WO2023198214A1 - 一种适用于油田回注水处理聚酰胺纳滤膜的制备方法 - Google Patents

一种适用于油田回注水处理聚酰胺纳滤膜的制备方法 Download PDF

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WO2023198214A1
WO2023198214A1 PCT/CN2023/088554 CN2023088554W WO2023198214A1 WO 2023198214 A1 WO2023198214 A1 WO 2023198214A1 CN 2023088554 W CN2023088554 W CN 2023088554W WO 2023198214 A1 WO2023198214 A1 WO 2023198214A1
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membrane
preparation
water
chloride
prepare
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PCT/CN2023/088554
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English (en)
French (fr)
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刘宝山
聂明
陈爱民
梁松苗
胡利杰
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中海油天津化工研究设计院有限公司
中国海洋石油集团有限公司
沃顿科技股份有限公司
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Publication of WO2023198214A1 publication Critical patent/WO2023198214A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present application relates to the technical field of water treatment membranes, more specifically to the technical field of nanofiltration membranes, and in particular to a polyamide nanofiltration membrane that can efficiently treat oilfield reinjection water and its preparation method.
  • the mainstream method currently used is to inject water into the oil well formation to keep the oil layer pressure stable or increase, so as to achieve the purpose of stable and high production of oil wells and increase recovery rate.
  • the injected water and crude oil are extracted together.
  • Oilfield reinjection water requires low hardness and a certain salt content. Too high hardness can easily block the oil production pipeline due to inorganic scaling and increase production costs. Too low salt content in the injection water will lead to the occurrence of clay in the oil well. Expansion is not conducive to the extraction of crude oil; secondly, suspended solids and oil substances in the water body also need to be removed as much as possible.
  • Traditional reinjection water treatment processes include flocculation, sedimentation, filtration and other processes combined with microfiltration or ultrafiltration membrane treatment methods.
  • Traditional treatment processes It is difficult to achieve efficient removal of polymer and hardness.
  • the nanofiltration water treatment process has the advantages of low energy consumption, flexible system application, high selectivity, and little influence from the external environment. It can achieve efficient removal of low molecular organic polymers and calcium and magnesium ions.
  • conventional nanofiltration membranes have poor pollution resistance. Poor performance. In practical applications, it is easier to cause fouling of membrane elements, resulting in a significant decline in water production performance of membrane elements.
  • the technical problem to be solved by the present invention is to overcome the shortcomings of the existing technology and develop a pollution-resistant high-selector It is a nanofiltration membrane that is selectively suitable for oilfield reinjection water treatment. Under an operating pressure of 100 psi, the membrane's desalination rate for MgSO 4 is not less than 98.5%, and the membrane flux is above 25GFD.
  • the solution of the technology of the present invention is to use a support layer prepared by a blended polymer.
  • aqueous phase additives, polyamine monomers, acid acceptors and water are used to prepare aqueous phase solutions.
  • the aqueous phase additives can promote the diffusion of aqueous phase monomers into the oil phase during interfacial polymerization and increase the friction between the two phases.
  • the diffusion contact area increases the interfacial polymerization reaction rate and increases the cross-linking degree of the primary layer at the interface, which is beneficial to improving the desalination performance; secondly, the addition of water phase additives also significantly improves the pollution resistance of the composite membrane.
  • the present invention is a preparation method of a polyamide nanofiltration membrane suitable for oilfield reinjection water treatment, which includes the following steps:
  • the polymer in the casting liquid is one or more of polyethersulfone, polyvinylidene fluoride, polysulfone, and sulfonated polysulfone, and the total polymer content accounts for the mass percentage of the casting liquid. is 16-19%;
  • the polyamine monomer content is 1.0-5.0%, and the aqueous phase additive content is 0.5-5%.
  • the organic phase solution is composed of polybasic acid chloride and organic solvent, wherein the mass percentage of polybasic acid chloride is 0.2-1.0%.
