CN1986037A - Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application - Google Patents
Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application Download PDFInfo
- Publication number
- CN1986037A CN1986037A CN200610134322.0A CN200610134322A CN1986037A CN 1986037 A CN1986037 A CN 1986037A CN 200610134322 A CN200610134322 A CN 200610134322A CN 1986037 A CN1986037 A CN 1986037A
- Authority
- CN
- China
- Prior art keywords
- nanotube
- composite separating
- membrane
- doped tio
- separating membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 147
- 239000002071 nanotube Substances 0.000 title claims abstract description 113
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 238000005516 engineering process Methods 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 102
- 239000002351 wastewater Substances 0.000 claims description 37
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 Titanium alkoxide Chemical class 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003651 drinking water Substances 0.000 claims description 3
- 235000020188 drinking water Nutrition 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000003403 water pollutant Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 17
- 239000000975 dye Substances 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 208000028659 discharge Diseases 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 241000336120 Melipona titania Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to membrane technology, and is especially composition separating membrane of Si-doped TiO2 nanotube and its preparation and application. The process of preparing composition separating membrane of Si-doped TiO2 nanotube includes the following steps: cleaning and stoving porous inorganic ceramic membrane carrier with pores of 10-200 nm diameter, preparing TiO2 sol containing Si in 5-50 mol%, soaking the carrier in the sol, drying, roasting at 400-700 deg.c, and cooling to obtain the composition separating membrane with TiO2 nanotube of inside diameter 1-200 nm. The composition separating membrane of Si-doped TiO2 nanotube is used in water treatment.
Description
Technical field
The present invention relates to a kind of diffusion barrier product and its production and application, in particular, relate to the porous, inorganic ceramic membrane, belong to the membrane technology field as composite separating membrane of Si-doped TiO 2 nanotube of carrier and template and its production and application.
Background technology
Membrane separation technique is the gas phase or the liquid phases separation of carrying out under the effect of pressure reduction motive force, it because of have no phase transformation, energy consumption is low, equipment is simple, occupation of land is few etc. obviously advantage be subjected to common concern.Membrane separation technique is tentatively industrialization now, and what occur the earliest is ultrafiltration and micro-filtration technology.Zsigmondy in 1918 have proposed the preparation method of commodity micro-filtration membrane, patent in nineteen twenty-one.Along with the development of membrane separation technique, it has extensive use in a lot of fields, as fields such as food industry, bioengineering, water treatment industry, chemical industry, petrochemical industry, metallurgical industry.
Inorganic ceramic membrane has more actual using value and prospect, it have high temperature resistant, chemical stability good, mechanical strength is high, anti-microbe ability is strong and advantage such as narrow pore size distribution range; Yet its weak point is: the filling area is little, and operating cost is higher, and film pollutes easily, and the pollutant of separation needs after-treatment, and film only plays the simple filtering function in separation process, and film separates can not thoroughly decompose removal to pollutant.If membrane separation technique is combined (as photocatalysis technology) with other technology, then may overcome the above problems.
The basic principle of photocatalytic degradation be semiconductor catalyst under the irradiation of ultraviolet light, the electronics on its valence band is excited on the conduction band, forms electron-hole pair, thereby has strong redox ability.This method treatment effeciency is higher, oxidant utilization ratio height, selectivity is good and do not bring other impurity into.In recent years, TiO
2Nanostructured (as nano particle, nanotube, nanometer rods etc.) is because of having excellent photocatalysis activity, and gets more and more people's extensive concerning.At TiO
2On the basis of nanostructured,, make TiO by some noble metals of load or some inorganic elements that mix
2The spectrum of photochemical catalyst utilizes scope to broaden and photocatalytic activity improves greatly.Si doped Ti O as preparations such as Jung
2The nano particle photochemical catalyst is used to handle trichloro-ethylene, and treatment effeciency is 5 times of German Degussa P25.
Although photocatalysis technology has many good qualities, this method is difficult to industrialization, and its subject matter is: (1) powdered form catalyst granules loses with treatment fluid or flow of process air easily, is difficult to recycle; (2) TiO of non-loaded or doped chemical
2The common spectrum of photochemical catalyst utilizes scope narrower, surface hydrophilicity a little less than, mechanical strength is lower, causes the photocatalytic activity of catalyst and use stability lower.
