CN113274897B - Preparation method of polyether functional oil-water separation membrane with amide bond in-situ crosslinking function - Google Patents
Preparation method of polyether functional oil-water separation membrane with amide bond in-situ crosslinking function Download PDFInfo
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- CN113274897B CN113274897B CN202110695515.8A CN202110695515A CN113274897B CN 113274897 B CN113274897 B CN 113274897B CN 202110695515 A CN202110695515 A CN 202110695515A CN 113274897 B CN113274897 B CN 113274897B
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- 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
- B01D71/52—Polyethers
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- 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
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- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- 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
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- 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
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- 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
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Abstract
The invention provides a preparation method of an amido bond in-situ crosslinked polyether functionalized oil-water separation membrane. Specifically, polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC) or Polytetrafluoroethylene (PTFE) high molecular polymer and polystyrene-maleic anhydride amphiphilic copolymer (SMA) are blended to prepare membrane casting solution, a non-solvent induced phase inversion method is adopted to prepare a blended membrane with an anhydride group on the surface, and amidation reaction between the anhydride on the surface of the membrane and amine-terminated polyether is utilized to graft the amine-terminated polyether onto the surface of the polymer membrane. The amine-terminated polyether surface grafted polymer film has a demulsification function and can destroy the stability of an oil-in-water emulsion; meanwhile, the surface of the membrane is provided with a hydrophilic polyether chain, so that the membrane shows super-hydrophilic and super-oleophobic properties under water. After the oil extraction sewage is demulsified by polyether on the surface of the membrane, water permeates the membrane and enters the permeation side, and oil is intercepted by the membrane, so that the high-efficiency oil-water separation is realized.
Description
Technical Field
The invention belongs to the technical field of functional polymer membrane separation, and particularly relates to a preparation method of an amido bond in-situ crosslinked polyether functional oil-water separation membrane.
Background
With the rapid development of the oil production industry and the frequent occurrence of oil leakage in recent years, oily sewage has become one of the most serious ecological environmental problems in the world today. The membrane separation technology is a green and efficient method for treating various oily sewage, but the low permeation flux and poor antigen oil pollution are bottlenecks in the industrial treatment of the oily sewage by the current membrane separation technology.
Because the mining oil wastewater has high mineralization, the mining oil wastewater usually contains oil displacement agents such as surfactants, polymers and the like and crude oil with certain concentration to form an oil-in-water emulsion. Conventional methods for treating oil extraction wastewater include gravity precipitation, adsorption, chemical methods, and the like. The gravity precipitation method is used for treating oil extraction sewage by utilizing the principle that oil and water are mutually incompatible. The method needs long settling time and large equipment. The adsorption method is to use an adsorbent (oleophilic material) to adsorb oil in sewage to realize oil-water separation, and the treatment and regeneration of the adsorbent are the main problems faced by the adsorption method at present. The chemical law is the most important and mature method for treating oil extraction sewage, and the used chemical agents are mainly reverse demulsifier and flocculant. Reverse demulsifiers are typically positively charged polymeric surfactants that can break oil-in-water emulsions by electrical neutralization to disrupt oil-water interfacial films and further separate oil (actually floe) water under the action of flocculants (polyaluminum chloride, polyferric chloride, etc.). Although the reverse demulsification and flocculation technology can thoroughly remove suspended matters and emulsified oil in the oil production wastewater, the practical effect of the technology is not satisfactory in recent years. This is because the oil production wastewater contains suspended matter, emulsified oil, and residual flooding polymer (partially hydrolyzed polyacrylamide, HPAM). The polymer oil sludge is negatively charged, and after the polymer oil sludge acts with a cation reverse-phase demulsifier and a flocculant, the polymer oil sludge is wrapped and carried with crude oil to form complex polymer-containing oil sludge which is deposited at the bottom of an oil extraction sewage treatment tank or causes the blockage of pipelines and filters. Not only influences the normal production of the oil field, but also causes environmental pollution because of a large amount of polymer-containing oil sludge removed from the bottom of the tank and pipelines.