  • the porogen of the casting liquid is selected from one or more of polyethylene glycol, polyvinylpyrrolidone, N-methylpyrrolidone, lithium chloride, and hydroxymethylcellulose, and the total amount Control it between 0.4-4.0%.
  • the polyamine monomer in the water phase is cyclohexanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, piperazine, p-phenylenediamine, benzidine, polyethyleneimine, polyamide One or more imines.
  • the water phase additive is selected from one of polyethylene glycol, ammonium citrate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, ethanolamine, phosphonic acid additives, carboxylic acid betaine zwitterionic polymer, or Various.
  • a mass percentage of 0.5-2.5% sodium phosphate is selected as the acid acceptor
  • one or more of terephthaloyl chloride, isophthaloyl chloride and trimesoyl chloride is selected as the organic phase monomer.
  • the organic solvent selected for the organic phase in the above preparation method includes one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, ISOPAR-E, and ISOPAR-G. kind.
  • the invention further provides the polyamide nanofiltration membrane prepared by the above preparation method.
  • the present invention further provides an application of the above-mentioned polyamide nanofiltration membrane in oil field reinjection water treatment.
  • the present invention uses water-phase additives that are cheap and easy to obtain, and can effectively increase the diffusion rate of water-phase monomers to the organic phase interface, increase the contact area between the two phases, and make the interfacial polymerization reaction proceed more completely. It can improve the anti-pollution performance of the membrane surface to a certain extent; on the other hand, blending polymer is selected as the support layer of the composite membrane, which not only adjusts the hydrophilicity, but also improves the integrity of the surface microstructure and has a significant impact on the overall mechanical strength of the composite membrane. improve.
  • the polyamide nanofiltration membrane of the present invention has a raw water concentration (MgSO 4 ) of 2000 ppm and a temperature of 25°C.
  • the membrane flux is not less than 25GFD and the membrane desalination rate is not less than 98.5%.
  • the desalination rate represents (raw water concentration - pure water concentration)/raw water concentration
  • the flux represents the water flow rate per unit membrane area of the membrane.
  • the unit is recorded as Gal ⁇ ft 2 /d (GFD), and bovine serum albumin ( BSA) is used to evaluate the resistance of diaphragms to organic pollution.
  • step (2) Preparation of porous support layer:
  • the blended casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed in the coagulation bath.
  • gel-cured In the process, a porous support layer blend membrane is obtained by scraping, in which the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and the transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the porous blended polymer membrane obtained in step (2) into the aqueous phase solution for 1 min, take it out and drain the surface water beads, then immerse it into the oil phase solution for 0.5 min, take it out After drying, rinse with deionized water for 2 minutes, soak in a glycerin aqueous solution with a glycerol content of 12.5wt% for 2 minutes, and finally dry the membrane at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, the organic pollution resistance verification experiment is performed on the membrane, and 100 ppm bovine serum is prepared. The protein BSA cycle was run for 24 hours, and the contaminated membrane was cycled and cleaned with 2000 ppm NaOH for 4 hours. The measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed in the coagulation bath.
  • a porous support layer polysulfone membrane is obtained by scraping, in which the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and the transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the porous blended polymer membrane obtained in step (2) into the aqueous phase solution for 1 min, take it out and drain the surface water beads, then immerse it into the oil phase solution for 0.5 min, take it out After drying, rinse with deionized water for 2 minutes, soak in a glycerin aqueous solution with a glycerol content of 12.5wt% for 2 minutes, and finally dry the membrane at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, an organic pollution test is performed on the membrane to prepare 100 ppm bovine serum albumin BSA. Run the cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours. The measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed in the coagulation bath.
  • a porous support layer polysulfone membrane is obtained by scraping, in which the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and the transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process take the porous membrane of the blended polymer prepared in step (2) and immerse it in Put it in the aqueous solution for 1 minute, remove and drain the surface water beads, and then immerse it in the oil solution for 0.5 minutes. Take it out to dry and rinse with deionized water for 2 minutes. Soak it in a glycerin aqueous solution with a glycerin content of 12.5wt% for 2 minutes. Finally, the membrane Dry at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, an organic pollution test is performed on the membrane to prepare 100 ppm bovine serum albumin BSA. Run the cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours. The measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended polymer casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed and solidified.