Pluses and minuses based on membrane separation technique and photocatalysis technology, the publication number that on July 30th, 2005 was proposed by Dalian University of Technology is the titanium dioxide nanometer pipe composite separating membrane of CN1745886A and its production and application patent application, become the typical case of prior art, this technology is separated two unit operations that are mutually independent with inorganic photocatalysis composite membrane with photocatalysis and is merged into a unit operations with film, has the integrated function that photocatalysis Decomposition is separated with film, but also have deficiency: owing to there is not the doping of element, can not effectively suppress the growth of titania, the minimum-value aperture that causes composite membrane to prepare only is 20nm, photocatalysis treatment rate 4-6h reaches 80-95%, and the surface hydrophilicity angle of wetting is easily cracked with the film surface greater than 10 °.
Summary of the invention
Purpose of the present invention and task will overcome prior art and exist: the film minimum-value aperture of (1) preparation only is 20nm, can not effectively handle little molecular contaminants, (2) photocatalytic activity is limited, in water treatment, reach 80-95% and need 4-6h, time is longer, (3) film moistened surface angle is greater than 10 °, hydrophily is low, (4) the film surface strength is low, easily cracked deficiency, and provide a kind of composite separating membrane of Si-doped TiO 2 nanotube that on porous, inorganic ceramic membrane carrier, prepares to be applied in the water-treatment technology field the special technical solution that proposes composite separating membrane of Si-doped TiO 2 nanotube of the present invention and its production and application.
Basic design of the present invention is, the sol-gel film technique is simple and feasible, a technology maturation and the membrane technology that is coated with industrial prospect, utilize esters of silicon acis doped silicon element in the glue process of sol-gel film technique, can control the growth of titania by the molar content that changes silicon doping, and with the porous, inorganic ceramic membrane as carrier and template, utilize the template action of fenestra, thereby by the littler membrane aperture of dipping pulling film forming preparation, the more highlight catalytic active and the composite separating membrane of Si-doped TiO 2 nanotube of great machinery intensity more.
Composite separating membrane of Si-doped TiO 2 nanotube proposed by the invention, comprise that the aperture is 10-200nm, pitch of holes is the porous, inorganic ceramic membrane carrier of 20-150nm and the preparation of titanium dioxide nanometer pipe composite separating membrane, it is characterized in that: composite separating membrane of Si-doped TiO 2 nanotube is to be 10-200nm with the aperture, pitch of holes is that the porous, inorganic ceramic membrane of 20-150nm is a carrier, mix the silicon glue by sol-gel technique, carrier film is through dipping, dry, roasting, inside and outside the duct of carrier, form titania nanotube, thereby the formation aperture is 1-200nm, pitch of holes is the composite separating membrane of Si-doped TiO 2 nanotube of 20-150nm, and, titania nanotube is perpendicular to diaphragm, and its element silicon doping molar content is 5-50%.
The preparation method of composite separating membrane of Si-doped TiO 2 nanotube proposed by the invention is characterized in that, the method step of preparation is as follows:
The first step, the preliminary treatment of carrier
Will be as the inoranic membrane of carrier with washed with de-ionized water and with after the 50-100 ℃ of oven dry, it is standby to reduce to room temperature naturally;
Second step, the preparation of Si-doped TiO 2 colloidal sol
Titanium alkoxide and silicon alkoxide are mixed into 1 part of precursor material in the ratio of silicon molar content 5-50%, be dissolved in stir in 0.5-2 part absolute ethyl alcohol after, slowly add the mixed solution and the stirring of 0.1-1 part hydrochloric acid or nitric acid, 0.5-2 part absolute ethyl alcohol, 0.1-1 part water again, slowly hydrolysis obtains light yellow transparent Si-doped TiO 2 colloidal sol;
The 3rd step, the preparation of composite separating membrane of Si-doped TiO 2 nanotube
Inoranic membrane is immersed among this colloidal sol 1-30min, after the taking-up drying, be warming up to 400-700 ℃ of insulation 0.5-4h; Reduce to room temperature with 50-500 ℃/h then, preparation is finished.
