阅读说明：本技术 一种石油吸油材料及其应用 (Petroleum oil absorption material and application thereof ) 是由 陈巧 姚坤 程庚 范宇 刘建金 于 2020-05-25 设计创作，主要内容包括：本申请公开了一种石油吸油材料及其应用。本申请的石油吸油材料为熔体拉伸法或相分离法制备的聚烯烃微孔膜,聚烯烃微孔膜的透气值为30-500s/100mL,水接触角为80-120°,吸油量大于9.3g/m<Sup>2</Sup>。本申请的石油吸油材料,由于采用特殊工艺和参数的聚烯烃微孔膜,具有高效的吸油率和疏水性,不仅吸油量高、吸油速度快,而且吸油后的保持效果良好,可应用于所有需要吸油材料的领域。本申请的石油吸油材料可以有效的进行石油回收,使用简单方便,并且,其材料本身可以回收利用,成本低、操作安全。(The application discloses a petroleum oil absorption material and application thereof. The petroleum oil absorption material is a polyolefin microporous membrane prepared by a melt stretching method or a phase separation method, the air permeability value of the polyolefin microporous membrane is 30-500s/100mL, the water contact angle is 80-120 degrees, and the oil absorption is more than 9.3g/m 2 . The petroleum oil absorption material adopts the polyolefin microporous membrane with special process and parameters,the oil absorption material has high oil absorption rate and hydrophobicity, high oil absorption amount, high oil absorption speed and good retention effect after oil absorption, and can be applied to all fields needing oil absorption materials. The oil absorption material can effectively recover oil, is simple and convenient to use, can recycle the material, and is low in cost and safe to operate.)

1. A petroleum oil absorption material is characterized in that: the petroleum oil absorption material is a polyolefin microporous membrane prepared by a melt stretching method or a phase separation method, the air permeability value of the polyolefin microporous membrane is 30-500s/100mL, the water contact angle is 80-120 degrees, and the oil absorption is more than 9.3g/m²。

2. The petroleum oil absorbing material of claim 1, wherein: the polyolefin microporous membrane is prepared from polypropylene, polyethylene or polypropylene-polyethylene copolymer.

3. The petroleum oil absorbing material of claim 2, wherein: the polyolefin microporous membrane is of a single-layer or multi-layer structure.

4. A petroleum oil absorbing material according to any one of claims 1 to 3, wherein: the thickness of the polyolefin microporous membrane is 3-3000 mu m;

preferably, the polyolefin microporous membrane has an average pore diameter of 10 to 2000 nm;

preferably, the polyolefin microporous membrane has a porosity of 10 to 95%;

preferably, the polyolefin microporous membrane has a tensile strength greater than or equal to 100N;

preferably, the polyolefin microporous membrane has a puncture strength of greater than or equal to 25N.

5. The use of the petroleum oil absorption material according to any one of claims 1 to 4 in marine petroleum pollution remediation or water surface oil slick recovery.

6. The use of the petroleum oil absorbing material according to any one of claims 1 to 4 in kitchen oil absorption, food or environment-friendly safe oil filtration, or moisture-proof, water-proof and rust-proof paper packaging.

7. The application of the polyolefin microporous membrane in the petroleum oil absorption material is characterized in that: the polyolefin microporous membrane is a single-layer or multi-layer microporous membrane prepared by a melt stretching method or a phase separation method, the air permeability value of the polyolefin microporous membrane is 30-500s/100mL, the water contact angle is 80-120 degrees, and the oil absorption is more than 9.3g/m²。

8. Use according to claim 7, characterized in that: the polyolefin microporous membrane is prepared from polypropylene, polyethylene or polypropylene-polyethylene copolymer.

9. Use according to claim 8, characterized in that: the polyolefin microporous membrane is of a single-layer or multi-layer structure.

10. Use according to any one of claims 7 to 9, characterized in that: the thickness of the polyolefin microporous membrane is 3-3000 mu m;

preferably, the polyolefin microporous membrane has an average pore diameter of 10 to 2000 nm;

preferably, the polyolefin microporous membrane has a porosity of 10 to 95%;

preferably, the polyolefin microporous membrane has a tensile strength greater than or equal to 100N;

preferably, the polyolefin microporous membrane has a puncture strength of greater than or equal to 25N.

Technical Field

The application relates to the field of oil absorption materials, in particular to a petroleum oil absorption material and application thereof.

