CN106110905A - A kind of carbon containing isolating membrane and its preparation method and application - Google Patents

A kind of carbon containing isolating membrane and its preparation method and application Download PDF

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Publication number
CN106110905A
CN106110905A CN201610625355.9A CN201610625355A CN106110905A CN 106110905 A CN106110905 A CN 106110905A CN 201610625355 A CN201610625355 A CN 201610625355A CN 106110905 A CN106110905 A CN 106110905A
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membrane
microporous filter
graphene oxide
ceo
filter membrane
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CN201610625355.9A
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不公告发明人
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Zhenjiang Dantu District Shuoyuan Material Technology Co Ltd
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Zhenjiang Dantu District Shuoyuan Material Technology Co Ltd
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Priority to CN201610625355.9A priority Critical patent/CN106110905A/en
Publication of CN106110905A publication Critical patent/CN106110905A/en
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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
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • 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
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a kind of carbon containing isolating membrane, described composite membrane successively by microporous filter membrane, containing carbon composite layer and microporous filter membrane up of three layers, the aperture of described microporous filter membrane is 10nm～100 μm, the material of this microporous filter membrane is macromolecule, metal or oxide, and described is the graphene oxide CeO containing partial reduction containing carbon composite layer2.The composite membrane of the present invention is mainly used for isolating hydrone and the various ions in water, it is possible to intercepts the salt ion in water, and allows hydrone pass through, can be used for sewage treatment area.The efficiency of desalination of the present invention is high, and clearance is more than 99%.

Description

A kind of carbon containing isolating membrane and its preparation method and application
Technical field
The present invention relates to ion isolation field, be specifically related to a kind of carbon containing isolating membrane and its preparation method and application.
Background technology
Along with the development of industrial and agricultural production, water pollutes and has changed into serious problem, how to remove the various ions in water, Particularly contaminated ion, has become as an important problem.
Chinese invention patent 103553167A proposes a kind of solar energy evaporating sea water desalting device, to solve existing sea water Desalination technology investment is big, cost high, energy consumption high, to the pre-processing requirements height of sea water, the asking of heavy dependence fossil, electric power energy Topic.The hydrophobic film of this invention seals and covers on thin film skeleton, and sea water storage tank is arranged on the lower end of hydrophobic film, and sea water enters water Pipe is located in the bottom of hydrophobic film, and concentrated seawater discharge pipe is located in the bottom of sea water storage tank, and water leg is arranged on sea water storage tank With the intersection of hydrophobic film, header tank is vertically arranged in sea water storage tank, and the upper surface of header tank with water leg same In plane, desalination water outlet pipe is located in the bottom of header tank, and described exhaustor is vertically located in the upper end of hydrophobic film, aeration Head is arranged in sea water storage tank, in air inlet pipe is located in sea water storage tank and is connected with aeration head.
Chinese invention patent 102398962A provides a kind of sea water potential energy and carries out the device of desalination by reverse osmosis, its feature It is, including: desalinization unit, salt manufacturing unit, pipeline, wherein desalinization unit includes reverse osmosis membrane unit, and being used for will The first process sea water introduced from primary Seawater Treatment enters reverse osmosis membrane unit by pipeline, and reverse osmosis membrane unit is placed in horizontal plane The position of certain drop degree of depth, will have the seawater eroding of potential energy in reverse osmosis membrane unit, thus sea water is passed through reverse osmosis membrane Desalting, described reverse osmosis membrane unit soars pump by fresh water extraction by using after desalinization.
Chinese patent 105668839A provides a kind of technique utilizing tangleweed to process heavy metal wastewater thereby, including following Operation: (1) Wastewater Pretreatment；(2) nonactive tangleweed filtering ponds process；(3) nonactive tangleweed adsorption tank processes； (4) reverse osmosis membrane assembly removes residual gravity metal ion (5) qualified discharge, the heavy metal waste water treatment process of the present invention is simple, Cost is relatively low, is respectively provided with nonactive tangleweed filtering ponds and nonactive tangleweed adsorption tank before reverse osmosis process, can Effectively removing heavy metal ion, organic pollution and the inorganic pollution in sewage, the pollution alleviating reverse osmosis membrane assembly is born Lotus, reduces the replacing number of times of membrane module, and antiseptic property is greatly improved, and can regularly replace, not result in secondary pollution.