  • a porous support layer polysulfone membrane is obtained by scraping.
  • the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and The transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the porous blended polymer membrane obtained in step (2) into the aqueous phase solution for 1 min, take it out and drain the surface water beads, then immerse it into the oil phase solution for 0.5 min, take it out After drying, rinse with deionized water for 2 minutes, soak for 2 minutes in a glycerin aqueous solution with a glycerin content of 12.5wt%, and finally The membrane was then dried at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, an organic pollution test is performed on the membrane to prepare 100 ppm bovine serum albumin BSA. Run the cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours. The measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended polymer casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed and solidified.
  • a porous support layer polysulfone membrane is obtained by scraping.
  • the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and The transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the porous blended polymer membrane obtained in step (2) into the aqueous phase solution for 1 min, take it out and drain the surface water beads, then immerse it into the oil phase solution for 0.5 min, take it out After drying, rinse with deionized water for 2 minutes, soak in a glycerin aqueous solution with a glycerol content of 12.5wt% for 2 minutes, and finally dry the membrane at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing.
  • the test pressure is 100 psi and the raw water concentration MgSO 4 is 2000 ppm.
  • the organic pollution test of the membrane is carried out.
  • For the test prepare 100ppm bovine serum albumin BSA and run it in a cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours.
  • the measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended polymer casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed and solidified.
  • a porous support layer polysulfone membrane is obtained by scraping.
  • the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and The transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the porous blended polymer membrane obtained in step (2) into the aqueous phase solution for 1 min, take it out and drain the surface water beads, then immerse it into the oil phase solution for 0.5 min, take it out After drying, rinse with deionized water for 2 minutes, soak in a glycerin aqueous solution with a glycerol content of 12.5wt% for 2 minutes, and finally dry the membrane at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, an organic pollution test is performed on the membrane to prepare 100 ppm bovine serum albumin BSA. Run the cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours. The measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended polymer casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed and solidified.
  • a porous support layer polysulfone membrane is obtained by scraping.
  • the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and The transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the porous blended polymer membrane obtained in step (2) into the aqueous phase solution for 1 min, take it out and drain the surface water beads, then immerse it into the oil phase solution for 0.5 min, take it out After drying, rinse with deionized water for 2 minutes, soak in a glycerin aqueous solution with a glycerol content of 12.5wt% for 2 minutes, and finally dry the membrane at 80°C for 2 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, an organic pollution test is performed on the membrane to prepare 100 ppm bovine serum albumin BSA. Run the cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours. The measured performance is as follows:
  • step (2) Preparation of porous support layer:
  • the blended polymer casting liquid obtained in step (1) is evenly spread on the polyester non-woven fabric, and the conveying speed is controlled so that the non-woven fabric covered with the casting liquid is slowly immersed and solidified.
  • a porous support layer polysulfone membrane is obtained by scraping.
  • the main component of the coagulation bath is deionized water.
