阅读说明：本技术 一种高通量抗污染特种管式超滤膜的制备方法 (A kind of preparation method of high throughput antipollution special type tubular ultra-filtration membrane ) 是由 钱铖 刘媛媛 曾凡付 许白羽 于 2019-09-04 设计创作，主要内容包括：本发明公开了一种高通量抗污染特种管式超滤膜的制备方法,具体包括以下步骤：S1、原料的选取和称量,S2、配置铸膜液,S3、卷膜涂覆,S4、膜管的漂洗处理,本发明涉及特种管式超滤膜技术领域。该高通量抗污染特种管式超滤膜的制备方法,此制备方法简单、工业化应用前景大,在传统的印染废水预处理的技术基础上,将此特种管式膜组件应用到印染废水的深度处理系统中,利用特种管式膜的筛分特性,大大缩短了印染废水的预处理时间,同时也显著提高了反渗透系统进水水质,有效的提高了反渗透系统的使用寿命,使用自制管式超滤膜,显著降低废水浊度,有利于后续采用生化法进行处理从而实现达标排放,显著降低了污水处理后期难度。(The invention discloses a kind of preparation methods of high-throughput antipollution special type tubular ultra-filtration membrane, specifically includes the following steps: the selection and weighing of S1, raw material, S2, configuration casting solution, S3, wound membrane coating, the rinsing processing of S4, membrane tube, the present invention relates to extraordinary tubular type ultrafiltration membrane technique fields.The preparation method of the high throughput antipollution special type tubular ultra-filtration membrane, this preparation method is simple, industrial applications prospect is big, in traditional pretreated technical foundation of dyeing waste water, this special type tubular membrane component is applied in the advanced treatment system of dyeing waste water, utilize the screening characteristics of extraordinary tubular membrane, substantially reduce the pretreatment time of dyeing waste water, counter-infiltration system influent quality is also significantly increased simultaneously, effectively raise the service life of counter-infiltration system, use self-control tubular ultra-filtration membrane, significantly reduce turbidity of wastewater, be conducive to subsequent use biochemical method and carry out processing to realize qualified discharge, significantly reduce sewage treatment later period difficulty.)

1. a kind of preparation method of high throughput antipollution special type tubular ultra-filtration membrane, it is characterised in that: specifically includes the following steps:

The selection and weighing of S1, raw material: sulfonated polyether-ether-ketone of the desired weight than part is distinguished by weighing equipment first (SPSF), n,N-dimethylacetamide (DMAc), pore-foaming agent polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) -400 are fitted Sulfonated polyether-ether-ketone, DMAC N,N' dimethyl acetamide and the pore-foaming agent of amount；

S2, configuration casting solution: opening stirring, then aqueous solution be added in stirring container, opens stirring in the case where stirring at low speed, adds : the 150r/min that enters pore-foaming agent PVP and PEG-400, be warming up to 60 DEG C, mixing speed stirs for about 30min, determines pore-foaming agent After completely dissolution, SPEEK toner is added, slowly increases mixing speed, guarantees that SPEEK toner does not fall to spinning kettle Bottom；Stirring continues for 24 hours under the conditions of 60 DEG C, 650r/min, until casting solution is uniformly dissolved, closing temperature control, stirring rate It is down to 100r/min, until casting solution temperature is down to room temperature, reaction kettle accesses vacuum pump, vacuumizes 30min, pressure valve is closed, Keeping negative pressure state in reaction kettle, room temperature standing and defoaming, it is ensured that casting solution deaeration is complete, the appropriate discharge before wound membrane coats, until Feed liquid clear homogeneous, bubble-free is discharged, while casting solution appropriate is discharged in clean flask, is used for viscosity test；

S3, wound membrane coating: installation center bar to tubular membrane membrane equipment center-pole fixed frame；Reaction kettle feeder sleeve is connected to center Bar；Non-woven fabrics is fixed on belt disc, sequentially passes through strap control-rod and strap collet；Belt winding center-pole and two sides are turned Axis, and non-woven fabrics is wrapped on center-pole；Tubular membrane membrane equipment power supply is opened, ultrasonic bonding debugging, operation master are carried out Axis rotation, so that non-woven fabrics follows belt to be rotationally advancing；Ultrasonic welding is opened simultaneously, is adjusted strap angle and belt tension, is made Obtaining solder joint is in 2 ± 0.5mm width, stable operation 5m membrane tube, it is ensured that can start to apply with rosin joint without losing shape；Reaction kettle connects Air compressor opens charging pump；Control feed pump speed makes load up to 2 ± 0.3g/min, so that the welding of coating Uniformly there is casting solution thin layer in pipe surface；

The rinsing processing of S4, membrane tube: the coated membrane tube of clip suitable length is put into vertical gel slot；It will be pure in membrane tube After water carries out 5-8 displacement, membrane tube is taken out, is put into No. 1 potcher, impregnates；It is transferred to No. 2 potchers again, impregnates rinsing, drift After washing, membrane tube is taken out, is immersed in a certain proportion of glycerol-water mixed solution for 24 hours；After immersion, taking-up is dried, Both high-throughput antipollution special type tubular ultra-filtration membrane, extraordinary tubular ultra-filtration membrane membrane tube.

2. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: The raw material of the high throughput antipollution special type tubular ultra-filtration membrane by weight part include 18-20 parts of sulfonated polyether-ether-ketones (SPSF), 70-72 parts of n,N-dimethylacetamide (DMAc), 2.5-5 parts of pore-foaming agent polyvinylpyrrolidones (PVP) and 5-7.5 parts of poly- second two Alcohol (PEG) -400, suitable sulfonated polyether-ether-ketone, n,N-dimethylacetamide and pore-foaming agent.

3. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: The raw material of the formula A of the high throughput antipollution special type tubular ultra-filtration membrane includes 18 parts of sulfonated polyether-ether-ketones by weight part (SPSF), 70 parts of n,N-dimethylacetamide (DMAc), 2.5 parts of pore-foaming agent polyvinylpyrrolidones (PVP) and 5 parts of polyethylene glycol (PEG) -400, suitable sulfonated polyether-ether-ketone, n,N-dimethylacetamide and pore-foaming agent.

4. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: The raw material of the formula B of the high throughput antipollution special type tubular ultra-filtration membrane includes 20 parts of sulfonated polyether-ether-ketones by weight part (SPSF), 72 parts of n,N-dimethylacetamide (DMAc), 5 parts of pore-foaming agent polyvinylpyrrolidones (PVP) and 7.5 parts of polyethylene glycol (PEG) -400, suitable sulfonated polyether-ether-ketone, n,N-dimethylacetamide and pore-foaming agent.

5. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: Vacuum pressure is -0.1MPa in reaction kettle in the step S2.

6. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: The room temperature standing and defoaming time is most short for for 24 hours in the step S2.

7. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: Reacting kettle inner pressure is 0.2Mpa in the step S3.

8. a kind of preparation method of high-throughput antipollution special type tubular ultra-filtration membrane according to claim 1, it is characterised in that: Soaking time is 6 hours in No.1 potcher in the step S4, and soaking time is for 24 hours in No. 2 potchers.

Technical field

The present invention relates to extraordinary tubular type ultrafiltration membrane technique field, specially a kind of high-throughput antipollution special type tubular ultra-filtration membrane Preparation method.

Background technique

China is textile printing and dyeing big country, and textile printing and dyeing industry is the discharge rich and influential family of industrial wastewater, and wastewater flow rate accounts for about entire work The one third of industry wastewater discharge, water is big, salinity is high, high organic content, coloration are high, alkalinity is strong, change of water quality is big etc. It is the distinguishing feature of dyeing waste water, has become one of the important environomental pollution source in China and refractory reason harmful waste water, it is whole at present A textile industry wastewater recycle rate is one of the industry that wastewater recycle rate is minimum in the existing industry in China, water resource less than 10% Deficient status has become one of the important limiting factor for restricting the progress of China's textile printing and dyeing industry, meanwhile, with new Type dye, auxiliary agent are continually developed, and the continuous increase of application processing difficulty, and increasingly stringent with discharge standard, Also constantly gone up with water rate, therefore, in order to realize the sustainable development of dyeing, is eliminating the potential danger of environmental pollution Evil, dyeing waste water advanced treating and reuse technology are becoming the major issue urgently studied and solved.

Main method currently used for treatment of dyeing wastewater has physico-chemical process, biochemical method, chemical method and several techniques to combine Processing method, and pretreatment in wastewater treatment is removed oil removal and can directly be settled primarily to improve waste water quality Impurity, adjust waste water quality and water, reduce waste water temperature etc., improving the overall effect of wastewater treatment, it is ensured that entire processing The stability of system, therefore pre-process with extremely important status in treatment of dyeing wastewater, with the development of film industry, film Isolation technics becomes one of the technology of printing-dying wastewater recycling most feasibility, the membrane technology currently used for treatment of dyeing wastewater Mainly there is reverse osmosis, hyperfiltration treatment system, dyeing waste water still uses conventional processes before hyperfiltration treatment, to change Kind waste water quality, the heavy load removed oil removal, reduce hyperfiltration treatment system.