Membrane separation is a new technology of separation which rises rapidly after the 60's in the 20 th century, and is introduced into the field of oil-water separation because of its advantages of low energy consumption, high separation efficiency, simple process, etc. Compared with the conventional separation method, the membrane separation can be carried out at normal temperature, the process has no phase change, the single-stage separation efficiency is high, and the process is flexible and simple. Therefore, in recent years, the separation of oily sewage by using membrane separation technology has become a hot research. For example, the application of the chinese invention CN 10269871A discloses that a porous membrane is prepared by using polylactic acid, and then the porous membrane is subjected to surface modification to obtain a degradable oil-water separation membrane with hydrophobic property, although the material shows stronger hydrophobic property, the material has low pressure bearing capacity due to poor mechanical property of the polymer, and the application of the material is limited. The patent CN103961905A discloses a preparation method of a super-hydrophobic oleophilic oil-water separation net film with low cost and high oil-water separation efficiency. According to the invention, inorganic matters with low cost are used as partial raw materials, a mild preparation process is adopted, a nano-scale mastoid structure is formed on a metal net by a sol method, and the constructed nano-silica is modified by using a low-surface-energy organic modifier to prepare the super-hydrophobic oleophilic oil-water separation net film, but the material can only separate immiscible oil-water mixtures due to the large pore size of the net film, and has no separation effect on oil-water emulsion. The CN109316981B patent discloses a preparation method of a super-hydrophilic polymer membrane with a demulsification function. Polyvinylidene fluoride (PVDF), polypropylene (PP) or Polytetrafluoroethylene (PTFE) are used as base membrane materials to be blended with styrene-maleic anhydride copolymer (SMA) to prepare membrane casting solution, a non-solvent induced phase inversion method is adopted to prepare a PVDF/SMA ultrafiltration membrane, and a hyperbranched polyether demulsifier is grafted to the surface of a polymer membrane by utilizing the chemical reaction between anhydride on the surface of the membrane and hydroxyl at the end of the hyperbranched polyether demulsifier.
As is well known, polyether substances can be generally used as demulsifiers of petroleum produced fluids, and long polyether chain segments can be adsorbed on an oil-water interface to destroy the stability of an interfacial film of an emulsion and break the emulsion.
Based on the research, the invention combines a chemical demulsification method with a membrane separation technology. Firstly, blending poly PVDF, PVC or PTFE high molecular polymer and SMA to prepare a membrane casting solution, and preparing a blended membrane with anhydride groups on the surface by adopting a non-solvent phase-induced inversion method; then, the amine-terminated polyether is grafted to the surface of the polymer film by using the in-situ amidation reaction between the anhydride on the surface of the film and the amine-terminated polyether. Because the polyether is grafted with the SMA/PVDF blend membrane through an amido bond, the polyether on the surface of the membrane is ensured to keep chemical stability under the severe condition of oil extraction wastewater. The surface and the pore wall of the membrane have polyether groups, so that the membrane has good hydrophilicity and underwater super-oleophobic property, and meanwhile, the polyether on the surface of the membrane has a demulsification function, so that the membrane can be used for demulsification and oil-water separation of oil production sewage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a polyether functional oil-water separation membrane with amide bonds crosslinked in situ.
The invention relates to a preparation method of an amido bond in-situ crosslinked polyether functionalized oil-water separation membrane, which comprises the following steps: (1) PVDF, PVC or PTFE high molecular polymer, SMA and pore-forming agent are dissolved in an organic solvent to prepare a casting solution with a certain concentration, the casting solution is defoamed, poured on a glass plate and scraped into a liquid film, and then the liquid film is transferred into a coagulating bath to prepare a polymer-based film with anhydride groups on the surface by a non-solvent phase-induced conversion method; (2) Dissolving polyether with terminal amino groups in water to prepare a terminal amino group polyether solution with a certain concentration; (3) Soaking a polymer base film with an anhydride group on the surface in an amine-terminated polyether solution, reacting in a constant-temperature water bath oscillator, carrying out in-situ amidation reaction on the anhydride on the surface of the film and an amine-terminated group on