Background

In recent years, with rapid development of economy and improvement of living standard of people, increasingly depletion of non-renewable energy sources and increased environmental pollution are accompanied. People pay more attention to sustainable development of ecological environment and environment-friendly society. Petroleum, known as "industrial blood", is an important resource and strategic reserve. Oil spill pollution events can occur in the processes of storage, transportation and use of petroleum. According to statistics, the petroleum and petroleum products discharged into the ocean through various channels account for about 0.5 percent of the total petroleum quantity all over the world every year, the amount of the petroleum poured into the ocean is up to 200-1000 ten thousand tons, and the petroleum pollutants discharged into the ocean due to shipping are up to 160-200 ten thousand tons, wherein about 1/3 is caused by petroleum leakage caused by accidents of oil tankers at the ocean. Various oil spilling accidents at sea are important reasons for the over-standard oil content of seawater in coastal areas, and the problem of marine oil pollution is very serious.

At present, the offshore oil treatment is mainly divided into the following steps: (1) isolation, namely isolating oil leakage by using a fence device to prevent further large-scale diffusion, and is mainly suitable for a static water area; (2) recovering large-area floating oil by using an oil absorption material, such as an oil absorption felt, crop straws, a fiber braided fabric and the like, or removing thick oil leakage of 2mm or more by a combustion method; (3) the bio/chemical process degrades/disperses the resid.

The oil absorption material is used for absorbing petroleum, and is the key for large-area floating oil recovery. As a petroleum oil absorption material, the oil absorption material has the characteristics of high oil absorption rate and hydrophobicity so as to ensure maximum oil absorption. The oil absorption materials commonly used at present comprise the following materials: (1) traditional natural organic materials such as wheat straw, wool, cotton, and the like; (2) traditional natural inorganic materials such as clay, zeolite, bentonite, diatomaceous earth, graphite, and the like; (3) chemically synthesizing oil absorption materials which are divided into three types of high oil absorption resin, organic polymer fiber, gel and the like; (4) novel oil absorption materials, such as stainless steel meshes, films, sponges and the like which can be used for oil-water separation.

With the increasing pollution of marine oil, the requirements on oil absorption materials are higher and higher. The conventional non-woven fabric, oil absorption felt, sponge and other oil absorption materials are low in price, but the oil absorption amount is low, the oil absorption speed is slow, the oil absorption and retention effects on petroleum are poor, and the use requirements are difficult to meet. The traditional natural organic material has the advantages of easily obtained raw materials, low cost and safe operation; however, the oil absorption was small and the recycling rate was poor. Other oil-absorbing materials are either high in cost or complex in preparation process.

Therefore, the development of a petroleum oil absorption material which has the advantages of simple preparation process, low cost, high oil absorption amount, high oil absorption speed and good petroleum absorption and retention effects is urgently needed.

Disclosure of Invention

The application aims to provide a novel petroleum oil absorption material and application thereof.

In order to achieve the purpose, the following technical scheme is adopted in the application:

one aspect of the application discloses a petroleum oil absorption material which is a polyolefin microporous membrane prepared by a melt stretching method or a phase separation method, wherein the polyolefin microporous membrane has the air permeability value of 30-500s/100mL, the water contact angle of 80-120 degrees and the oil absorption of more than 9.3g/m²。

The polyolefin microporous membrane with special process and parameters is used as the oil absorption material, and the porosity and hydrophobicity of the polyolefin microporous membrane are utilized, so that the oil absorption capacity of petroleum is improved, the oil absorption speed is improved, the oil absorption and retention effects on the petroleum are good, the oil absorption material can be well suitable for offshore petroleum treatment, and the efficiency and the quality of large-area floating oil recovery are improved.

It should be noted that, unlike the existing organic polymer fiber or film oil absorption material, the petroleum oil absorption material of the present application uses a polyolefin microporous membrane prepared by a melt stretching method or a phase separation method. The melt stretching method and the phase separation method are microporous membrane preparation methods used in battery diaphragm preparation, wherein the melt stretching method is also called dry stretching, and the phase separation method is also called wet stretching. Therefore, the oil absorption material is simple in preparation method, low in price and high in performance and cost performance. The key point of the application is that the polyolefin microporous membrane with special parameter performance in the battery diaphragm is creatively used as the petroleum oil absorption material, so that the petroleum oil absorption efficiency and quality are improved; as for the specific melt-drawing method and the phase separation method, the existing battery separator preparation process can be referred to.

Preferably, the polyolefin microporous membrane is prepared from polypropylene, polyethylene or polypropylene-polyethylene copolymer.

Preferably, the polyolefin microporous membrane is a monolayer or multilayer structure.