Chinese invention patent 105236610A discloses a kind of desalinization integrated equipment, belongs to desalinization and processes neck Territory, integration apparatus includes sea water storage tank, sea water intake pump, cartridge filter, hyperfiltration membrane assembly, backwash water pump, middle water Case, middle water pump, dense water storage tank, fresh water storage tank, pole water storage tank, dense water-circulating pump, fresh water circulating pump, pole water-circulating pump, electricity drive The devices such as dynamic membrane stack, commutator, high-pressure pump, reverse osmosis unit, dosing pump, cleaning pump, cleaning case, potable water tank, drinking water faucet；Sea Water can retain float therein, algae and some antibacterials etc. effectively by ultrafiltration apparatus, and its water outlet enters through intermediate water tank Electric drive membranous system, the fresh water of output by after reverse osmosis membrane, reaches drinking water standard, thus reaches sea under high-pressure pump effect The purpose of water desalination.This equipment is the sea water desalting equipment of a kind of integration, have that salt rejection rate is high, aquifer yield is big, operating cost is low, The feature such as efficient integrated and automatization.
Chinese patent 103657611A provides a kind of nano adsorption material for water pollution control, by percentage by weight It is the nano-tourmaline of 30～55%, 20～the modified activated carbon of 35%；10～the nano concave earth of 20%；8～the modification of 22% Graphene oxide；1～5% synthetic resin compounding form.The present invention uses nano-tourmaline, modified activated carbon, modified oxidized The nanometer materials such as Graphene, nano concave earth and resin material compound, have great specific surface area, fine three dimensional structure and Suitably surface adsorption electric charge, can develop enormous amount, species high micro-life abundant, active as microbial membrane carrier Thing group, and by the Organic substance in the metabolism efficient degradation waste water of microorganism.The present invention is as a kind of adsorption material simultaneously Material, it is also possible to the effectively heavy metal in absorption effluent, float, overcomes tradition adsorbing material and may be only available for single occasion Not enough.
Summary of the invention
Goal of the invention: the technique that the current method using membrane filtration carries out desalinization is the most immature, and it has its source in That filters is inefficient.In order to extract fresh water from sea water with realizing high-efficiency and low-cost, technology to be solved by this invention is asked Topic there is provided a kind of carbon containing isolating membrane.
The present invention also to solve the technical problem that the preparation method that there is provided a kind of carbon containing isolating membrane.
The present invention also to solve the technical problem that the application that there is provided a kind of carbon containing isolating membrane.
For achieving the above object, the technical solution used in the present invention is: a kind of carbon containing isolating membrane, described composite membrane successively by Microporous filter membrane, containing carbon composite layer and microporous filter membrane up of three layers, the aperture of described microporous filter membrane is 10nm～100 μm, this micropore The material of filter membrane is macromolecule, metal or oxide, described containing carbon composite layer be the graphene oxide containing partial reduction, CeO2。
Wherein, the thickness of above-mentioned composite membrane is 100nm～100 μm.
Wherein, above-mentioned macromolecule is PP and/or PE material.
Wherein, above-mentioned oxide is aluminium oxide.
The preparation method of above-mentioned isolating membrane, comprises the following steps:
1) by the aqueous solution of graphene oxide, CeO2Aqueous solution uniformly mix；
2) with microporous filter membrane as substrate, vacuum filtration method is used to make graphene oxide, CeO2Mixture solution take off under negative pressure Water, and then in microporous filter membrane substrate, it is stacked with self assembly for containing carbon composite layer；By another layer of micropore filter during sucking filtration Film is coated on containing carbon composite layer, constitutes the composite membrane of sandwich structure；
3) composite membrane of sandwich structure is dried under the conditions of 40～80 DEG C 4～24h；
4) irradiated 3～10 days by ultraviolet light, utilize CeO2Photocatalysis characteristic make graphene oxide partial reduction, final To isolating membrane.
Wherein, the aqueous solution volume mass concentration of above-mentioned graphene oxide is 5～50mg/L, CeO2Aqueous solution volume matter Amount concentration is 5～30mg/L.
Wherein, above-mentioned graphene oxide, CeO2Mass ratio be 1: 0.1～0.2.
The application in terms of desalinization of the above-mentioned isolating membrane.The isolating membrane of the present invention may be used for the removing of various salt, It is particularly suitable for applications in field of seawater desalination.
The present invention use microporous filter membrane as support, more than micron order granule in insulating sea water, use containing carbon composite layer As the various salt ions in abjection sea water.Containing the CeO2 in carbon composite layer as light-sensitive catalyst, under the irradiation of ultraviolet light Electron-hole pair, partly redox graphene can be produced, be allowed to produce one and can allow for hydrone by still energy Enough isolate the isoionic passages such as sodium, magnesium, potassium, calcium.The most sizeable channel size just can bring preferable filter effect.
Beneficial effect: compared with prior art, the composite membrane of the present invention has two-layer microporous filter membrane to protect due to both sides to the present invention Protecting, mechanical property is high, it is ensured that be difficult to be destroyed containing carbon composite layer.Can allow for hydrone containing carbon composite layer to pass through, but The percent of pass such as sodium ion in sea water, calcium ion, magnesium ion are extremely low.The efficiency of desalination of the present invention is high, clearance more than 99%, Higher than prior art.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
Embodiment 1: the preparation of isolating membrane
1) by the aqueous solution of graphene oxide, CeO2Aqueous solution uniformly mix；The aqueous solution volume mass of graphene oxide is dense Degree is 50mg/L, CeO2Aqueous solution volume mass concentration is 10mg/L, graphene oxide, CeO2Mass ratio be 1: 0.15；
2) with PP microporous filter membrane that average pore size is 0.6 micron as substrate, vacuum filtration method is used to make graphene oxide, CeO2's Mixed solution is dehydrated under negative pressure, and then is stacked with self assembly in microporous filter membrane substrate for containing carbon composite layer；In sucking filtration mistake The PE microporous filter membrane that another layer of average pore size is 3.7 microns is coated on containing carbon composite layer by journey, constitutes sandwich structure Composite membrane；
3) composite membrane of sandwich structure is dried under the conditions of 40 DEG C 4h；
4) irradiated 3 days by ultraviolet light, utilize CeO2Photocatalysis characteristic make graphene oxide partial reduction, finally give thickness Degree is the isolating membrane of 12 microns.Preparation, containing 5wt% magnesium chloride, the mixed solution of 5at% sodium chloride, uses suction method to measure this thin The film desalination effect to this solution, the effect going demagging is 99.4%, and the effect removing sodium is 99.5%.
Embodiment 2: the preparation of isolating membrane
1) by the aqueous solution of graphene oxide, CeO2Aqueous solution uniformly mix；The aqueous solution volume mass of graphene oxide is dense Degree is 5mg/L, CeO2Aqueous solution volume mass concentration is 5mg/L, graphene oxide, CeO2Mass ratio be 1:0.2；
2) with aluminum oxide porous film that average pore size is 0.01 micron as substrate, use vacuum filtration method make graphene oxide, CeO2Solution is dehydrated under negative pressure, and then is stacked with self assembly in microporous filter membrane substrate for containing carbon composite layer；In sucking filtration mistake The PP microporous filter membrane that another layer of average pore size is 0.05 micron is coated on containing carbon composite layer by journey, constitutes sandwich structure Composite membrane；
3) composite membrane of sandwich structure is dried under the conditions of 80 DEG C 14h；
4) irradiated 10 days by ultraviolet light, utilize CeO2Photocatalysis characteristic make graphene oxide partial reduction, finally give thickness Degree is the isolating membrane of 0.10 micron.
Preparation, containing 5wt% magnesium chloride, the mixed solution of 5at% sodium chloride, uses suction method to measure this thin film to this solution Desalination effect, the effect going demagging is 99.1%, remove sodium effect be 99.3%.
Embodiment 3: the preparation of isolating membrane
1) by the aqueous solution of graphene oxide, CeO2Aqueous solution uniformly mix；The aqueous solution volume mass of graphene oxide is dense Degree is 25mg/L, CeO2Aqueous solution volume mass concentration is 20mg/L, graphene oxide, CeO2Mass ratio be 1:0.2；
2) with PE microporous filter membrane that average pore size is 0.32 micron as substrate, vacuum filtration method is used to make graphene oxide, CeO2 Mixed solution be dehydrated under negative pressure, and then in microporous filter membrane substrate, be stacked with self assembly for containing carbon composite layer；At sucking filtration During the PE microporous filter membrane that another layer of average pore size is 6.8 microns is coated on containing carbon composite layer, constitute sandwich knot The composite membrane of structure；
3) composite membrane of sandwich structure is dried under the conditions of 60 DEG C 14h；
4) irradiated 5 days by ultraviolet light, utilize CeO2Photocatalysis characteristic make graphene oxide partial reduction, finally give thickness Degree is the isolating membrane of 0.28 micron.
Preparation, containing 5wt% magnesium chloride, the mixed solution of 5at% sodium chloride, uses suction method to measure this thin film to this solution Desalination effect, the effect going demagging is 99.2%, remove sodium effect be 99.8%.