the amine-terminated polyether, and grafting the amine-terminated polyether to the surface of the polymer film. Wherein the content of PVDF, PVC or PTFE high molecular polymer in the membrane casting solution accounts for 8-18% of the total mass of the membrane casting solution, the molecular weight of SMA is between 3000-100000 Da, and the content of SMA accounts for 2-12% of the total mass of the membrane casting solution. The amine-terminated polyether comprises monoamino-substituted polyether or polyamino-substituted polyether, the polyether can be straight-chain or branched chain polyoxybutylene ether, polyoxypropylene ether, polyoxyethylene ether or block polyether, the molecular weight range of the amine-terminated polyether is 200-10000, and the concentration of the amine-terminated polyether solution is 0.2-10 g/L. The organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide. The pore-foaming agent is one of polyvinylpyrrolidone, polyethylene glycol or lithium chloride, and the content of the pore-foaming agent accounts for 0.5-20% of the total mass of the membrane casting solution. The coagulating bath is one or more of water, ethanol, methanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. The surface of the high molecular polymer and SMA blended membrane is provided with rich anhydride groups, and the high molecular polymer and SMA blended membrane is soaked in an amine-terminated polyether solution, so that amidation reaction can be carried out in situ on the anhydride groups on the membrane surface, and polyether is supported on the membrane surface through chemical bonding, so that the polymer membrane has excellent hydrophilic and underwater super-oleophobic properties, the pure water contact angle of the membrane surface is less than 50 degrees, and the underwater oil contact angle is more than 150 degrees. In addition, the amide bond in-situ crosslinked polyether functionalized membrane has excellent oil-water separation property, and the oil-water separation rate of oil extraction wastewater is more than 98%.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
(1) 6g of PVDF and 4g of SMA are dissolved in 38g of N, N-dimethylacetamide, 2g of lithium chloride is added as a pore-forming agent, the mixture is heated and stirred at 70 ℃ for reaction for 8 hours to form a transparent homogeneous phase solution, and then the solution is kept at a constant temperature of 70 ℃ for defoaming for 4 hours to prepare a membrane casting solution. Uniformly scraping the casting solution on a glass plate at room temperature to form a liquid film with the thickness of 300 mu m, quickly immersing the liquid film in water for phase transformation to form a film, and taking out the formed SMA/PVDF film and putting the SMA/PVDF film into deionized water for immersion;
(2) Soaking an SMA/PVDF film of 5cm multiplied by 5cm in a polyetheramine D230 aqueous solution with the concentration of 4%, and placing the SMA/PVDF film in a constant-temperature water bath oscillator for reaction at the reaction temperature of 50 ℃ for 10h. After the reaction is finished, washing with deionized water to obtain a D230 surface grafted SMA/PVDF film named D230@ SMA/PVDF;
(3) The pure water contact angle of D230@ SMA/PVDF film is 28 degrees, the underwater oil (kerosene) contact angle is 151 degrees, and the pure water flux is 420L m under 0.1MPa -2 ·h -1 (ii) a After the oil extraction wastewater with the mineralization degree of 5032mg/L and the oil content of 135mg/L is treated by the D230@ SMA/PVDF film, the removal rate of the crude oil in the water reaches 99.6 percent.
Example 2
(1) 6g of PVC and 4g of SMA are dissolved in 38g of N, N-dimethylacetamide, 2g of lithium chloride is added as a pore-forming agent, the mixture is heated and stirred at 70 ℃ for reaction for 8 hours to form a transparent homogeneous phase solution, and then the solution is kept at a constant temperature of 70 ℃ for defoaming for 4 hours to prepare a membrane casting solution. Uniformly scraping the casting solution on a glass plate at room temperature to form a liquid film with the thickness of 300 mu m, quickly immersing the liquid film in water for phase transformation to form a film, and taking out the formed SMA/PVC film and putting the SMA/PVC film into deionized water for immersion;
(2) Soaking an SMA/PVC film of 5cm multiplied by 5cm in a polyetheramine CAED600 water solution with the concentration of 4%, and placing the SMA/PVC film in a constant-temperature water bath oscillator for reaction at the reaction temperature of 50 ℃ for 10h. After the reaction is finished, washing with deionized water to obtain a CAED600 surface grafted SMA/PVC film named CAED600@ SMA/PVC;
(3) CAED600@ SMA/PVC film pure water contact angle of 25 degrees, underwater oil (kerosene) contact angle of 153 degrees, pure water flux of 540L m under 0.1MPa -2 ·h -1 (ii) a After the oil extraction sewage with the mineralization degree of 8310mg/L and the oil content of 85mg/L is treated by the CAED600@ SMA/PVC film, the removal rate of the crude oil in the water reaches 99.9 percent.