The polyolefin microporous membrane serving as the petroleum oil absorption material of the present application can refer to the microporous membrane in the existing battery diaphragm, and can be a single-layer polypropylene microporous membrane, a polyethylene microporous membrane, or a microporous membrane of polypropylene and polyethylene copolymer; or may be a multilayer structure such as a multilayer polyethylene microporous film, a multilayer polypropylene microporous film, a polyethylene/polypropylene composite multilayer film (e.g., a polyethylene/polypropylene composite film, a polyethylene/polypropylene/polyethylene composite film, a polypropylene/polyethylene/polypropylene composite film, etc.), or other multilayer structures of 2 to 10 layers or 3 to 5 layers; the specific selection can be determined according to the performance requirement of the petroleum oil absorption material, and is not particularly limited herein.

It should be further noted that the polyolefin microporous membrane of the petroleum oil absorption material of the present application can be directly obtained commercially, or prepared by using the polyolefin microporous membrane preparation method in patent documents CN110391384A, CN109461871A, CN109802079A or CN110744840A, which is not limited herein.

Preferably, the polyolefin microporous membrane has a thickness of 3 to 3000. mu.m.

The thickness of the polyolefin microporous membrane serving as the petroleum oil absorption material determines the oil absorption and the liquid absorption speed of petroleum; on one hand, the mechanical strength of the petroleum oil absorption material is directly influenced; the application generally adopts a polyolefin microporous membrane with the thickness of 3-3000 mu m as the petroleum oil absorption material, for example, the thickness is 8-120 mu m, 12-100 mu m or 20-40 mu m. In particular, single or multilayer polyolefin microporous membranes of 9-40 μm are used in implementations of the present application.

Preferably, the polyolefin microporous membrane has an average pore size of 10 to 2000 nm.

It should be noted that, the average pore diameter of the polyolefin microporous membrane used as the oil absorption material of petroleum is also a key factor directly influencing the oil absorption of petroleum; polyolefin microporous membranes having an average pore size of 10 to 2000nm, such as 20 to 120nm, 30 to 100nm, or 50 to 80nm, are used herein as desired.

Preferably, the polyolefin microporous membrane has a porosity of 10 to 95%.

It should be noted that the porosity of the polyolefin microporous membrane petroleum oil absorption material directly affects the oil absorption amount and speed of petroleum oil, and the polyolefin microporous membrane with a porosity of 10-95% is generally used as the petroleum oil absorption material in the present application, for example, the porosity is 20-90% or 50-80%. In the implementation mode of the application, a polyolefin microporous membrane with the porosity of 43-75% is specifically adopted.

Preferably, the polyolefin microporous membrane has a tensile strength of greater than or equal to 100N.

Preferably, the polyolefin microporous membrane has a puncture strength of greater than or equal to 25N.

The tensile strength and the puncture strength of the polyolefin microporous membrane are mechanical strength indexes of the polyolefin microporous membrane, and in the petroleum oil absorption material, the tensile strength and the puncture strength of the polyolefin microporous membrane can ensure that the petroleum oil absorption material is not easy to damage, so that the phenomenon that the quality and the efficiency of oil absorption are influenced due to the fact that the petroleum oil absorption material is damaged by some foreign matters or impurities in the oil absorption process is avoided. In general, the polyolefin microporous membrane with the tensile strength of more than or equal to 100N, such as 320-840N, and the puncture strength of more than or equal to 25N, such as more than or equal to 98.5N, can be used for well meeting the use requirements of the petroleum oil absorption material. In the implementation manner of the present application, the tensile strength in the MD direction can reach 750-; the puncture strength is 98.5-151.3N; has good mechanical strength.

The application also discloses an application of the petroleum oil absorption material in marine petroleum pollution treatment or water surface floating oil recovery.

It should be noted that, the petroleum oil absorption material of the present application has good oil absorption and oil absorption speed, and the retention effect after absorption is good; therefore, the method can be used for marine oil pollution treatment or water surface floating oil recovery.

The application also discloses an application of the petroleum oil absorption material in kitchen oil absorption, food or environment-friendly safe oil filtration, or moisture-proof, waterproof and antirust oil paper packaging.

It should be noted that the petroleum oil absorption material of the present application, though developed for marine petroleum pollution; however, the oil absorption speed and the oil absorption retaining effect are excellent, and the oil absorption, the oil absorption speed and the oil absorption retaining effect can be also used for treating other oil or grease, such as kitchen oil absorption, food or environment-friendly safe oil filtering, moisture-proof and waterproof antirust oil paper packaging and the like. It is understood that the petroleum oil absorbent material of the present application can be used as long as it needs a large amount of oil absorption or package for isolating oil, and is not particularly limited herein. The oil may be petroleum, engine oil, edible oil, etc.

