阅读说明：本技术 一种掺杂纤维素纳米晶须的复合膜及其制备方法和应用 (A kind of composite membrane and its preparation method and application of doping Cellulose nanocrystal palpus ) 是由 王斌 葛洲 李金鹏 陈克复 于 2019-08-16 设计创作，主要内容包括：本发明公开了一种掺杂纤维素纳米晶须的复合膜及其制备方法和应用。该方法包括如下步骤：(1)将纤维素纳米晶须加入水中,配制成纤维素纳米晶须悬浮液；然后加入硫氢化钠,搅拌溶解,再加入功能助剂,搅拌溶解后再进行乳化,得到混合液；(2)将聚丙烯腈加入到混合液中,搅拌至聚丙烯腈完全溶解,然后在真空条件下静止脱泡至气泡消除完全,得到共混液；(3)将共混液制成膜后立刻放入凝固浴中浸泡,浸泡后再取出冲洗干净并自然晾干,得到掺杂纤维素纳米晶须的复合膜。本发明工艺简单,成本较低,获得的复合膜具有极强的亲水性、良好的持水能力和较好的吸附能力等特点,可以用于污水处理领域。(The invention discloses a kind of composite membranes and its preparation method and application of doping Cellulose nanocrystal palpus.This method comprises the following steps: (1) must be added to the water Cellulose nanocrystal, being configured to Cellulose nanocrystal must suspension；Then NaHS is added, stirring and dissolving adds function additive, emulsified again after stirring and dissolving, obtain mixed liquor；(2) polyacrylonitrile is added in mixed liquor, stirring to polyacrylonitrile is completely dissolved, and then discontinuous degassing to bubble is eliminated completely under vacuum conditions, obtains blended liquid；(3) blended liquid is made to be put into coagulating bath at once after film and is impregnated, further taken out after immersion and rinse simultaneously naturally dry well, obtain the composite membrane of doping Cellulose nanocrystal palpus.Present invention process is simple, and cost is relatively low, and the composite membrane of acquisition has the characteristics that extremely strong hydrophily, good moisture holding capacity and preferable adsorption capacity, can be used for sewage treatment field.)

1. a kind of preparation method of the composite membrane of doping Cellulose nanocrystal palpus, which comprises the steps of:

(1) Cellulose nanocrystal must be added to the water, being configured to Cellulose nanocrystal must suspension；Then NaHS is added, Stirring and dissolving obtains mixed liquor A；Function additive is added in mixed liquor A again, is emulsified after stirring and dissolving, is mixed Liquid B；

(2) polyacrylonitrile is added in mixed liquid B obtained in step (1), stirring is completely dissolved to polyacrylonitrile, is then existed Discontinuous degassing to bubble is eliminated completely under vacuum condition, obtains blended liquid C；

(3) blended liquid C obtained in step (2) is made to be put into coagulating bath at once after film and is impregnated, taking-up is rushed with water after immersion Wash clean, naturally dry obtain the composite membrane of doping Cellulose nanocrystal palpus.

2. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:

Function additive described in step (1) is at least one of polyvinylpyrrolidone and polyethylene glycol；

Coagulating bath described in step (3) is one or more of ethyl alcohol, distilled water and n-hexane.

3. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 2, it is characterised in that:

Function additive described in step (1) be molecular weight 45000~58000 polyvinylpyrrolidone and molecular weight 2000~ 8000 polyethylene glycol；

The dosage of the polyvinylpyrrolidone is account for the blended liquid C mass 1~2%；

The dosage of the polyethylene glycol is account for the blended liquid C mass 1~2%.

4. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:

The concentration of the suspension of the palpus of Cellulose nanocrystal described in step (1) is mass percent 0.5~1.5%；

The concentration of NaHS is mass percent 40~60% in mixed liquor A described in step (1)；

The dosage of polyacrylonitrile described in step (2) is account for blended liquid C mass 10~20%.

5. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:

Cellulose nanocrystal described in step (1) must account for the 1~10% of the polyacrylonitrile quality.

6. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, which is characterized in that step (3) film is made in blended liquid C is achieved by the steps of described in: blended liquid C is spread on simple glass plate with scraper Plate membrane.

7. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:

The time of immersion described in step (3) is one day or more；

Doping Cellulose nanocrystal described in step (3) must composite membrane with a thickness of 0.10~0.15mm.

8. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:

The condition of emulsification described in step (1) are as follows: 10000rpm emulsifies 20min；

The molecular weight of polyacrylonitrile described in step (2) is 50000~150000；

The condition of stirring described in step (2) are as follows: under 60~80 DEG C of water bath conditions, 800rpm stir 2h；

The condition of discontinuous degassing described in step (2) are as follows: pressure 0.1MPa, 50~70 DEG C of temperature, time 36h.

9. a kind of composite membrane of doping Cellulose nanocrystal palpus, it is characterised in that: by according to any one of claims 1 to 8 Method is prepared.

10. application of the composite membrane of doping Cellulose nanocrystal palpus as claimed in claim 9 in water treatment field.

Technical field

The invention belongs to UF membrane field, in particular to the composite membrane of a kind of doping Cellulose nanocrystal palpus and its preparation side Method and application.

Background technique

As social progress, industrial development and quality of life improve, water pollution problems is on the rise, and wherein trade effluent is Mostly important pollution sources.It investigates and shows according to authoritative institution, the world, having 80% disease in developing country is by water pollution It is caused, at least cause 00,000 people of global 200d dead every year；More areas once occurred different degrees of due to toxic chemical in the world Extensive disease's spread phenomenon caused by article or the waste water of heavy metal ion, water pollution people be referred to as " world is No.1 Killer.With the propulsion that national sustainable development requires, the recycling of discharge of wastewater and water resource is increasingly by social each The attention on boundary, waste water control have become a very intractable and unavoidable problem.Preferable water process knot in order to obtain Fruit, people have used various methods, and wherein membrane processing method has proven to be a kind of efficient, convenient and low energy The mode of consumption.

With deepening continuously for membrane separation technique research, more convenience, more effective membrane separation technique constantly emerges, must More values will be created for sustainable development.Since polyacrylonitrile film has, chemical stability is good, thermal stability is strong and resistance to organic The advantages that solvent, is widely used in UF membrane field.Application No. is a kind of 94116066.1, entitled " systems of polyacrylonitrile film Make method " Chinese patent be using polyacrylonitrile matrix as material, by the water-immersed method preparative separation film of gel-like film, this Kind method and process is simple, and condition relatively easily controls, and can be very good to reduce cost, but the water flux of the seperation film is smaller, real It is not strong with property.Application No. is the China of 201110331954.7, entitled " a kind of preparation method of modified polyacrylonitrile film " specially Benefit is to add the mode of fibroin protein using polyacrylonitrile as material preparation is blended, this method improves the water flux of seperation film And hydrophily, extend polyacrylonitrile film uses the time.But the hydrophily of fibroin albumen itself is bad, does not add corresponding Micropore auxiliary agent is controlled, the final effect that promoted is not obvious.

Currently, there are many researchers prepares composite membrane with polyacrylonitrile blended using different water wetted materials, though Certain effect is so achieved, but the water flux of seperation film and porosity are not promoted significantly still, or even there are some hydrophilic materials Inherently there are harmful components in material, therefore, it is necessary to research and develop the composite membrane of a kind of environmentally friendly, high water flux and high porosity To meet the demand in market.

Summary of the invention

The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of doping Cellulose nanocrystal The preparation method of the composite membrane of palpus.

Another object of the present invention is to provide the composite membranes for the doping Cellulose nanocrystal palpus that the method is prepared.

A further object of the present invention is to provide the applications of the composite membrane of the doping Cellulose nanocrystal palpus.

The purpose of the invention is achieved by the following technical solution: a kind of preparation of the composite membrane of doping Cellulose nanocrystal palpus Method includes the following steps:

(1) Cellulose nanocrystal must be added to the water, being configured to Cellulose nanocrystal must suspension；Then sulphur hydrogenation is added Sodium, stirring and dissolving obtain mixed liquor A；Function additive is added in mixed liquor A again, is emulsified after stirring and dissolving, is mixed Close liquid B；

(2) polyacrylonitrile is added in mixed liquid B obtained in step (1), stirring to polyacrylonitrile is completely dissolved, so (vacuum heat-preserving) discontinuous degassing to bubble is eliminated completely under vacuum conditions afterwards, obtains blended liquid C；

(3) blended liquid C obtained in step (2) is made to be put into coagulating bath at once after film and is impregnated, taken out and use after immersion Water is rinsed well, naturally dry, obtains the composite membrane of doping Cellulose nanocrystal palpus.

Water described in step (1) is preferably deionized water.

Cellulose nanocrystal described in step (1) must suspension concentration be preferably mass percent 0.5~ 1.5%.