Example 3
(1) 7g of PVDF and 5g of SMA are dissolved in 35g of N, N-dimethylacetamide, 3g of lithium chloride is added as a pore-forming agent, the mixture is heated and stirred at 70 ℃ for 8 hours to react to form a transparent homogeneous phase solution, and then the solution is kept at a constant temperature of 70 ℃ for defoaming for 4 hours to prepare a membrane casting solution. Uniformly scraping the casting solution on a glass plate at room temperature to form a liquid film with the thickness of 300 mu m, quickly immersing the liquid film in water for phase transformation to form a film, and taking out the formed SMA/PVDF film and putting the SMA/PVDF film into deionized water for immersion;
(2) Soaking an SMA/PVDF film of 5cm multiplied by 5cm in a polyether amine T403 aqueous solution with the concentration of 6%, and placing the SMA/PVDF film in a constant-temperature water bath oscillator for reaction at the reaction temperature of 70 ℃ for 10h. After the reaction is finished, washing with deionized water to obtain a T403 surface grafted SMA/PVDF film named as T403@ SMA/PVDF;
(3) T403@ SMA/PVDF film pure water contact angle of 38 degrees, underwater oil (kerosene) contact angle of 148 degrees, pure water flux of 340 L.m under 0.1MPa -2 ·h -1 (ii) a After the oil extraction wastewater with the mineralization degree of 6352mg/L and the oil content of 200mg/L is treated by the T403@ SMA/PVDF membrane, the removal rate of crude oil in water reaches 99.0 percent.
Claims (3)
1. A preparation method of an amido bond in-situ crosslinked polyether functionalized oil-water separation membrane is characterized by comprising the following steps: (1) Dissolving polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC) or Polytetrafluoroethylene (PTFE) high molecular polymer, polystyrene-maleic anhydride amphiphilic copolymer (SMA) and pore-forming agent in an organic solvent to prepare a casting solution with a certain concentration, defoaming, pouring the casting solution on a glass plate, scraping the casting solution into a liquid film, and transferring the liquid film into a coagulating bath to prepare a polymer base film with anhydride groups on the surface by a non-solvent induced phase inversion method; (2) Dissolving polyether with terminal amino groups in water to prepare a terminal amino group polyether solution with a certain concentration; (3) Soaking a polymer base film with an anhydride group on the surface in an amine-terminated polyether solution, reacting in a constant-temperature water bath oscillator, carrying out amidation reaction on the anhydride on the surface of the film and an amine-terminated group on the amine-terminated polyether, and grafting the amine-terminated polyether to the surface of the polymer film;
the content of PVDF, PVC or PTFE high molecular polymer in the casting solution accounts for 8-18% of the total mass of the casting solution, the molecular weight of SMA is between 3000-100000 Da, and the content of SMA accounts for 2-12% of the total mass of the casting solution;
the amine-terminated polyether comprises monoamine-substituted polyether or polyamine-substituted polyether, the polyether can be straight-chain or branched chain polyoxybutylene ether, polyoxypropylene ether, polyoxyethylene ether or block polyether, the molecular weight range of the amine-terminated polyether is 200-10000, and the concentration of the amine-terminated polyether solution is 0.2-10 g/L;
the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide;
the pore-foaming agent is one of polyvinylpyrrolidone, polyethylene glycol or lithium chloride, and the content of the pore-foaming agent accounts for 0.5 to 20 percent of the total mass of the casting solution;
the coagulating bath is one or more of water, ethanol, methanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
2. The preparation method of the polyether functionalized oil-water separation membrane with the in-situ crosslinked amido bond as claimed in claim 1, wherein the surface of the high molecular polymer and SMA blended membrane is rich in anhydride groups, the high molecular polymer and SMA blended membrane is soaked in an amine-terminated polyether solution, the in-situ amidation reaction of the anhydride groups on the membrane surface can be realized, and the polyether is supported on the membrane surface through chemical bonding, so that the polymer membrane has excellent hydrophilic and underwater superoleophobic properties, the pure water contact angle of the membrane surface is less than 50 degrees, and the underwater oil contact angle is more than 150 degrees.
3. The method for preparing the polyether functionalized oil-water separation membrane with the in-situ crosslinked amide bond as claimed in claim 1, wherein the polyether functionalized oil-water separation membrane with the in-situ crosslinked amide bond has excellent oil-water separation property, and the oil-water separation rate of the oil extraction wastewater is more than 98%.
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