Use composite separating membrane of Si-doped TiO 2 nanotube proposed by the invention is handled the application of water, it is characterized in that: when pending water passes through composite separating film, producing scope by compression pump or vavuum pump provides separation process needed driving force for the pressure reduction of 0.02-1.0MPa, water pollutant is carried out film to be separated, composite separating film is when ultra violet lamp simultaneously, titanium dioxide is activated, produce photohole-duplet, in course of reaction, continue bubbling air, film is held back or adsorbent generation redox reaction and degraded, and its treatment effeciency reaches 81-95% behind 2-4h.
Of the present invention being further characterized in that: porous, inorganic ceramic membrane carrier is alchlor, zirconia, silica; Titania nanotube is to have the titania nanotube of anatase crystal or contain the titanium dioxide mixed crystal nanotube that anatase crystal is the master; The composite separating membrane of Si-doped TiO 2 nanotube layer is can be through mixing or surface-treated composite separating film layer again; Use composite separating membrane of Si-doped TiO 2 nanotube, can be applicable to the water-treatment technology field of organic pollutant wastewater processing, dirty waste water advanced treatment recovery, drinking water disinfection, high purity water preparation and desalinization.
Organic pollutant wastewater is handled and dirty waste water advanced treatment recovery comprises dye class, and chemical intermediate class (as phenol, chlorophenol, nitro thing, amido thing, chlorohydrocarbon etc.) is surfactant-based, pesticide, classes of herbicides, hydro carbons, polychlorinated biphenyl, bonding agent waste water.
Titanium dioxide nanometer pipe composite separating membrane provided by the present invention, in preparation process, by the control dip time, can obtain the titanium dioxide nanometer pipe composite separating membrane in different apertures, when the time that inoranic membrane floods in Si-doped TiO 2 colloidal sol is taken off limit value 1min, the prepared composite separating membrane of Si-doped TiO 2 nanotube of same apertures inorganic ceramic membrane carrier has bigger aperture, and when handling organic pollution, it is relatively low to obtain rejection; When the time of carrier impregnation capping value 30min, the aperture of the composite separating membrane of Si-doped TiO 2 nanotube that same apertures inorganic ceramic membrane carrier is prepared is less, and it is higher relatively to obtain rejection; In the preparation process, the calcining heat of composite separating film, temperature retention time and cooling rate have significant effects to the formation of composite separating film inside titania nanotube, when the calcining heat of inoranic membrane is lower than 400 ℃, the titanium dioxide nano-crystal that constitutes composite separating film does not grow into anatase crystal as yet fully, do not possess good photocatalytic activity, when the calcining heat of inoranic membrane is higher than 700 ℃, the titanium dioxide nano-crystal of anatase crystal partly changes rutile crystal type into, to reduce the photocatalysis treatment effect, when the temperature retention time of inoranic membrane is lower than 0.5h, growth is incomplete as yet for the titanium dioxide nano-crystal of anatase crystal, after the temperature retention time of inoranic membrane is higher than 4h, the titanium dioxide nano-crystal of anatase crystal is grown fully substantially, prolonging temperature retention time will not make significant difference to crystal formation, when the cooling rate of inoranic membrane is lower than 50 ℃/h, cause among the preparation technology temperature fall time long, when the cooling rate of inoranic membrane is higher than 500 ℃/h, expands with heat and contract with cold and to cause the cracked of film surface; Composite separating film is in application, different pressure reduction can influence its membrane flux, handle water water quality etc., for guaranteeing that technology has bigger membrane flux when moving, when membrane aperture is 1-100nm, adopt pressure differential 0.1-1.0MPa to move driving force as film, when membrane aperture is 100-200nm, adopt pressure differential 0.02-0.1MPa to move driving force as film.Because have experiment condition and the inevitably influence of experimental error, some parameters of composite separating membrane of Si-doped TiO 2 nanotube provided by the present invention and preparation thereof and application are the value range that statistical mathematics is calculated.
Use composite separating membrane of Si-doped TiO 2 nanotube provided by the present invention in water treatment field, aspect organic pollutant wastewater processing, dirty waste water advanced treatment recovery, drinking water disinfection, high purity water preparation and desalinization, use as the main technique unit of flow process or the preliminary treatment or the advanced treatment process of main technique unit; When it handled organic pollutant wastewater and dirty waste water advanced treatment recovery, the organic contamination substrate concentration should be less than 500mg/L.