  • the temperature of the coagulation bath needs to be controlled at 13-16°C, and The transmission speed is 6m/min;
  • Interfacial polymerization and post-treatment process Immerse the polysulfone porous membrane prepared in step (2) into the aqueous phase solution for 1 minute, take it out and drain the surface water beads, then immerse it in the oil phase solution for 0.5 minutes, take it out and dry it Then rinse with deionized water for 2 minutes, soak in a glycerin aqueous solution with a glycerol content of 12.5wt% for 2 minutes, and finally dry the membrane at 100°C for 4 minutes to prepare a composite nanofiltration membrane;
  • Membrane performance test Take the composite nanofiltration membrane obtained in the above steps and place it in a mold for performance testing. The test pressure is 100 psi and the raw water concentration is MgSO 4 2000 ppm. At the same time, an organic pollution test is performed on the membrane to prepare 100 ppm bovine serum albumin BSA. Run the cycle for 24 hours, and clean the contaminated membrane with 2000ppm NaOH for 4 hours. The measured performance is as follows:

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  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

一种适用于油田回注水处理聚酰胺纳滤膜的制备方法，包括：在高极性有机溶剂中加入致孔剂和聚合物，加热下搅拌溶解，配制得到铸膜液，并刮涂在聚酯无纺布上制成膜；将所刮制的膜片作为支撑层浸入含有水相添加剂、酸接受剂和多元胺单体的水相溶液中0.5-2min，阴干并除去表面多余水珠，再将其浸入含多元酰氯的有机相溶液中0.5-2min，膜片取出常温下晾干，经去离子水水洗、烘干得到聚酰胺复合纳滤膜。

Description

一种适用于油田回注水处理聚酰胺纳滤膜的制备方法 技术领域
本申请涉及水处理膜技术领域，更具体地涉及纳滤膜技术领域，特别涉及一种高效处理油田回注水的聚酰胺纳滤膜及其制备方法。
背景技术
在油田开采过程中，随着开采时间的延长，油田开发不断深入、油层压力逐渐下降，当油层压力下降到一定程度时，原油中油气比上升，导致原油粘度增加，流动性降低，使得原油开采相对困难，开采效率降低。为保持油层压力，延长油井开采寿命，目前采用的主流方法就是向油井地层中注水，使油层压力保持稳定或上升，达到油井稳产高产，提高采收率的目的。在注水采油过程中，注入水和原油一起采出，经过油水分离后会产生大量的油田废水，若将含油废水直接外排，将造成严重的环境污染问题，同时又浪费了水资源，如果将废水处理后重新回注地层补充油井压力，不但可以避免环境污染，而且节约了大量的水资源。
油田回注水要求注水水质需要满足低硬度，且需要保持一定含盐量，硬度过高容易因为无机结垢堵塞采油管道，增大开采成本，而注水中盐量过低将会导致油井中粘土发生膨胀，不利于原油的开采；其次对于水体中的悬浮物及油类物质也需要尽可能的脱除。
传统回注水处理工艺包括絮凝、沉淀、过滤等工序再结合微滤或超滤膜处理方式，随着采油技术的发展，水中聚合物含量升高、废水中水质矿化硬度较高，传统处理工艺难以实现聚合物及硬度的高效脱除。纳滤水处理工艺具有能耗低、系统应用灵活、选择性高且受外部环境影响小等优点，可实现低分子有机聚合物和钙镁离子的高效脱除，然而常规纳滤膜耐污染性能较差，实际应用中较容易产生膜元件污堵情况，导致膜元件产水性能大幅衰减。
因此，如何开发一款适用于油田回注水处理的高选择性耐污染纳滤膜是目前回注水处理领域一个亟待解决的问题。
发明内容
本发明所需要解决的技术问题是克服现有技术的不足，开发一种耐污染高选 择性的适用于油田回注水处理的纳滤膜，该纳滤膜能在100psi的运行压力下，膜片对于MgSO4的脱盐率不低于98.5％，同时膜片通量在25GFD以上。