Summary of the invention

(1) the technical issues of solving

In view of the deficiencies of the prior art, the present invention provides a kind of preparation sides of high-throughput antipollution special type tubular ultra-filtration membrane Method, solving mainly has reverse osmosis, hyperfiltration treatment system currently used for the membrane technology for the treatment of of dyeing wastewater, before hyperfiltration treatment Dyeing waste water still use conventional processes, go oil removal, hyperfiltration treatment system heavy load the problem of.

(2) technical solution

In order to achieve the above object, the present invention is achieved by the following technical programs: a kind of high throughput antipollution special pipe The preparation method of formula ultrafiltration membrane, specifically includes the following steps:

The selection and weighing of S1, raw material: sulfonated polyether ether of the desired weight than part is distinguished by weighing equipment first Ketone (SPSF), n,N-dimethylacetamide (DMAc), pore-foaming agent polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) -400, Suitable sulfonated polyether-ether-ketone, DMAC N,N' dimethyl acetamide and pore-foaming agent；

S2, configuration casting solution: opening stirring, then aqueous solution be added in stirring container, opens stirring and is stirring at low speed Under, pore-foaming agent PVP and PEG-400 is added, is warming up to 60 DEG C, mixing speed: 150r/min, stirring are determined and are caused for about 30min After completely dissolution, SPEEK toner is added in hole agent, slowly increases mixing speed, guarantees that SPEEK toner does not fall to spinning Silk bottom portion；Stirring continues for 24 hours under the conditions of 60 DEG C, 650r/min, until casting solution is uniformly dissolved, closing temperature control, stirring Rate is down to 100r/min, until casting solution temperature is down to room temperature, reaction kettle accesses vacuum pump, vacuumizes 30min, closes pressure control Valve keeps negative pressure state in reaction kettle, room temperature standing and defoaming, it is ensured that and casting solution deaeration is complete, the appropriate discharge before wound membrane coats, To discharge feed liquid clear homogeneous, bubble-free, while casting solution appropriate is discharged in clean flask makes for viscosity test With；

S3, wound membrane coating: installation center bar to tubular membrane membrane equipment center-pole fixed frame；Connection reaction kettle feeder sleeve arrives Center-pole；Non-woven fabrics is fixed on belt disc, sequentially passes through strap control-rod and strap collet；Belt is wound into center-pole and two Side shaft, and non-woven fabrics is wrapped on center-pole；Tubular membrane membrane equipment power supply is opened, ultrasonic bonding debugging, fortune are carried out Row main axis, so that non-woven fabrics follows belt to be rotationally advancing；Ultrasonic welding is opened simultaneously, adjusts strap angle and belt pine Tightly, so that solder joint is in 2 ± 0.5mm width, stable operation 5m membrane tube, it is ensured that can start to apply with rosin joint without losing shape；Instead It answers kettle to connect air compressor, opens charging pump；Control feed pump speed makes load up to 2 ± 0.3g/min, so that coating Welding pipe surface uniformly there is casting solution thin layer；

The rinsing processing of S4, membrane tube: the coated membrane tube of clip suitable length is put into vertical gel slot；It will be in membrane tube Pure water carry out 5-8 time displacement after, membrane tube is taken out, is put into No. 1 potcher, immersion；It is transferred to No. 2 potchers again, impregnates drift It washes, after rinsing, membrane tube is taken out, be immersed in a certain proportion of glycerol-water mixed solution for 24 hours；After immersion, take out Dry, both high-throughput antipollution special type tubular ultra-filtration membrane, extraordinary tubular ultra-filtration membrane membrane tube.

Preferably, the raw material of the high-throughput antipollution special type tubular ultra-filtration membrane includes 18-20 parts of sulfonation by weight part Polyether-ether-ketone (SPSF), 70-72 parts of n,N-dimethylacetamide (DMAc), 2.5-5 parts of pore-foaming agent polyvinylpyrrolidones (PVP) With 5-7.5 parts of polyethylene glycol (PEG) -400, suitable sulfonated polyether-ether-ketone, n,N-dimethylacetamide and pore-foaming agent.

Preferably, the raw material of the formula A of the high-throughput antipollution special type tubular ultra-filtration membrane includes 18 parts by weight part Sulfonated polyether-ether-ketone (SPSF), 70 parts of n,N-dimethylacetamide (DMAc), 2.5 parts of pore-foaming agent polyvinylpyrrolidones (PVP) With 5 parts of polyethylene glycol (PEG) -400, suitable sulfonated polyether-ether-ketone, n,N-dimethylacetamide and pore-foaming agent.

Preferably, the raw material of the formula B of the high-throughput antipollution special type tubular ultra-filtration membrane includes 20 parts by weight part Sulfonated polyether-ether-ketone (SPSF), 72 parts of n,N-dimethylacetamide (DMAc), 5 parts of pore-foaming agent polyvinylpyrrolidones (PVP) and 7.5 parts of polyethylene glycol (PEG) -400, suitable sulfonated polyether-ether-ketone, n,N-dimethylacetamide and pore-foaming agent.