The preparation of embodiment 4 isolating membrane
1) by the aqueous solution of graphene oxide, CeO2Aqueous solution uniformly mix；Graphene oxide water solution volume mass concentration For 40mg/L, CeO2Aqueous solution volume mass concentration be 30mg/L；Graphene oxide, CeO2Mass ratio be 1:0.1；
2) with PP microporous filter membrane that average pore size is 56 microns as substrate, vacuum filtration method is used to make graphene oxide, CeO2's Mixture solution is dehydrated under negative pressure, and then is stacked with self assembly in microporous filter membrane substrate for containing carbon composite layer；At sucking filtration During the PP microporous filter membrane that another layer of average pore size is 100 microns is coated on containing carbon composite layer, constitute sandwich knot The composite membrane of structure；
3) composite membrane of sandwich structure is dried under the conditions of 40 DEG C 24h；
4) irradiated 6 days by ultraviolet light, utilize CeO2Photocatalysis characteristic make graphene oxide partial reduction, finally give thickness Degree is the isolating membrane of 100 microns.
Preparation, containing 5wt% magnesium chloride, the mixed solution of 5at% sodium chloride, uses suction method to measure this thin film to this solution Desalination effect, the effect going demagging is 99.8%, remove sodium effect be 99.5%.
Comparative example
1) aqueous solution of the aqueous solution of graphene oxide, the aqueous solution of nano-titanium oxide is uniformly mixed；The water of graphene oxide Liquor capacity mass concentration is 40mg/L, and the aqueous solution volume mass concentration of titanium oxide is 50mg/L；Graphene oxide, nanometer The mass ratio of titanium oxide is 1:0.1；
2) with aluminum oxide porous film that average pore size is 1.6 microns as substrate, vacuum filtration method is used to make graphene oxide, nanometer The mixture solution of titanium oxide is dehydrated under negative pressure；
3) under the conditions of 80 DEG C, 14h it is dried；
4) irradiated 3 days by ultraviolet light, make graphene oxide partial reduction, finally give the desalinization that thickness is 7.8 microns Film.
Preparation, containing 5wt% magnesium chloride, the mixed solution of 5at% sodium chloride, uses suction method to measure this thin film to this solution Desalination effect, the effect going demagging is 91.2%, remove sodium effect be 89.4%.After using 3 times, find containing oxidation The layer of titanium/graphene oxide has obscission.
It can be seen that the technique effect of embodiments of the invention is better than comparative example.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (8)

1. a carbon containing isolating membrane, it is characterised in that described composite membrane successively by microporous filter membrane, containing carbon composite layer and microporous filter membrane Up of three layers, the aperture of described microporous filter membrane is 10nm～100 μm, and the material of this microporous filter membrane is macromolecule, metal or oxidation Thing, described is the graphene oxide containing partial reduction and CeO containing carbon composite layer2。
Isolating membrane the most according to claim 1, it is characterised in that the thickness of described composite membrane is 100nm～100 μm.
Isolating membrane the most according to claim 1, it is characterised in that described macromolecule is PP and/or PE material.
Isolating membrane the most according to claim 1, it is characterised in that described oxide is aluminium oxide.
5. the preparation method of the isolating membrane described in any one of claim 1 ~ 4, it is characterised in that comprise the following steps:
1) by the aqueous solution of graphene oxide, CeO2Aqueous solution uniformly mix；
2) with microporous filter membrane as substrate, vacuum filtration method is used to make graphene oxide, CeO2Mixed solution be dehydrated under negative pressure, And then in microporous filter membrane substrate, it is stacked with self assembly for containing carbon composite layer；By another layer of microporous filter membrane bag during sucking filtration Overlay on containing carbon composite layer, constitute the composite membrane of sandwich structure；
3) composite membrane of sandwich structure is dried under the conditions of 40～80 DEG C 4～24h；
4) irradiated 1～5 day by ultraviolet light, utilize CeO2Photocatalysis characteristic make graphene oxide partial reduction, finally give Isolating membrane.
The preparation method of isolating membrane the most according to claim 5, it is characterised in that the aqueous liquid of described graphene oxide Long-pending mass concentration is 5～50mg/L, CeO2Aqueous solution volume mass concentration be 5～30mg/L.
The preparation method of isolating membrane the most according to claim 5, it is characterised in that described graphene oxide, CeO2Quality Ratio is 1: 0.1～0.2.
8. the application in terms of ion isolation of the isolating membrane described in any one of claim 1 ~ 4.
CN201610625355.9A 2016-08-03 2016-08-03 A kind of carbon containing isolating membrane and its preparation method and application Pending CN106110905A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545072A (en) * 2020-05-19 2020-08-18 林志华 Composite membrane for sewage treatment and preparation method thereof

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