Major advantage of the present invention has:
(1) it is littler that the doping of element silicon can be controlled the composite separating film aperture, and minimum reaches 1nm, can be widely used in water-treatment technology field;
(2) composite separating membrane of Si-doped TiO 2 nanotube has photocatalytic activity, surface hydrophilicity and the application stability of enhancing simultaneously, therefore is applied in the water treatment, and the 2-4h treatment effeciency can reach 81-95%;
(3) preparation and technique for applying are simple, both can be used for experimental implementation, but large-scale industrial production again.
The subordinate list explanation
The present invention is provided with 6 subordinate lists altogether, now is respectively described below:
Table 1 is that composite separating membrane of Si-doped TiO 2 nanotube is mixed silicon amount and anatase crystal titanium dioxide nanocrystalline particle size parameter values table
Behind the doped silicon element, the titanium dioxide nanocrystalline particle size of anatase crystal obviously diminishes, and is 6.1-11nm in titanium dioxide nanometer pipe composite separating membrane; And it is less that crystallite dimension is influenced by calcining heat.This shows that the doping of silicon can significantly suppress the growth of titanium dioxide nanocrystalline grain, therefore mixing silicon can prepare the littler titanium dioxide nanometer pipe composite separating membrane in aperture.
Table 2 is that composite separating membrane of Si-doped TiO 2 nanotube is used to handle and contains each parameter values table that surface active agent wastewater adopts
Composite separating membrane of Si-doped TiO 2 nanotube concentration of treatment in the Application Example 2 is 50mg/L, and wastewater flow rate is the surfactant solution of 1L, and circular treatment is after 2 hours, and its treatment effeciency reaches 90%, exceeds independent separation and independent photocatalysis 12-18%.
Table 3 is that composite separating membrane of Si-doped TiO 2 nanotube is used for each parameter values table that Phenol-Containing Wastewater Treatment adopts
Composite separating membrane of Si-doped TiO 2 nanotube concentration of treatment in the Application Example 3 is 40mg/L, and wastewater flow rate is the pentachlorophenol solution of 1L, and circular treatment is after 2 hours, and its treatment effeciency reaches 95%, exceeds independent separation and independent photocatalysis 13-39%.
Table 4 is that composite separating membrane of Si-doped TiO 2 nanotube is used for each parameter values table that dye wastewater treatment using adopts
Composite separating membrane of Si-doped TiO 2 nanotube concentration of treatment in the Application Example 5 is 500mg/L, and wastewater flow rate is directly black 168 solution of 1L, and circular treatment is after 4 hours, and its treatment effeciency reaches 81%, exceeds independent separation and independent photocatalysis 11-22%.
Table 5 is to mix silicon and the non-impurity-doped titanium dioxide nanometer pipe composite separating membrane is used for each parameter values table that dye wastewater treatment using adopts
Composite separating membrane of Si-doped TiO 2 nanotube concentration of treatment in the Application Example 2 is 100mg/L, and wastewater flow rate is the dye solution of 1L, and circular treatment is after 2 hours, and its treatment effeciency reaches 92%; And use the non-impurity-doped titanium dioxide nanometer pipe composite separating membrane, and circular treatment is after 4 hours, and its treatment effeciency only reaches 86%.
Table 6 is that composite separating membrane of Si-doped TiO 2 nanotube is used to prepare each parameter values table that different purposes pure water are adopted
Composite separating membrane of Si-doped TiO 2 nanotube in the Application Example 1 prepares different purposes pure water, is under the 0.5MPa at pressure reduction, and the film separation can obtain the pure water that electrical conductivity is 1.00-6.00 μ S/cm separately; Under same pressure differential, answer photoactivation-isolation integral function, can obtain the ultra-pure water that resistivity is 0.0625-0.1000 μ S/cm; And be under the 0.2MPa at pressure reduction, can obtain the high purity water that resistivity is 0.0588-0.055 μ S/cm.
