阅读说明：本技术 一种淀粉改性滤纸及其制备方法和应用 (Starch modified filter paper and preparation method and application thereof ) 是由 张帆 谭颖 徐昆 白云刚 王丕新 于 2020-07-03 设计创作，主要内容包括：本发明提供了一种淀粉改性滤纸的制备方法,包括以下步骤：将淀粉纳米微球水分散液喷涂在平均孔径为20～30微米的纤维素定性滤纸表面,再放入交联剂溶液中,反应,后处理,得到淀粉改性滤纸。本发明提供的方法简单,在纤维素定性滤纸表面修饰上纳米级的亲水微粒,能够调控滤纸表面的微纳米结构,可实现其作为油水分离材料。以淀粉纳米微球修饰定性滤纸表面,能够降低原料成本,又可使制备的分离膜具有生物降解性,且淀粉可再生。淀粉改性滤纸水下二氯乙烷接触角为148.5°～155.5°；油水混合物分离效率为99.81±0.02％～99.96±0.02％；乳液分离效率为99.75±0.02％～99.95±0.02％。(The invention provides a preparation method of starch modified filter paper, which comprises the following steps: and (3) spraying the starch nano microsphere aqueous dispersion on the surface of the cellulose qualitative filter paper with the average pore diameter of 20-30 microns, then putting the cellulose qualitative filter paper into a cross-linking agent solution, reacting, and performing post-treatment to obtain the starch modified filter paper. The method provided by the invention is simple, the surface of the cellulose qualitative filter paper is modified with the nano-scale hydrophilic particles, the micro-nano structure on the surface of the filter paper can be regulated and controlled, and the cellulose qualitative filter paper can be used as an oil-water separation material. The starch nano microspheres are used for modifying the surface of qualitative filter paper, so that the raw material cost can be reduced, the prepared separation membrane has biodegradability, and the starch can be regenerated. The underwater dichloroethane contact angle of the starch modified filter paper is 148.5-155.5 degrees; the separation efficiency of the oil-water mixture is 99.81 plus or minus 0.02 percent to 99.96 plus or minus 0.02 percent; the separation efficiency of the emulsion is 99.75 +/-0.02-99.95 +/-0.02%.)

1. A preparation method of starch modified filter paper comprises the following steps:

and (3) spraying the starch nano microsphere aqueous dispersion on the surface of the cellulose qualitative filter paper with the average pore diameter of 20-30 microns, then putting the cellulose qualitative filter paper into a cross-linking agent solution, reacting, and performing post-treatment to obtain the starch modified filter paper.

2. The preparation method of claim 1, wherein the mass concentration of the aqueous dispersion of starch nanospheres is 0.05-0.5%.

3. The method of claim 1, wherein the cross-linking agent in the cross-linking agent solution is selected from one or more of glyoxal, succinaldehyde, and glutaraldehyde.

4. The production method according to claim 1, wherein the reaction time is 30 minutes to 5 hours;

the reaction temperature is 25-50 ℃.

5. The preparation method of claim 1, wherein the particle size of the starch nanospheres in the aqueous dispersion of starch nanospheres is 80-120 nm.

6. The method of manufacturing according to claim 1, wherein the post-treatment comprises:

and washing the reacted filter paper with ethanol and deionized water alternately and repeatedly, and drying to obtain the starch modified filter paper.

7. The preparation method of claim 1, wherein the aqueous dispersion of starch nanospheres is prepared by the following method:

esterifying starch with acetic anhydride and succinic anhydride to obtain starch ester;

and dripping water into the acetone solution of the starch ester to obtain a nano microsphere dispersion, and drying to obtain the starch nano microsphere aqueous dispersion.

8. A starch-modified filter paper prepared by the method of any one of claims 1 to 7.

9. The starch-modified filter paper prepared by the preparation method of any one of claims 1 to 7 or the starch-modified filter paper of claim 8 is applied to oil-water separation of oil-containing wastewater and/or demulsification separation of oil-water emulsion.

Technical Field

The invention belongs to the technical field of functional materials, and particularly relates to starch modified filter paper and a preparation method and application thereof.