本发明技术的解决方案是采用共混聚合物制备的支撑层，通过调节共混聚合物比例控制支撑层亲水性，改善支撑层表面水相单体分布的均匀性，更利于形成无缺陷的聚酰胺分离层结构；同时选用水相添加剂、多元胺单体、酸接受剂和水配制水相溶液，水相添加剂能够促进界面聚合过程中水相单体向油相的扩散，增加两相间的扩散接触面积，提升界面聚合反应速率，增大界面处初生层交联度，利于脱盐性能的提升；其次，水相添加剂的加入对复合膜的耐污染性能也有明显提升。
本发明一种适用于油田回注水处理聚酰胺纳滤膜的制备方法，包含步骤如下：
1)在高极性有机溶剂中加入致孔剂和聚合物，加热下搅拌溶解，配制得到铸膜液，并刮涂在聚酯无纺布上制成膜；
2)将所刮制的膜片作为支撑层浸入含有水相添加剂、酸接受剂和多元胺单体的水相溶液中0.5-2min，阴干并除去表面多余水珠，再将其浸入含多元酰氯的有机相溶液中0.5-2min，膜片取出，经去离子水水洗、烘干得到聚酰胺复合纳滤膜；
其中，所述的聚合物为铸膜液中聚合物为聚醚砜、聚偏氟乙烯、聚砜、磺化聚砜的一种或多种，聚合物总含量占所述铸膜液质量百分比为16-19％；
所述的水相溶液中，多元胺单体含量为1.0-5.0％、水相添加剂含量为0.5-5％。
所述有机相溶液由多元酰氯和有机溶剂组成，其中多元酰氯的质量百分含量为0.2-1.0％。
作为优选，上述制备方法中铸膜液致孔剂选取聚乙二醇、聚乙烯吡咯烷酮、N-甲基吡咯烷酮、氯化锂、和羟甲基纤维素中的一种或多种，且总量控制在0.4-4.0％之间。
作为优选，水相中多元胺单体选取环己二胺、对苯二胺、间苯二胺、邻苯二胺、哌嗪、对苯二甲胺、联苯胺、聚乙烯亚胺、聚酰亚胺中的一种或多种。
作为优选，水相添加剂选择聚乙二醇、柠檬酸铵、十二烷基苯磺酸钠、聚乙烯醇、乙醇胺、膦酸类助剂、羧酸型甜菜碱两性离子聚合物的一种或多种。
作为优选，上述制备方法中，选取质量百分比为0.5-2.5％磷酸钠作为酸接受剂；
作为优选，上述制备方法中，选取对苯二甲酰氯、间苯二甲酰氯和均苯三甲酰氯中的一种或多种作为有机相单体。
作为优选，上述制备方法中有机相选取的有机溶剂包含正己烷、正庚烷、环己烷、甲基环己烷、乙基环己烷、ISOPAR-E、ISOPAR-G中的一种或多种。
本发明进一步提供了由上述制备方法制备得到的聚酰胺纳滤膜。
本发明进一步提供了一种上述的聚酰胺纳滤膜在聚酰胺纳滤膜在油田回注水处理中的应用。
与现有技术比较，本发明采用水相添加剂廉价易得，能高效地提升水相单体向有机相界面的扩散速率，增大两相的接触面，使界面聚合反应进行得更完全，同时能一定程度上提升膜面抗污染性能；另一方面，选用共混聚合作为复合膜支撑层，调节亲水性的同时，改善了表层微观结构的完整性，对复合膜的整体机械强度也有明显提高。本发明聚酰胺纳滤膜在100psi压力下，原水浓度(MgSO4)2000ppm，温度25℃，膜片通量不低于25GFD且膜片脱盐率不低于98.5％。
具体实施方式
下面就本发明的具体实施方式举例说明；
以下实例阐述了基于一种简单新型高通量纳滤膜的制备方法，下述实例仅提供说明而非限定本发明；
以下实例中脱盐率代表(原水浓度-纯水浓度)/原水浓度，通量则代表通过膜片单位膜面积的产水流量，单位记作Gal·ft2/d(GFD)，牛血清蛋白(BSA)用于评测膜片耐有机污染性能。
实施例1
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g聚砜(17wt％)和90g聚偏氟乙烯(2wt％)及36g氯化锂(0.8wt％)加入盛有3609gDMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过 程，刮制得到多孔支撑层共混膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(0.5wt％)加入纯水(96wt％)配制水相溶液；
(4)油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，置于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行耐有机污染验证实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppmNaOH循环清洗4h，分别测得性能如下表：
实施例2
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g磺化聚砜(17wt％)和90g聚偏氟乙烯(2wt％)及36g氯化锂(0.8wt％)加入盛有3609gDMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0 wt％)，柠檬酸铵(0.5wt％)加入纯水(96wt％)配制水相溶液；
(4)油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：
实施例3