Preferably, vacuum pressure is -0.1MPa in reaction kettle in the step S2.

Preferably, the room temperature standing and defoaming time is most short for for 24 hours in the step S2.

Preferably, reacting kettle inner pressure is 0.2Mpa in the step S3.

Preferably, soaking time is 6 hours in No.1 potcher in the step S4, and soaking time is in No. 2 potchers 24h。

(3) beneficial effect

The present invention provides a kind of preparation methods of high-throughput antipollution special type tubular ultra-filtration membrane.Compared with prior art, Have it is following the utility model has the advantages that

(1), the preparation method of the high throughput antipollution special type tubular ultra-filtration membrane, passes through the selection and weighing in S1, raw material: Desired weight is distinguished than the sulfonated polyether-ether-ketone (SPSF) of part, n,N-dimethylacetamide by weighing equipment first (DMAc), pore-foaming agent polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) -400, suitable sulfonated polyether-ether-ketone, N, N- bis- Methylacetamide and pore-foaming agent, this preparation method is simple, industrial applications prospect is big, in traditional pretreated skill of dyeing waste water On the basis of art, this special type tubular membrane component is applied in the advanced treatment system of dyeing waste water, the sieve of extraordinary tubular membrane is utilized It is intrinsic, the pretreatment time of dyeing waste water is substantially reduced, while also significantly increasing counter-infiltration system influent quality, effectively The service life for improving counter-infiltration system.

(2), the preparation method of the high throughput antipollution special type tubular ultra-filtration membrane, by S2, configuration casting solution: unlatching is stirred It mixes, then aqueous solution is added in stirring container, open stirring in the case where stirring at low speed, pore-foaming agent PVP and PEG-400 is added, rise Temperature is to 60 DEG C, and mixing speed: 150r/min stirs for about 30min, determines pore-foaming agent after completely dissolution, and SPEEK resin is added Powder slowly increases mixing speed, guarantees that SPEEK toner does not fall to spinning bottom portion；Stirring is in 60 DEG C, 650r/min Under the conditions of continue for 24 hours, until casting solution is uniformly dissolved, closing temperature control, stirring rate is down to 100r/min, until casting solution temperature Degree is down to room temperature, and reaction kettle accesses vacuum pump, vacuumizes 30min, closes pressure valve, keeps negative pressure state in reaction kettle, room temperature Standing and defoaming, it is ensured that casting solution deaeration is complete, the appropriate discharge before wound membrane coats, until discharge feed liquid clear homogeneous, bubble-free are Can, while casting solution appropriate is discharged in clean flask, it is used for viscosity test, uses self-control tubular ultra-filtration membrane, special pipe Formula film can effectively remove suspended matter in dyeing waste water, significantly reduce turbidity of wastewater, be conducive to subsequent using at biochemical method Reason significantly reduces sewage treatment later period difficulty to realize qualified discharge.

(3), the preparation method of the high throughput antipollution special type tubular ultra-filtration membrane passes through the rinsing processing in S4, membrane tube: cutting The membrane tube that suitable length is coated is taken, is put into vertical gel slot；After pure water in membrane tube is carried out 5-8 displacement, by membrane tube It takes out, is put into No. 1 potcher, impregnate；It is transferred to No. 2 potchers again, impregnates rinsing, after rinsing, membrane tube is taken out, impregnates In a certain proportion of glycerol-water mixed solution for 24 hours；After immersion, taking-up is dried, both high-throughput antipollution special type tubular type Ultrafiltration membrane, extraordinary tubular ultra-filtration membrane membrane tube, polysulfones (PSF), polyether sulfone (PES), can be in macromolecular structures after concentrated acid sulfonation Middle introducing sulfonic acid lateral group obtains sulfonated polyether-ether-ketone (SPSF), sulfonated polyether sulfone (SPES), in both sulfonated polymer high scores Sulfonic group in subchain has charge, can generate electrical charge rejection effect, sulfonated polyether-ether-ketone and sulfonated polyether sulfone are applied to Extraordinary tubular type membrane material can play electrical charge rejection effect in application process, efficiently reduce pollutant to the attached of film inner wall , slow down the stifled water flux and its service life to effectively improve membrane tube of dirt of extraordinary tubular membrane, reduces extraordinary tubular membrane Use cost.

Detailed description of the invention

Fig. 1 is flow chart prepared by the present invention；

Specific embodiment

Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.

Referring to Fig. 1, the embodiment of the present invention provides two kinds of technical solutions: a kind of high throughput antipollution special type tubular ultra-filtration membrane Preparation method, specifically includes the following steps: