CN112827358B - Preparation method of hollow fiber heavy metal adsorption ultrafiltration membrane - Google Patents

Preparation method of hollow fiber heavy metal adsorption ultrafiltration membrane Download PDF

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CN112827358B
CN112827358B CN201911155884.7A CN201911155884A CN112827358B CN 112827358 B CN112827358 B CN 112827358B CN 201911155884 A CN201911155884 A CN 201911155884A CN 112827358 B CN112827358 B CN 112827358B
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membrane
hollow fiber
heavy metal
soaking
ultrafiltration membrane
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CN112827358A (en
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倪澄峰
卜凡敏
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Ningbo Fotile Kitchen Ware Co Ltd
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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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre 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
    • B01D71/26—Polyalkenes
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
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  • Hydrology & Water Resources (AREA)
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  • Organic Chemistry (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A hollow fiber heavy metal ultrafiltration membrane is characterized in that stock solution of the ultrafiltration membrane adopts at least one of PVDF, polysulfone, polyethersulfone, PVC and PMIA as polymer resin, and imidazole groups and epoxy groups in the polymer resin. The invention also discloses a membrane component and a preparation method of the ultrafiltration membrane. Compared with the prior art, the invention has the advantages that: the heavy metal removal rate of the obtained product can reach more than 95 percent, and the product can simultaneously remove conventional mineral ions Na in water+、K+、Ca2+、Mg2+And the heavy metal ions can not be removed, so that the conventional mineral ions can be retained in the water purification process to remove the heavy metal ions.

Description

Preparation method of hollow fiber heavy metal adsorption ultrafiltration membrane
Technical Field
The invention relates to a filtering membrane, belongs to the technical field of water treatment of membranes, and also relates to a membrane module and a preparation method of the membrane.
Background
The existing ultrafiltration membrane generally removes organic matters with relative molecular weight of more than 1000, the ultrafiltration membrane can not remove heavy metal in the purification process of drinking water, and the phenomenon that the drinking water filtered by the ultrafiltration membrane exceeds the standard after long-term drinking exists.
Technical documents for achieving removal of heavy metal particles by modifying ultrafiltration membranes have been disclosed for a long time, and specifically, methods for modifying ultrafiltration membranes mainly include physical methods and chemical methods. The former method is, like the blending method, to physically mix the substance with heavy metal adsorption sites with the film forming material to make the hollow fiber membrane filament, and the blending introduces a large amount of mixture, so that the uniformity of the membrane casting solution is affected, and the formation of the membrane pore structure is affected. The chemical method mainly comprises modification by radiation such as corona, ultraviolet and plasma, and the modification only improves the performance of the material in a short time.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide an ultrafiltration membrane modified by imidazole groups to improve the removal rate of heavy metals, in view of the above technical situation.
The second technical problem to be solved by the invention is to provide an ultrafiltration membrane module which is modified by imidazole groups so as to improve the removal rate of heavy metals.
The third technical problem to be solved by the invention is to provide a preparation method of the ultrafiltration membrane, wherein the imidazole group is used for modification so as to improve the removal rate of heavy metal.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a hollow fiber heavy metal adsorption ultrafiltration membrane is characterized in that stock solution of the ultrafiltration membrane adopts at least one of PVDF, polysulfone, polyethersulfone, PVC and PMIA as polymer resin, and the molar ratio of imidazole groups to epoxy groups in the polymer resin meets the following conditions:
Figure GDA0003466588590000011
—CH(O)CH—＝5:1～1:6；
the ultrafiltration membrane meets the following conditions:
the external pressure pure water flux is 100-600 (L/M2H bar);
the molecular weight cut-off is between 1 and 7 ten thousand Da.
Preferably, the ultrafiltration membrane has a heavy metal removal rate of 95% or more.
Preferably, the heavy metal is at least one of Cd, Cr, Pb and As.
The technical scheme adopted by the invention for solving the second technical problem is as follows: a membrane component with a hollow fiber heavy metal adsorption ultrafiltration membrane is characterized by comprising a shell and the hollow fiber heavy metal ultrafiltration membrane arranged in the shell.
The technical scheme adopted by the invention for solving the third technical problem is as follows: a preparation method of a hollow fiber heavy metal adsorption ultrafiltration membrane is characterized by comprising the following steps:
firstly, preparing a membrane stock solution, dissolving polymer resin and an additive in a solvent, wherein the solvent is at least one of DMAC, DMF, NMP and DMSO, and polyethylene glycol or polyvinylpyrrolidone or lithium chloride is added as the additive;
secondly, manufacturing a hollow fiber membrane, namely spraying membrane manufacturing stock solution inside and outside a double-layer tubular nozzle at the same time, and soaking the membrane manufacturing stock solution in a coagulating bath containing pure water or salt water to form the hollow fiber membrane;
removing the organic solvent, and removing the organic solvent from the hollow fiber membrane to obtain a nascent hollow fiber membrane;
soaking the nascent hollow fiber membrane in a solution containing
Figure GDA0003466588590000021
Soaking in the radical water solution for the first time, and then adding glutaraldehyde and potassium sulfate for the second time; the primary soaking time is 10-240 min, and the soaking temperature is 5-30 ℃; the secondary soaking time is 5-60 min, and the soaking temperature is 40-80 ℃;
and fifthly, removing redundant organic molecules after soaking to obtain the hollow fiber heavy metal ultrafiltration membrane.
Preferably, the polymer resin is present in the film-forming dope in a concentration of 15 to 35% by weight.
Preferably, the solvent is contained in the film-forming dope in a concentration of 55.45 to 75.45% by weight.
Preferably, the PVP-K30 concentration by weight percentage is 1-10%.
Preferably, the
Figure GDA0003466588590000022
The radical substance is polyvinyl imidazole, and the weight percentage concentration is 1-8%.
Preferably, the concentration of glutaraldehyde is no more than 4%.
Preferably, the potassium persulfate concentration is no more than 2% by weight.
Compared with the prior art, the invention has the advantages that: imidazole molecules contain a large number of amino groups, can be subjected to preliminary cross-linking reaction with epoxy groups, the amino groups can provide a large number of electrons, heavy metals can provide empty tracks in water, and therefore the imidazole molecules can effectively remove heavy metal ions, and glutaraldehyde can be subjected to cross-linking reaction with imidazole, so that the imidazole molecules can be well and firmly bonded on the surface and inner holes of the membrane. The heavy metal removal rate of the obtained product can reachMore than 95 percent and simultaneously to the conventional mineral ions Na in water+、K+、Ca2+、Mg2+And the heavy metal ions can not be removed, so that the conventional mineral ions can be retained in the water purification process to remove the heavy metal ions.
Drawings
FIG. 1 is a first photomicrograph of example 9.
FIG. 2 is a second photomicrograph of example 9.
FIG. 3 is a photomicrograph of three of example 9.
FIG. 4 is a fourth photomicrograph of example 9.
FIG. 5 is a cross-sectional view of a specific cross-flow type membrane module.
FIG. 6 is a cross-sectional view of another specific cross-flow type membrane module.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Examples 1 to 15: the composite material is prepared from a polymer membrane material (PVDF (polyvinylidene fluoride), polysulfone, polyethersulfone, PVC (polyvinyl chloride) and PMIA (poly-m-phenyleneisophthalamide)), wherein the mass percent of the polymer is 15-35%, the mass percent of the solvent is 55.45-75.45% and the mass percent of the additive PVPK30 is 5% (DMAC (dimethylacetamide), DMF (dimethylformamide), NMP (N-methylpyrrolidone) and DMSO (dimethyl sulfoxide)). This was stirred for 8 hours and dissolved to prepare a film-forming stock solution. The dope was fed to a spinneret (a double-layer tubular nozzle for producing hollow fibers having a double-layer tube structure) by a constant rate pump and extruded at 4 g/min. The spinneret used had an outer diameter of 0.5mm and an inner diameter of 0.3 mm. Pure water was passed through the internal liquid at a liquid feed rate of 2.0 g/min. The extruded dope for spinning was passed through an air gap of 10mm, put into a coagulating bath of a pure water solution, cooled and solidified, and wound at a winding speed of 20 m/min. The obtained hollow fiber is immersed in water for 24 hours and the solvent is extracted, thereby obtaining a nascent hollow fiber heavy metal adsorption filtration membrane. Soaking a nascent hollow fiber filtering membrane in 4% PVIm (polyvinyl imidazole) solution for 2h, then adding 0.5% of glutaraldehyde and 0.05% of potassium persulfate, soaking the membrane for 30min, raising the temperature to 70 ℃, taking out membrane wires after fully reacting for 2h, placing the membrane wires in pure water, and soaking for 24h to obtain the hollow fiber heavy metal adsorption filtering membrane.
The microstructure of the product obtained in example 9 can be seen with reference to FIGS. 1 to 4.
Examples 16 to 27: the polysulfone polymer membrane material is 22% of polysulfone, the solvent is DMAC, the solvent is 55.45-75.45% of the mass, and the additive is PVPK 30% of the mass. This was stirred for 8 hours and dissolved to prepare a film-forming stock solution. The dope was fed to a spinneret (a double-layer tubular nozzle for producing hollow fibers having a double-layer tube structure) by a metering pump, and extruded at 4 g/min. The spinneret used had an outer diameter of 0.5mm and an inner diameter of 0.3 mm. Pure water was passed through the internal liquid at a liquid feed rate of 2.0 g/min. The extruded dope for spinning was passed through an air gap of 10mm, put into a coagulating bath of a pure water solution, cooled and solidified, and wound at a winding speed of 20 m/min. The obtained hollow fiber is immersed in water for 24 hours and the solvent is extracted, thereby obtaining a nascent hollow fiber heavy metal adsorption filtration membrane. Soaking a nascent hollow fiber heavy metal adsorption filtration membrane in 1-8% PVIm (polyvinyl imidazole) aqueous solution for 2h, then adding 0-4% of glutaraldehyde and 0-2% of potassium persulfate, soaking the membrane for 30min, raising the temperature to 70 ℃, taking out membrane filaments after fully reacting for 2h, placing the membrane filaments in pure water, and soaking for 24h to obtain the hollow fiber heavy metal adsorption filtration membrane.
Example 28: manufacture of cross-flow type assembly
The hollow fiber membranes obtained in example 21 were cut to a length of 180mm, 5000 pieces were bundled, and both ends were plugged with self-made PVC alloy plug glue. A cylindrical tube having an outer diameter of 80mm, an inner diameter of 75mm and a length of 150mm was prepared. Here, in an aluminum material can having the same outer inner diameter as the assembly box and a length of 25mm, a han-high two-component epoxy resin glue potting agent is scraped and filled, one end of the assembly is mounted on the upper portion, and the membrane bundle is extruded from the top to the bottom contacting the aluminum material can. The mixture was left standing for 10 hours in this state, and one end was sealed. After curing, the aluminum can was pulled out while stretching, and the assembly was cut from the epoxy resin for each bundle of films to expose the hollow portion. The end of the other bundle is also sealed and cut in the same manner, so that the hollow portion is exposed at both ends. Both ends of the membrane were covered with covers having inlet and outlet ports and adhered to each other to prepare a cross-flow module having an effective membrane length of 120mm × 5000 membranes.
Example 29: manufacture of cross-flow type assembly
The hollow fiber membrane obtained in example 21 was cut into 360mm lengths, 2500 pieces were bundled, and the holes were plugged with home-made PVC alloy plug glue at both ends. A cylindrical tube having an outer diameter of 80mm, an inner diameter of 75mm and a length of 150mm was prepared. Here, in an aluminum material can having the same outer inner diameter as the assembly box and a length of 25mm, a han-high two-component epoxy resin glue potting agent is scraped and filled, one end of the assembly is mounted on the upper portion, and the membrane bundle is extruded from the top to the bottom contacting the aluminum material can. The mixture was left standing for 10 hours in this state, and one end was sealed. After curing, the aluminum can was pulled out while stretching, and the assembly was cut from the epoxy resin for each bundle of films to expose the hollow portion. The end of the other bundle is also sealed and cut in the same manner, so that the hollow portion is exposed at both ends. Both ends of the membrane were covered with covers having inlet and outlet ports and adhered to each other to prepare a cross-flow module having an effective membrane length of 200mm × 2500 membranes.
The product of example 9 was tested for monovalent and divalent ion rejection rates according to: ultrafiltration membrane and module HY/T112-. The testing device for the ion removal rate of the testing instrument. And (3) testing conditions are as follows: the test medium is distilled water, the water temperature is 25 ℃, the test pressure is 0.1MPa, the solution concentration is 250mg/L, and the operation mode is as follows: and continuously operating for 20min under the test pressure by adopting an external pressure method. The test method comprises the following steps: and testing the conductivity of the raw water and the produced water of the membrane module after the operation is contrasted, and sequentially corresponding to the ion removal rate by the technology. Test objects: magnesium sulfate, calcium chloride, magnesium chloride and sodium chloride. The test results are given in the following table:
test object Magnesium sulfate Calcium chloride Magnesium chloride Sodium chloride
Conductivity of raw water (mu s/cm) 333 326 287 521
Conductivity of produced water (mu s/cm) 333 326 287 521
Removal Rate (%) 0 0 0 0
In example 2, the detection results of the cadmium 3-fold national standard limiting concentration of the prepared membrane chromatography ultrafiltration filter element are shown in the following table:
Figure GDA0003466588590000041
Figure GDA0003466588590000051
the detection results of the cadmium 5 times of the national standard limiting concentration are shown in the following table:
Figure GDA0003466588590000052
the results of the detection of the 3-fold international limit concentration of chromium (6-valent) are shown in the following table:
Figure GDA0003466588590000053
Figure GDA0003466588590000061
the results of the detection of 5 times the international limit concentration of chromium (6 valent) are shown in the following table:
Figure GDA0003466588590000062
the detection results of lead with 3 times of national standard limiting concentration are shown in the following table:
Figure GDA0003466588590000063
the detection results of the lead 5 times of the national standard limiting concentration are shown in the following table:
Figure GDA0003466588590000064
Figure GDA0003466588590000071
the detection results of arsenic 3 times the national standard limiting concentration are shown in the following table:
Figure GDA0003466588590000072
the detection results of arsenic 5 times the national standard limiting concentration are shown in the following table:
Figure GDA0003466588590000073
fig. 5 is a specific cross-flow membrane module, and the specific structure comprises a housing 1 and a filter element assembly arranged in the housing 1, wherein a water inlet 11 and a water production port 12 are respectively arranged at two axial ends of the housing 1, a concentrated water outlet 13 is formed in the lateral direction, the filter element assembly comprises a plurality of membrane filaments 2, and adhesive sealing layers 3 are respectively formed at two ends of the membrane filaments.
Fig. 6 shows another specific cross-flow membrane module, which includes a housing 1 and a filter element assembly disposed in the housing 1, wherein a water outlet 12 is formed at one axial end of the housing 1, a water inlet 11 is formed at a lateral side of the housing, and the filter element assembly includes a plurality of membrane filaments 2 and sealant layers 3 formed at two ends of the membrane filaments.
Figure GDA0003466588590000081
Figure GDA0003466588590000091
Figure GDA0003466588590000101

Claims (9)

1. A preparation method of a hollow fiber heavy metal adsorption ultrafiltration membrane is characterized in that stock solution of the ultrafiltration membrane adopts at least one of PVDF, polysulfone, polyethersulfone, PVC and PMIA as polymer resin, and the molar ratio of imidazole groups to epoxy groups in the polymer resin meets the following conditions:
Figure FDA0003517930830000011
:—CH(O)CH—＝5:1～1:6；
the ultrafiltration membrane meets the following conditions:
the external pressure pure water flux is 100-600 (L/M2H bar);
the intercepted molecular weight is between 1 and 7 ten thousand Da;
the method comprises the following steps:
firstly, preparing a membrane stock solution, dissolving polymer resin and an additive in a solvent, wherein the solvent is at least one of DMAC, DMF, NMP and DMSO, and PVP-K30 is added as the additive;
secondly, manufacturing a hollow fiber membrane, namely spraying membrane manufacturing stock solution inside and outside a double-layer tubular nozzle at the same time, and soaking the membrane manufacturing stock solution in a coagulating bath containing pure water or salt water to form the hollow fiber membrane;
removing the organic solvent, and removing the organic solvent from the hollow fiber membrane to obtain a nascent hollow fiber membrane;
soaking the nascent hollow fiber membrane in a solution containing
Figure FDA0003517930830000012
Performing primary soaking in a group water solution, and then adding glutaraldehyde and potassium persulfate to perform secondary soaking; the primary soaking time is 10-240 min, and the soaking temperature is 5-30 ℃; the secondary soaking time is 5-60 min, and the soaking temperature is 40-80 ℃;
and fifthly, removing redundant organic molecules after soaking to obtain the hollow fiber heavy metal adsorption ultrafiltration membrane.
2. The method according to claim 1, wherein the ultrafiltration membrane has a heavy metal removal rate of 95% or more.
3. The method according to claim 2, wherein the heavy metal is at least one of Cd, Cr, Pb and As.
4. The method according to claim 1, wherein the polymer resin is contained in the dope at a concentration of 15 to 35% by weight.
5. The method according to claim 1, wherein the solvent is contained in the dope at a concentration of 55.45 to 75.45% by weight.
6. The method according to claim 1, wherein the PVP-K30 is present at a concentration of 1-10 wt%.
7. The method according to claim 1, wherein the reaction mixture is heated to a temperature sufficient to cause the reaction
Figure FDA0003517930830000013
The radical substance is polyvinyl imidazole, and the weight percentage concentration is 1-8%.
8. The method according to claim 1, wherein the concentration of glutaraldehyde is not more than 4%.
9. The process according to claim 1, wherein the concentration of potassium persulfate is not more than 2% by weight.
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