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g磺化聚砜(17wt％)和90g聚醚砜(2wt％)及36g氯化锂(0.8wt％)加入盛有3609gDMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(0.5wt％)加入纯水(96wt％)配制水相溶液；
(4)油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入 水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：
实施例4
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g磺化聚砜(17.0wt％)和90g聚醚砜(2.0wt％)及36g氯化锂(0.8wt％)加入盛有3609gDMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混聚合物铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(0.75wt％)加入纯水(95.75wt％)配制水相溶液；
(4)油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最 后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：
实施例5
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g磺化聚砜(17.0wt％)和90g聚醚砜(2.0wt％)及36g氯化锂(0.8wt％)加入盛有3609gDMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混聚合物铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(1.0wt％)加入纯水(95.5wt％)配制水相溶液；
(4)油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实 验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：
实施例6
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g磺化聚砜(17wt％)和90g聚醚砜(2wt％)及36gN-甲基吡咯烷酮NMP(0.8wt％)加入盛有3609gDMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混聚合物铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(0.75wt％)加入纯水(95.75wt％)配制水相溶液；
(4)油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：

实施例7
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g聚砜(17wt％)和90g聚醚砜(2wt％)及36g N-甲基吡咯烷酮NMP(0.8wt％)加入盛有3609g DMF(80.2wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混聚合物铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(0.75wt％)加入纯水配制水相溶液；
(4)油相溶液的配制：油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于正己烷中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得共混聚合物多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于80℃烘干2min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：

实施例8
(1)配制铸膜液：以所述共混铸膜液的总质量计，分别称取765g磺化聚砜(17.0wt％)和90g聚醚砜(2.0wt％)及36gN-甲基吡咯烷酮NMP(0.8wt％)加入盛有1804g DMF(40.1wt％)和1804g DMAC(40.1wt％)烧杯中，于150℃下搅拌溶解，冷却至室温(若冷却后聚合物溶液中有气泡，需置于0.06MPa的负压下经真空脱泡处理)，密封放置备用；
(2)多孔支撑层的制备：步骤(1)所制得共混聚合物铸膜液均匀刮涂在聚酯无纺布上，控制传送速度使覆有铸膜液的无纺布缓慢浸入凝固浴中，经过凝胶固化过程，刮制得到多孔支撑层聚砜膜，其中凝固浴主要成分为去离子水，为保证两相间溶剂的扩散速率，凝固浴温度需控制在13-16℃，且传送速度为6m/min；
(3)水相溶液的配制：称取无水哌嗪PIP(2.5wt％)，磷酸钠Na3PO4(1.0wt％)，柠檬酸铵(0.75wt％)加入纯水(95.5wt％)配制水相溶液；
(4)油相溶液的配制：油相溶液的配制：称取0.25wt％的均三苯甲酰氯TMC，搅拌下溶于ISOPAR-L中配制成为有机相溶液；