Cellulose nanocrystal described in step (1) must suspension configuration method it is as follows: must be by Cellulose nanocrystal 25 DEG C, stir evenly under 800rpm, obtaining Cellulose nanocrystal must suspension.

Cellulose nanocrystal described in step (1) must account for the 1~10% of the polyacrylonitrile quality.

The concentration of NaHS is preferably mass percent 40~60% in mixed liquor A described in step (1).

Function additive described in step (1) is at least one of polyvinylpyrrolidone and polyethylene glycol；Preferably Polyvinylpyrrolidone and polyethylene glycol；The more preferably polyvinylpyrrolidone and molecular weight of molecular weight 45000~58000 2000~8000 polyethylene glycol；The most preferably poly- second two of the polyvinylpyrrolidone of molecular weight 58000 and molecular weight 2000 Alcohol.

The dosage of the polyvinylpyrrolidone is account for the blended liquid C mass 1~2%.

The dosage of the polyethylene glycol is account for the blended liquid C mass 1~2%.

Emulsification described in step (1) is to be emulsified using mulser.

The condition of emulsification described in step (1) is preferred are as follows: 10000rpm emulsifies 20min.

The molecular weight of polyacrylonitrile described in step (2) is 50000~150000；Preferably 50000.

The dosage of polyacrylonitrile described in step (2) is account for blended liquid C mass 10~20%.

The condition of stirring described in step (2) is preferred are as follows: under 60~80 DEG C of water bath conditions, 800rpm stir 2h.

The condition of discontinuous degassing described in step (2) is preferred are as follows: pressure 0.1MPa, 50~70 DEG C of temperature, time 36h.

Coagulating bath described in step (3) is one or more of ethyl alcohol, distilled water and n-hexane；Preferably distilled water.

Film is made in blended liquid C described in step (3) to realize preferably by following steps: with scraper by blended liquid C In spreading to plate membrane on simple glass plate.

Doping Cellulose nanocrystal described in step (3) must composite membrane with a thickness of 0.10~0.15mm；Preferably 0.12mm。

The time of immersion described in step (3) is preferably one day or more.

Water described in step (3) is preferably distilled water.

A kind of composite membrane of doping Cellulose nanocrystal palpus, is prepared by method described in any of the above embodiments.

Application of the composite membrane of the doping Cellulose nanocrystal palpus in water treatment field.

The water process includes sewage treatment etc..

The present invention has the following advantages and effects with respect to the prior art:

1, polyacrylonitrile must sufficiently be blended the content of present invention with Cellulose nanocrystal, be obtained using coagulating bath film build method Composite membrane, achieved the effect that simplified technique, processing cost it is lower, convenient for operation.

2, the Cellulose nanocrystal that the present invention is added must have specific surface area height, modulus big, and hydrophily is fabulous, and adsorption energy The strong feature of power makes composite membrane have the characteristics that extremely strong hydrophily, good moisture holding capacity, preferable adsorption capacity, and its Transparency is higher.Using the resulting composite membrane of this preparation method by with required high water flux and high porosity, show good Good antifouling property, can apply in sewage treatment field.

3, the Cellulose nanocrystal palpus and auxiliary agent that the present invention uses will not generate environment all for biodegradable material It influences, introduces new pollution sources when avoiding processing water.

Detailed description of the invention

Fig. 1 is the preparation method flow chart of the composite membrane of present invention doping Cellulose nanocrystal palpus.

Fig. 2 is the composite membrane pictorial diagram prepared in embodiment 6.

Specific embodiment

Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto. Unless stated otherwise, the method and apparatus that the present invention uses is the art conventional method and equipment.In the following example not The test method for indicating specific experiment condition, usually according to conventional laboratory conditions.

Cellulose nanocrystal in the embodiment of the present invention and comparative example must be purchased from Shanghai Kai Xiang new material Science and Technology Ltd. (nano cellulose crystal NCC)；Polyvinylpyrrolidone is purchased from Solution on Chemical Reagents in Shanghai company, Chinese Medicine group, and molecular weight is 45000~58000 (preferably 58000)；Polyethylene glycol is purchased from Tianjin Tian Li chemical reagent Co., Ltd, and molecular weight is 2000~8000 (preferably 2000)；NaHS is purchased from Tianjin good fortune morning chemical reagent factory；Polyacrylonitrile is purchased from Shanghai petroleum Chemical inc, molecular weight are 50000~150000 (preferably 50000).