The application also discloses an application of the polyolefin microporous membrane in petroleum oil absorption materials, the polyolefin microporous membrane is a single-layer or multi-layer microporous membrane prepared by a melt stretching method or a phase separation method, the air permeability value of the polyolefin microporous membrane is 30-500s/100mL, the water contact angle is 80-120 degrees, and the oil absorption is more than 9.3g/m²。

The key point of the application lies in that the polyolefin microporous membrane of the battery diaphragm is used as the petroleum oil absorption material creatively, particularly, the gas permeability value is 30-500s/100mL, the water contact angle is 80-120 degrees, and the oil absorption is more than 9.3g/m²Is particularly suitable for use in polyolefin microporous membranesCan be used as oil absorption material. The polyolefin microporous membrane of the present application may be a polyolefin microporous membrane of a conventional battery separator, such as a single-layer or multi-layer microporous membrane prepared from polypropylene, polyethylene, or polypropylene-polyethylene copolymer. In order to ensure the performance of the petroleum oil absorption material, the application preferably adopts a polyolefin microporous membrane with the thickness of 3-3000 mu m, the average pore diameter of 10-2000nm, the porosity of 10-95%, the tensile strength of more than or equal to 100N and the puncture strength of more than or equal to 25N as the petroleum oil absorption material.

Due to the adoption of the technical scheme, the beneficial effects of the application are as follows:

the oil absorption material has high oil absorption rate and hydrophobicity due to the adoption of the polyolefin microporous membrane with special process and parameters, is high in oil absorption amount and high in oil absorption speed, has a good retention effect after oil absorption, and can be applied to all fields needing oil absorption materials. The oil absorption material can effectively recover oil, is simple and convenient to use, can recycle the material, and is low in cost and safe to operate.

Drawings

FIG. 1 is a surface SEM image of a polypropylene microporous membrane petroleum oil absorption material in an example of the application;

FIG. 2 is a surface SEM image of a polyethylene microporous membrane petroleum oil absorption material in an example of the application;

FIG. 3 is a sectional SEM image of a petroleum oil absorption material with a three-layer polypropylene microporous membrane in the example of the application;

FIG. 4 is a sectional SEM image of a polypropylene/polyethylene/polypropylene three-layer co-extruded composite microporous membrane in the embodiment of the application.

Detailed Description

The existing oil absorption material, whether traditional natural organic or inorganic material, or chemically synthesized or newly developed oil absorption material, has different defects and insufficiencies, and is difficult to meet the use requirements of marine pollution treatment and large-area floating oil recovery.

The research of the application finds that the battery diaphragm has the performances of hydrophobicity, pore structure, wettability, moisture retention and the like, and is particularly suitable for being used as a petroleum oil absorption materialFeeding; therefore, the battery separator has the advantages that the gas permeability value is 30-500s/100mL, the water contact angle is 80-120 degrees, and the oil absorption is more than 9.3g/m²The polyolefin microporous membrane is used as a petroleum oil absorption material.

The polyolefin microporous membrane is creatively used as the oil absorption material, so that the oil absorption capacity and the oil absorption speed are improved, and a novel oil absorption material with high performance and high cost performance is provided for oil absorption. And based on the same principle, the petroleum oil absorption material can be used for absorbing petroleum and other grease, including but not limited to kitchen oil absorption, food or environment-friendly safe oil filtration, and moisture-proof and waterproof antirust oil paper packaging.

The melt drawing method is also called dry drawing, and mainly comprises the following steps:

(1) extrusion casting: extruding and casting polyolefin particles to obtain a casting film;

(2) annealing: carrying out high-temperature annealing treatment on the casting membrane to perfect the lamella to obtain an annealing membrane;

(3) stretching: performing cold drawing and hot drawing on the annealed membrane to obtain a stretched porous membrane;

(4) heat setting: and (3) performing heat setting on the stretched porous membrane to obtain the polyolefin microporous membrane.

The phase separation method is also called wet stretching, and mainly comprises the following steps:

(1) melt mixing: mixing polyolefin with a pore-forming agent with a high boiling point, heating, melting and mixing to obtain a mixed melt;

(2) tabletting and forming: carrying out high-temperature tabletting molding on the mixed melt to obtain a membrane;

(3) stretching: cooling the membrane, removing the pore-forming agent, and performing biaxial tension to obtain a stretched porous membrane;

(4) heat setting: and (3) performing heat setting on the stretched porous membrane to obtain the polyolefin microporous membrane.

Specifically, reference may be made to existing battery separator production processes, such as polyolefin microporous membrane preparation methods disclosed in patent documents CN109461871A, CN110391384A, CN109802079A, CN110744840A, and the like.

The present application is described in further detail below with reference to specific embodiments and the attached drawings. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application. Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.