Description of drawings
The present invention is provided with 3 width of cloth accompanying drawings altogether, now is respectively described below:
Fig. 1 is the ESEM front view (SEM) of composite separating membrane of Si-doped TiO 2 nanotube
The sem photograph of composite separating membrane of Si-doped TiO 2 nanotube of the present invention, accelerating potential are 20kV, and 20000 times of multiplication factors are taken along vertical composite separating film direction.As seen, composite separating membrane of Si-doped TiO 2 nanotube has cellular aperture 1 to be arranged among the figure, and the aperture is 40-100nm.Because the Si-doped TiO 2 nanotube that generates is perpendicular to diaphragm, so can only see the aperture 1 (stain place) of composite separating membrane of Si-doped TiO 2 nanotube among the figure, and cannot see the pipe range of Si-doped TiO 2 nanotube, but can see hole wall 2 terminations (netted in vain) of composite separating membrane of Si-doped TiO 2 nanotube.A-A is a section symbols.
Fig. 2 is that the A-A profile scanning Electronic Speculum of Fig. 1 is faced structural representation (SEM)
This A-A cross-sectional view, accelerating potential are 20kV, and 6000 times of multiplication factors are taken along vertical view 1A-A profile direction.Among the figure as seen, the aperture 1 of composite separating membrane of Si-doped TiO 2 nanotube (secret note shape), the duct all perpendicular to the face direction, is evenly distributed, discrete in order, the aperture is 40-100nm.By the carrier film 3 (informal voucher shape) that can also clearly see composite separating film among the figure.
Fig. 3 is the transmission electron microscope picture (TEM) of single Si-doped TiO 2 nanotube
The transmission electron microscope picture of single Si-doped TiO 2 nanotube of the present invention, accelerating potential are 200kV, and multiplication factor is 50000 times.As seen from the figure, the Si-doped TiO 2 nanotube outer tube diameter that obtains is approximately 150nm, and interior caliber is approximately 60nm, and pipe thickness is approximately 45nm.The interior caliber that can clearly see Si-doped TiO 2 nanotube is the aperture 1 (part between the secret note shape of the left and right sides) of composite separating film, and the tube wall 4 of single Si-doped TiO 2 nanotube (secret note shape part), the shot-like particle that seems more coarse on the nanotube is for constituting the Si-doped TiO 2 crystal grain 5 (grey point-like) of Si-doped TiO 2 nanotube tube wall.
The specific embodiment
Below by specific embodiment, further specify the details of composite separating membrane of Si-doped TiO 2 nanotube preparation method and application thereof.
Embodiment 1:
When requiring the little or aperture of composite separating film permeation flux hour, can use the composite separating membrane of Si-doped TiO 2 nanotube for preparing under the following condition.
With the aperture is 10nm, and pitch of holes is 30-70nm, and porosity is 30% ZrO
2Inoranic membrane is as carrier, and the preparation aperture is the composite separating membrane of Si-doped TiO 2 nanotube of 1-8nm, and step is:
The first step, the preliminary treatment of carrier
ZrO
2Inoranic membrane is with washed with de-ionized water and with after 50 ℃ of oven dry, and it is standby to reduce to room temperature naturally;
Second step, the preparation of Si-doped TiO 2 colloidal sol
With isopropyl titanate Ti (Oi-C
3H
7)
4With methyl silicate Si (OCH
3)
4Be mixed into 1 part in the ratio of mixing silicon molar content 5% and join in 0.5 part of absolute ethyl alcohol the mixed solution vigorous stirring; Getting 2 parts of absolute ethyl alcohols and 0.1 part of nitric acid and 0.5 part of water mixed solution then in addition slowly is added drop-wise in the above solution.Obtain light yellow vitreosol by the slow hydrolysis of sol-gel.
The 3rd step, the preparation of composite separating membrane of Si-doped TiO 2 nanotube
With ZrO
2Inoranic membrane immerses in this colloidal sol, takes out drying behind the 1min, is warming up to 500 ℃ of insulation 0.5h then, reduces to room temperature with 50 ℃/h at last.
Testing result: the composite separating membrane of Si-doped TiO 2 nanotube aperture is 1-8nm, the titania nanotube structure of composite separating film inside, and interior caliber 1-8nm, about outer tube diameter 20nm, pipe range 50-55 μ m.Titania nanotube is discrete in order, all perpendicular to the film direction.
Embodiment 2:
At handling the bigger wastewater treatment of molecular dimension,, use the composite separating membrane of Si-doped TiO 2 nanotube for preparing under the following condition as dye class, polychlorinated biphenyl etc.
With the aperture is 100nm, and pitch of holes is 30-60nm, and porosity is 40% Al
2O
3Inoranic membrane is as carrier, and the preparation aperture is the composite separating membrane of Si-doped TiO 2 nanotube of 10-50nm, and step is:
The first step, the preliminary treatment of carrier
Al
2O
3Inoranic membrane is with washed with de-ionized water and with after 70 ℃ of oven dry, and it is standby to reduce to room temperature naturally;
Second step, the preparation of Si-doped TiO 2 colloidal sol
Isopropyl titanate Ti (Oi-C just
3H
7)
4With ethyl orthosilicate Si (OC
2H
5)
4Be mixed into 1 part in the ratio of mixing silicon molar content 20% and join in 2 parts of absolute ethyl alcohols the mixed solution vigorous stirring; Getting 0.5 part of absolute ethyl alcohol and 0.2 part of nitric acid and 1 part of water mixed solution then in addition slowly is added drop-wise in the above solution.Obtain light yellow vitreosol by the slow hydrolysis of sol-gel.
The 3rd step, the preparation of composite separating membrane of Si-doped TiO 2 nanotube
With Al
2O
3Inoranic membrane immerses in this colloidal sol, takes out drying behind the 5min, is warming up to 400 ℃ of insulation 4h then, reduces to room temperature with 100 ℃/h at last.
Testing result: the composite separating membrane of Si-doped TiO 2 nanotube aperture is 10-50nm, the titania nanotube structure of composite separating film inside, and interior caliber 10-50nm, about outer tube diameter 100nm, pipe range 55-60 μ m.Si-doped TiO 2 nanotube is discrete in order, all perpendicular to the film direction.
Embodiment 3:
With the aperture is 200nm, and pitch of holes is 20-150nm, and porosity is 50% Al
2O
3Inoranic membrane is as carrier, and the preparation aperture is the composite separating membrane of Si-doped TiO 2 nanotube of 50-200nm, and step is:
The first step, the preliminary treatment of carrier
Al
2O
3With washed with de-ionized water and with after 100 ℃ of oven dry, it is standby to reduce to room temperature naturally;
Second step, the preparation of Si-doped TiO 2 colloidal sol
With isopropyl titanate Ti (Oi-C
3H
7)
4With ethyl orthosilicate Si (OC
2H
5)
4Be mixed into 1 part in the ratio of mixing silicon molar content 50% and join in 0.5 part of absolute ethyl alcohol the mixed solution vigorous stirring; Getting 0.5 part of absolute ethyl alcohol and 1 part of hydrochloric acid and 1 part of water mixed solution then in addition slowly is added drop-wise in the above solution.Obtain light yellow vitreosol by the slow hydrolysis of sol-gel.
The 3rd step, the preparation of composite separating membrane of Si-doped TiO 2 nanotube
With Al
2O
3Inoranic membrane immerses in this colloidal sol, takes out drying behind the 20min, is warming up to 700 ℃ of insulation 2h then, reduces to room temperature with 200 ℃/h at last.
Testing result: the composite separating membrane of Si-doped TiO 2 nanotube aperture is 50-200nm, the titania nanotube structure of composite separating film inside, and interior caliber 20-50nm, about outer tube diameter 200nm, pipe range 50-60 μ m.Si-doped TiO 2 nanotube is discrete in order, all perpendicular to the diaphragm direction.
Embodiment 4:
When the permeation flux that requires composite separating film is big, use the composite separating membrane of Si-doped TiO 2 nanotube for preparing under the following condition.
With the aperture is 200nm, and pitch of holes is 20-50nm, and porosity is 50% SiO
2Inoranic membrane is as carrier, and the preparation aperture is the composite separating membrane of Si-doped TiO 2 nanotube of 1-60nm, and step is:
The first step, the preliminary treatment of carrier
SiO
2With washed with de-ionized water and with after 80 ℃ of oven dry, it is standby to reduce to room temperature naturally;
Second step, the preparation of Si-doped TiO 2 colloidal sol
With butyl titanate Ti (OC
4H
9)
4With ethyl orthosilicate Si (OC
2H
5)
4Be mixed into 1 part in the ratio of mixing silicon molar content 33% and join in 1 part of absolute ethyl alcohol the mixed solution vigorous stirring; Getting 1 part of absolute ethyl alcohol and 0.2 part of hydrochloric acid and 0.5 part of water mixed solution then in addition slowly is added drop-wise in the above solution.Obtain light yellow vitreosol by the slow hydrolysis of sol-gel.
The 3rd step, the preparation of composite separating membrane of Si-doped TiO 2 nanotube
With SiO
2Inoranic membrane immerses in this colloidal sol, takes out drying behind the 30min, is warming up to 400 ℃ of insulation 4h then, reduces to room temperature with 500 ℃/h at last.
Testing result: the composite separating membrane of Si-doped TiO 2 nanotube aperture is 1-60nm, the titania nanotube structure of composite separating film inside, and interior caliber 1-60nm, about outer tube diameter 200nm, pipe range 55-60 μ m.Si-doped TiO 2 nanotube is discrete in order, all perpendicular to the diaphragm direction.
Embodiment 5: composite separating membrane of Si-doped TiO 2 nanotube is used for dirty waste water advanced treatment recovery
Dalian * * surface active agent wastewater that the chemical plant needs to be discharged handles reuse, and waste water quality: the surface active agent wastewater initial concentration is 50mg/L, and the water inlet flow velocity is 12.7L/h, and the water yield is 1.0L.
Composite separating membrane of Si-doped TiO 2 nanotube in the Application Example 4 is handled and is contained surface active agent wastewater.Under the room temperature condition, make surfactant solution flow through the film test cell by pump.At pressure reduction is 1.0MPa, and film separates when participating in, and adopts the surface of ultra violet lamp composite separating membrane of Si-doped TiO 2 nanotube, and bubbling air continues to stir in the course of reaction.After the circular treatment 2 hours, its treatment effeciency reaches 90%.Going out water concentration after the processing is 5mg/L, through advanced treating, reaches the recycle-water quality standard, can circulating and recovering.
Embodiment 6: composite separating membrane of Si-doped TiO 2 nanotube is used to handle organic pollutant wastewater
Dalian * * chemical plant need discharge pentachlorophenol waste water, waste water quality: pentachlorophenol waste water initial concentration is 40mg/L, and the water inlet flow velocity is 12.7L/h, and the water yield is 1.0L.
Composite separating membrane of Si-doped TiO 2 nanotube Phenol-Containing Wastewater Treatment in the Application Example 3.Under the room temperature condition, make pentachlorophenol solution by the film test cell by pump.At pressure reduction is 0.02MPa, and film separates when participating in, and adopts the surface of ultra violet lamp composite separating membrane of Si-doped TiO 2 nanotube, and bubbling air continues to stir in the course of reaction.After the circular treatment 2 hours, its treatment effeciency reaches 95%.Handling back pentachlorophenol waste strength is 2mg/L, reaches first discharge standard among the national sewage comprehensive emission standard GB 8978-1996, can discharge.
Embodiment 7: composite separating membrane of Si-doped TiO 2 nanotube is used for dye wastewater treatment using
Dalian * * directly black 168 waste water of printing and dyeing mill's discharging dyestuff, waste water quality: the directly black 168 waste water initial concentrations of dyestuff are 500mg/L, and the water inlet flow velocity is 7.0L/h, and the water yield is 1.0L.
Composite separating membrane of Si-doped TiO 2 nanotube in the Application Example 2 is handled directly black 168 waste water of dyestuff.Under the room temperature condition, make dye solution pass through the film test cell by pump.At pressure reduction is 0.2MPa, and film separates when participating in, and adopts the surface of ultra violet lamp composite separating membrane of Si-doped TiO 2 nanotube, and bubbling air continues to stir in the course of reaction.After the circular treatment 4 hours, its treatment effeciency reaches 81%.Handling directly black 168 waste strengths in back is 95mg/L, pass through advanced treating again after, waste water from dyestuff reaches secondary discharge standard among the national sewage comprehensive emission standard GB 8978-1996, can discharge.
Composite separating membrane of Si-doped TiO 2 nanotube in the Application Example 2 makes to mix silicon and the non-impurity-doped titanium dioxide nanometer pipe composite separating membrane deals with the effect contrast to waste water from dyestuff, it is 100mg/L that waste water from dyestuff is diluted to concentration of treatment, wastewater flow rate is 5L, employing pressure reduction is 0.1MPa, use composite separating membrane of Si-doped TiO 2 nanotube, after the circular treatment 2 hours, its treatment effeciency reaches 92%; And use the non-impurity-doped titanium dioxide nanometer pipe composite separating membrane, and circular treatment is after 4 hours, and its treatment effeciency only reaches 86%.
