acid to g of potassium permanganate, and uniformly mixing the potassium permanganate, the concentrated sulfuric acid and the proper amount of water to serve as an acidic oxidant;

weighing a proper amount of water, weighing a proper amount of cationic polyacrylamide and ferric chloride according to the mass ratio of the cationic polyacrylamide to the ferric chloride to the water of (3-10): 20-30): 2000, and uniformly mixing the cationic polyacrylamide and the ferric chloride with the water to form a cationic negative carrier liquid taking the cationic polyacrylamide and the ferric chloride as the cationic negative carrier liquid;

soaking the organic polymer filler in the acidic oxidant for more than 10 minutes to enable the surface of the organic polymer filler to be uniformly and chemically corroded, and then taking out the organic polymer filler subjected to chemical corrosion to clean to obtain a chemically modified organic polymer filler with a uniform and rough surface;

soaking the chemically modified organic polymer filler in a soaking pool filled with the cationic negative carrier liquid, wherein the cationic load liquid is used as a soaking liquid, so that the cationic load agent is uniformly attached to the surface of the chemically modified organic polymer filler; adding a proper amount of waterborne epoxy resin into a soaking pool, uniformly stirring the waterborne epoxy resin, the chemically modified organic polymer filler and the cationic loading liquid, adding a proper amount of curing agent into the soaking pool, stirring and soaking for 2 hours, so that the cationic loading agent is stably attached to the surface of the chemically modified organic polymer filler after the waterborne epoxy resin is cured, and the chemically modified organic polymer filler with the surface loaded with cations is formed;

drying the physicochemical modified organic polymer filler with the surface loaded with cations to stably solidify the waterborne epoxy resin attached to the surface of the filler to obtain the organic polymer filler with the surface stably loaded with cations;

and cleaning the organic polymer filler with the surface stably loaded with cations by using water and drying to obtain the surface modified organic polymer filler serving as a finished product.

In the above technical solution, the method further includes:

soaking the organic polymer filler in the acidic oxidant, placing the organic polymer filler in an ultrasonic environment for more than 10 minutes to ensure that the surface of the organic polymer filler is uniformly and chemically corroded, and then taking out the organic polymer filler subjected to chemical corrosion for cleaning.

In the above technical solution, the cleaning process of the organic polymer filler subjected to chemical corrosion includes:

cleaning the organic polymer filler subjected to chemical corrosion by using a hydrochloric acid solution, and soaking the organic polymer filler in a phosphate buffer solution to enable the organic polymer filler to be acid-base neutral, so as to obtain a chemically modified organic polymer filler with a uniform and rough surface;

the hydrochloric acid solution is 5% -10% hydrochloric acid solution; the phosphate buffer solution is neutral phosphate buffer solution.

In the technical scheme, the soaking solution is added into the water-based epoxy resin according to the volume ratio of the water-based epoxy resin to the cation negative carrier liquid of 1 (50-100).

In the technical scheme, the curing agent is an aqueous cationic system curing agent and is added according to half of the volume of the aqueous epoxy resin.

In the technical scheme, the aqueous cationic system curing agent is an aliphatic polyamine curing agent, and the main components of the curing agent comprise ethylenediamine, triethylene tetramine and hexamethylene diamine. In the above technical scheme, the organic polymer filler is a hydrophobic organic polymer filler, and includes any one or a mixture of a polyurethane filler, a polyethylene filler, and a polyvinyl chloride filler.

The invention has the advantages that: the surface of the filler is rough through chemical corrosion and is further loaded with cations on the surface of the filler so as to achieve the aim of modification, so that the surface of the organic polymer filler is easy to be attached with a biological membrane, the biological membrane formation is promoted, and the method has the advantages of simple operation method, low cost and the like.

Drawings

FIG. 1 is a schematic view of an organic polymer filler according to an embodiment of the present invention.

FIG. 2 is a schematic diagram illustrating the chemical corrosion effect of the organic polymer filler in the embodiment of the present invention.

FIG. 3 is a schematic diagram illustrating the surface modification effect of the organic polymer filler in the embodiment of the present invention.

Detailed Description

The following describes the embodiments and operation of the present invention with reference to the accompanying drawings.

The invention provides a surface modification method of an organic polymer filler, which is suitable for surface modification of hydrophobic organic polymer fillers such as polyurethane fillers, polyethylene fillers, polyvinyl chloride fillers and the like.

The surface modification of the organic polymer filler mainly comprises two processes, namely, the surface of the organic polymer filler is uniformly and chemically corroded by an acidic oxidant to obtain a uniform and rough surface, so that microorganisms are easy to form a film; and cations are stably loaded on the surface of the filler, and positive charges can be adsorbed in an aqueous phase environment, so that microorganisms are further adsorbed to promote biofilm formation.

Measuring a proper amount of water, weighing a proper amount of potassium permanganate according to the ratio of (10-25) g of potassium permanganate to L of water, measuring a proper amount of concentrated sulfuric acid according to the ratio of 1mL of concentrated sulfuric acid to 1g of potassium permanganate, and uniformly mixing the potassium permanganate, the concentrated sulfuric acid and the proper amount of water to serve as an acidic oxidant.