(5)界面聚合和后处理过程：取步骤(2)中所制得聚砜多孔膜浸入水相溶液中1min，取出沥干表面水珠，再将其浸入油相溶液0.5min，取出晾干后用去离子水冲洗2min，于甘油含量为12.5wt％的甘油水溶液浸泡2min，最后膜片于100℃烘干4min，制备得到复合纳滤膜；
(6)膜片性能测试：取上述步骤得到的复合纳滤膜置于模具中进行性能测试，测试压力100psi，原水浓度MgSO42000ppm，同时对膜片进行有机污染实验，配制100ppm牛血清蛋白BSA循环运行24h，将污染后膜片用2000ppm NaOH循环清洗4h，分别测得性能如下表：
需要说明的是，尽管以具体实施例介绍了本发明的技术方案，但本领域技术人员能够理解，本发明应不限于此。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。本文中所用术语的选择，旨在最好地解释各实施例的原理、实际应用或对市场中的技术改进，或者使本技术领域的其它普通技术人员能理解本文披露的各实施例。

Claims (8)

  1. 一种用于油田回注水处理聚酰胺纳滤膜的制备方法，其特征在于，
    1)在高极性有机溶剂中加入致孔剂和聚合物，加热下搅拌溶解，配制得到铸膜液，并刮涂在聚酯无纺布上制成膜；
    2)将所刮制的膜片作为支撑层浸入含有水相添加剂、酸接受剂和多元胺单体的水相溶液中0.5-2min，阴干并除去表面多余水珠，再将其浸入含多元酰氯的有机相溶液中0.5-2min，膜片取出常温下晾干，经去离子水水洗、烘干得到聚酰胺复合纳滤膜；
    其中，所述的高极性有机溶剂选自N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮的一种或两种；所述的聚合物为铸膜液中聚合物为聚醚砜、聚偏氟乙烯、聚砜、磺化聚砜的一种或多种，聚合物总含量占所述铸膜液质量百分比为16-19％；
    所述的水相溶液中，所述的多元胺单体含量为1.0-5.0％，所述水相添加剂含量为0.5-5％；
    所述有机相溶液由多元酰氯和有机溶剂组成，其中多元酰氯的质量百分含量为0.2-1.0％。
  2. 根据权利1所述的制备方法，其特征在于，所述的致孔剂为聚乙烯吡咯烷酮、N-甲基吡咯烷酮、氯化锂和羟甲基纤维素中的一种或多种，且总量控制在0.4-4.0％。
  3. 根据权利1所述的制备方法，其特征在于，所述的多元胺单体为环己二胺、对苯二胺、间苯二胺、邻苯二胺、哌嗪、对苯二甲胺、联苯胺、聚乙烯亚胺、聚酰亚胺中的一种或多种。
  4. 根据权利1所述的制备方法，其特征在于，水相添加剂为聚乙二醇、柠檬酸铵、十二烷基苯磺酸钠、聚乙烯醇、乙醇胺、膦酸类助剂、羧酸型甜菜碱两性离子聚合物中的一种或多种。
  5. 根据权利1所述的制备方法，其特征在于，所述的酸接受剂选用氢氧化钠、磷酸钠、碳酸钠、碳酸氢钠或碳酸钾中的一种或几种。
  6. 根据权利1所述的制备方法，其特征在于，步骤2)有机相溶液中所述的多元酰氯包含邻苯二甲酰氯、对苯二甲酰氯、间苯二甲酰氯、均苯三甲酰氯、联苯二甲酰氯中的一种或多种；所述的有机相溶液中的有机溶剂为正己烷、正庚烷、正辛烷、环己烷、甲基环己烷、乙基环己烷、ISOPAR-E、ISOPAR-G中的一种 或多种。
  7. 一种权利要求1～6所述制备方法制得的聚酰胺纳滤膜。
  8. 一种权利要求7所述的聚酰胺纳滤膜在聚酰胺纳滤膜在油田回注水处理中的应用。
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US20180326362A1 (en) * 2017-03-06 2018-11-15 China University Of Petroleum (East China) Highly selective alicyclic polyamide nanofiltration membrane and making method thereof
CN110314559A (zh) * 2019-07-31 2019-10-11 朱军勇 一种界面聚合复合膜的制备方法
CN114130206A (zh) * 2020-09-04 2022-03-04 沃顿科技股份有限公司 聚酰胺复合纳滤膜及其制备方法
CN114950136A (zh) * 2022-04-15 2022-08-30 中海油天津化工研究设计院有限公司 一种适用于油田回注水处理聚酰胺纳滤膜的制备方法

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CN110314559A (zh) * 2019-07-31 2019-10-11 朱军勇 一种界面聚合复合膜的制备方法
CN114130206A (zh) * 2020-09-04 2022-03-04 沃顿科技股份有限公司 聚酰胺复合纳滤膜及其制备方法
CN114950136A (zh) * 2022-04-15 2022-08-30 中海油天津化工研究设计院有限公司 一种适用于油田回注水处理聚酰胺纳滤膜的制备方法

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