Background

With the rapid development of the economic society, the discharge of a large amount of industrial and domestic oily wastewater and the frequent accidents of offshore oil leakage cause serious environmental pollution, so that the demand for treating the oily wastewater is increased day by day. The research and development of new methods and new materials, and the improvement of the oil-water separation efficiency become one of the important research points.

At present, there are many methods for treating oily sewage, mainly including an additional demulsifying agent method, a physical method (including gravity separation, centrifugal separation, filtration separation), and a membrane separation method. The former two are more conventional and mature methods, the latter is a novel separation method which has emerged with membrane science in recent years. The membrane separation method is classified into a hydrophilic membrane and a hydrophobic membrane according to the properties of the membrane, and the hydrophobic membrane is currently studied and applied more. The base materials selected for the research of the oil-water separation membrane are mostly metal grids such as copper meshes and stainless steel, polymer membranes, nylon cloth and the like, and the nanostructure surface or hydrophilic/hydrophobic coating is formed by adopting electro-corrosion, soaking, electro-spinning, chemical reaction and the like. The hydrophobic membrane is usually composed of polyolefin polymers such as polyethylene, polyvinylidene fluoride and polytetrafluoroethylene, has good effect of removing a small amount of water impurities in oil, but is easy to seriously pollute the membrane, and has low repeated utilization rate. In addition, oil molecules tend to coalesce within the hydrophobic membrane and prevent the passage of water, causing a dramatic drop in water flux. Hydrophilic membranes have become a focus of research in recent years in order to allow oil to rapidly leave the membrane surface, prevent membrane fouling, and maintain water flux. However, the existing hydrophilic membrane has the problems of high raw material cost, complicated production process, difficult biodegradation and the like, so that the large-scale application of the hydrophilic membrane is limited.

Therefore, the research on a novel oil-water separation material remains an important subject in this field.

Disclosure of Invention

In view of the above, the invention aims to provide starch modified filter paper, a preparation method and an application thereof, the method is simple, and the prepared modified filter paper is suitable for oil-water separation of oily wastewater or demulsification separation of oil-water emulsion.

The invention provides a preparation method of starch modified filter paper, which comprises the following steps:

and (3) spraying the starch nanoparticle aqueous dispersion on the surface of the cellulose qualitative filter paper with the average pore diameter of 20-30 microns, putting the cellulose qualitative filter paper into a cross-linking agent solution with the mass concentration of 8-12%, reacting, and performing post-treatment to obtain the starch modified filter paper.

Preferably, the mass concentration of the aqueous dispersion of the starch nano microspheres is 0.05-0.5%.

Preferably, the cross-linking agent in the cross-linking agent solution is selected from one or more of glyoxal, succinaldehyde, and glutaraldehyde.

Preferably, the reaction time is 30 minutes to 5 hours;

the reaction temperature is 25-50 ℃.

Preferably, the particle size of the starch nanospheres in the starch nanosphere water dispersion liquid is 80-120 nm.

Preferably, the post-processing comprises:

and washing the reacted filter paper with ethanol and deionized water alternately and repeatedly, and drying to obtain the starch modified filter paper.

Preferably, the aqueous dispersion of the starch nanospheres is prepared by the following method:

esterifying starch with acetic anhydride and succinic anhydride to obtain starch ester;

and dripping water into the acetone solution of the starch ester to obtain a nano microsphere dispersion, and drying to obtain the starch nano microsphere aqueous dispersion.

The invention provides starch modified filter paper which is prepared by the preparation method of the technical scheme.

The invention provides the starch modified filter paper prepared by the preparation method in the technical scheme or the application of the starch modified filter paper in the technical scheme in oil-water separation of oily wastewater and/or demulsification separation of oil-water emulsion.