Weighing a proper amount of water, weighing a proper amount of cationic polyacrylamide and ferric chloride according to the mass ratio of the cationic polyacrylamide to the ferric chloride to the water of (3-10): 20-30): 2000, and uniformly mixing the cationic polyacrylamide and the ferric chloride with the water to form the cationic negative carrier liquid taking the cationic polyacrylamide and the ferric chloride as the cationic negative carrier.

Loading acidic oxidant into a soaking pool, and soaking the organic polymer filler (also called filler for short) in the acidic oxidant for more than 10 minutes to ensure that the surface of the organic polymer filler is uniformly and chemically corroded. Then taking out the organic polymer filler subjected to chemical corrosion to clean, and obtaining the chemically modified organic polymer filler with uniform and rough surface. As an optimized technical scheme, a soaking pool is placed in an ultrasonic environment, organic polymer fillers are soaked in an acidic oxidant for more than 10 minutes in the ultrasonic environment to be subjected to uniform chemical corrosion, and then the organic polymer fillers subjected to chemical corrosion are taken out to be cleaned. The process utilizes the rapid oscillation effect of ultrasonic waves on liquid to enable the acid oxidant to uniformly impact the surface of the filler so as to obtain a uniform rough surface. The rough surface of the organic polymer filler is not only beneficial to the attachment of microorganisms, but also beneficial to increasing the retention time of the nutrient solution, and finally the microorganisms are easier to form a film.

The cleaning process comprises the following steps: the organic polymer filler after chemical corrosion is cleaned by hydrochloric acid solution with the concentration of 5-10% and soaked in neutral phosphate buffer solution to make the organic polymer filler reach acid-base neutrality, so as to obtain the chemically modified organic polymer filler with uniform and rough surface.

The chemical modified organic polymer filler is soaked in a soaking pool filled with the cation negative carrier liquid, and the cation negative carrier liquid is used as a soaking liquid. In the soaking process, the cation negative carrier agent is uniformly dispersed around the chemically modified organic polymer filler and is uniformly attached. According to the volume ratio of the water-based epoxy resin to the cation negative carrier liquid of 1 (50-100), adding a proper amount of water-based epoxy resin into a soaking pool, uniformly stirring the water-based epoxy resin, the chemical modified organic polymer filler and the cation load liquid, uniformly mixing the water-based epoxy resin with the cation load agent, and soaking the mixture to be attached to the surface of the chemical modified organic polymer filler. Then adding a proper amount of curing agent into a soaking pool, stirring and soaking for 2 hours, and curing the waterborne epoxy resin under the action of the curing agent, so that the cationic polyacrylamide and ferric chloride are mixed and fixed on the surface of the chemically modified organic polymer filler, and cations are loaded on the surface of the organic polymer filler to form the cation loaded organic polymer filler. The curing agent is selected from an aqueous cationic system curing agent, usually an aliphatic polyamine curing agent, the main components of the curing agent comprise ethylenediamine, triethylene tetramine, hexamethylene diamine and the like, and the curing agent is added according to half of the volume of the aqueous epoxy resin. In the using process, iron ions fixed in the epoxy resin and a cationic functional group of polyacrylamide are matched to form a large-range positive charge cover, and microorganisms with negative charges on the general surface are further adsorbed through electrostatic action, so that the microbial biofilm formation is further enhanced.

And drying the cation-loaded organic polymer filler (the drying temperature is 60-90 ℃) to stably solidify the epoxy resin attached to the surface of the filler, thereby obtaining the organic polymer filler with the surface stably loaded with cations.

And washing the organic polymer with the surface stably loaded with the cations by using water and drying to obtain the surface modified organic polymer filler serving as a finished product.

One example of modifying the surface of a polyurethane filler is as follows.

17g of potassium permanganate and 17ml of concentrated sulfuric acid are uniformly dissolved in 1L of distilled water to prepare the acidic oxidant. Soaking polyurethane filler (shown in figure 1) in acidic oxidant, placing into an ultrasonic machine for 10 min, taking out the filler, washing with hydrochloric acid solution, and finally soaking in phosphate buffer solution for neutrality to obtain the polyurethane filler (figure 2) with uniform and rough surface. Then 3g of cationic polyacrylamide and 13.5g of ferric chloride are dissolved in 1L of distilled water to prepare the cationic negative carrier liquid. Soaking the polyurethane filler obtained before in a cationic negative carrier liquid, then adding 12.5ml of waterborne epoxy resin, stirring uniformly, then adding 6.5ml of curing agent, stirring and soaking for 2 hours. And finally, putting the soaked polyurethane filler into an oven to be dried at the temperature of 75 ℃. The polyurethane filler obtained was washed with distilled water and dried again (fig. 3). The surface change of the modified filler obtained through the steps is shown in figure 1. After replacing the original polyurethane filler and being filled into a biological filter tower, the filter tower operates to treat BTEX waste gas with TVOC of about 1000ppm, after 27 days of operation, the amount of increase of the biofilm amount on the surface of the filler is 2-3 times that of the filter tower assembled with unmodified filler, and the microbial activity of the biofilm is obviously improved. The removal rate under the action of the biological membrane is increased by about 1 time along with the formation of the biological membrane compared with the speed of the filter tower provided with the unmodified filler.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.