The invention provides a preparation method of starch modified filter paper, which comprises the following steps: and (3) spraying the starch nano microsphere aqueous dispersion on the surface of the cellulose qualitative filter paper with the average pore diameter of 20-30 microns, then putting the cellulose qualitative filter paper into a cross-linking agent solution, reacting, and performing post-treatment to obtain the starch modified filter paper. The method provided by the invention is simple, the surface of the cellulose qualitative filter paper is modified with the nano-scale hydrophilic particles, the micro-nano structure on the surface of the filter paper can be regulated and controlled, and the cellulose qualitative filter paper can be used as an oil-water separation material. The starch nano microspheres are used for modifying the surface of qualitative filter paper, so that the raw material cost can be reduced, the prepared separation membrane has biodegradability, the starch is renewable, the source is wide, and the large-scale production and application of the separation membrane are facilitated. The experimental results show that: the underwater dichloroethane contact angle of the starch modified filter paper is 148.5-155.5 degrees; the separation efficiency of the oil-water mixture is 99.81 plus or minus 0.02 percent to 99.96 plus or minus 0.02 percent; the separation efficiency of the emulsion is 99.75 +/-0.02-99.95 +/-0.02%.

Drawings

FIG. 1 shows an oil-water separator according to the present invention;

FIG. 2 is a scanning electron micrograph of the nano-starch, the raw filter paper and the cross-linked modified filter paper in example 1;

FIG. 3 is a test chart of the contact angle of the modified filter paper prepared in example 1 of the present invention in air and the contact angle of the underwater dichloroethane drop.

Detailed Description

The invention provides a preparation method of starch modified filter paper, which comprises the following steps:

and (3) spraying the starch nanoparticle aqueous dispersion on the surface of the cellulose qualitative filter paper with the average pore diameter of 20-30 microns, putting the cellulose qualitative filter paper into a cross-linking agent solution with the mass concentration of 8-12%, reacting, and performing post-treatment to obtain the starch modified filter paper.

In the invention, the starch modified filter paper mainly comprises cellulose, and countless micron-sized pores are formed on the surface of the starch modified filter paper and can be used for liquid to pass through; the surface of the filter paper is modified with nano-scale hydrophilic particles, and the micro-nano structure on the surface of the filter paper is regulated and controlled, so that the filter paper can be used as an oil-water separation material.

In the invention, the mass concentration of the starch nano microsphere water dispersion is 0.05-0.5%. The particle size of the starch nano-microsphere in the starch nano-microsphere aqueous dispersion is 80-120 nm. The starch nano microspheres are used for modifying the surface of qualitative filter paper, so that the raw material cost can be reduced, the prepared separation membrane has biodegradability, the starch is renewable, the source is wide, and the large-scale production and application of the separation membrane are facilitated. The starch nano microsphere aqueous dispersion is preferably prepared by the following method:

esterifying starch with acetic anhydride and succinic anhydride to obtain starch ester;

and dripping water into the acetone solution of the starch ester to obtain a nano microsphere dispersion, and drying to obtain the starch nano microsphere aqueous dispersion.

The esterification temperature is 45-55 ℃, and more preferably 50 ℃.

In the invention, the cellulose qualitative filter paper with the average pore diameter of 20-30 microns is preferably a commercially available product.

In the present invention, the cross-linking agent in the cross-linking agent solution is selected from one or more of glyoxal, succinaldehyde, and glutaraldehyde. The mass concentration of the cross-linking agent solution is 8-12%.

In the invention, the reaction temperature is preferably 25-50 ℃; the reaction time is 30 min-5 h.

In the present invention, the post-processing includes:

and washing the reacted filter paper with ethanol and deionized water alternately and repeatedly, and drying to obtain the starch modified filter paper.

The starch modified filter paper prepared by the method provided by the invention is a hydrophilic oil-water separation membrane.

The invention provides starch modified filter paper which is prepared by the method of the technical scheme.

The invention provides the starch modified filter paper prepared by the preparation method in the technical scheme or the application of the starch modified filter paper in the technical scheme in oil-water separation of oily wastewater and/or demulsification separation of oil-water emulsion.

FIG. 1 shows an oil-water separator according to the present invention. The separation device comprises a separated liquid containing glass vessel, a separated liquid containing glass vessel and a separation membrane between the two vessels. The oil-water performance of the starch modified filter paper is tested by adopting the oil-water separation device.

In order to further illustrate the present invention, the following examples are provided to describe a starch modified filter paper and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.