Embodiment 8: composite separating membrane of Si-doped TiO 2 nanotube is used for the high purity water preparation
Influent quality: municipal water supply pipe network water for industrial use water quality, water inlet electrical conductivity 100-150 μ S/cm, the water inlet flow velocity is 12.7L/h, the water yield is 3.0L.
Composite separating membrane of Si-doped TiO 2 nanotube in the Application Example 1 prepares different purposes pure water, in the time of 25 ℃, is under the 0.5MPa at pressure reduction, and independent film separation can obtain the pure water that electrical conductivity is 1.00-6.00 μ S/cm behind the reaction 2h; Under same pressure differential, answer photoactivation-isolation integral function, can obtain the ultra-pure water that electrical conductivity is 0.0625-0.1000 μ S/cm behind the reaction 2h, be used for conventional physico-chemical analysis, cell culture of animals, the preparation of Instrumental Analysis buffer solution etc.; And be under the 0.2MPa at pressure reduction, can obtain the high purity water that electrical conductivity is 0.0588-0.055 μ S/cm behind the reaction 2h, be used for being subjected to especially easily water quality impact, highly sensitive molecular biology experiment water.
Subordinate list
Table 1 composite separating membrane of Si-doped TiO 2 nanotube is mixed silicon amount and anatase crystal titanium dioxide nanocrystalline particle size parameter values table
When * mixing silicon molar percentage and being 50%, the titanium dioxide nanocrystalline type after 500 ℃, 600 ℃ and the 700 ℃ of calcinings is unformed shape.
Table 2 composite separating membrane of Si-doped TiO 2 nanotube is for the treatment of each the parameter values table that contains surface active agent wastewater and adopt
Each parameter values table that table 3 composite separating membrane of Si-doped TiO 2 nanotube adopts for the treatment of phenol wastewater
Each parameter values table that table 4 composite separating membrane of Si-doped TiO 2 nanotube adopts for the treatment of waste water from dyestuff
Table 5 is mixed each parameter values table that silicon and non-impurity-doped titanium dioxide nanometer pipe composite separating membrane adopt for the treatment of waste water from dyestuff
Each parameter values table that table 6 composite separating membrane of Si-doped TiO 2 nanotube adopts for the preparation of different purposes pure water
Claims (7)
1. composite separating membrane of Si-doped TiO 2 nanotube, comprise that the aperture is 10-200nm, pitch of holes is the porous, inorganic ceramic membrane carrier of 20-150nm and the preparation of titanium dioxide nanometer pipe composite separating membrane, it is characterized in that: composite separating membrane of Si-doped TiO 2 nanotube is to be 10-200nm with the aperture, pitch of holes is that the porous, inorganic ceramic membrane of 20-150nm is a carrier, mix the silicon glue by sol-gel technique, carrier film [3] is through dipping, dry, roasting, inside and outside the duct of carrier, form titania nanotube, thereby obtaining aperture [1] is 1-200nm, pitch of holes is the composite separating membrane of Si-doped TiO 2 nanotube of 20-150nm, and, titania nanotube is perpendicular to diaphragm, and its element silicon doping molar content is 5-50%.
2. composite separating membrane of Si-doped TiO 2 nanotube according to claim 1 is characterized in that: porous, inorganic ceramic membrane carrier is alchlor, zirconia, porous silica ceramic membrane.
3. composite separating membrane of Si-doped TiO 2 nanotube according to claim 1 is characterized in that: titania nanotube is to have the titania nanotube of anatase crystal or contain the titanium dioxide mixed crystal nanotube that anatase crystal is the master.
4. composite separating membrane of Si-doped TiO 2 nanotube according to claim 1 is characterized in that: the composite separating membrane of Si-doped TiO 2 nanotube layer is can be through mixing or surface-treated composite separating film layer again.
5. prepare the method for composite separating membrane of Si-doped TiO 2 nanotube as claimed in claim 1, it is characterized in that, preparation process is as follows:
The first step, the preliminary treatment of carrier
Will be as the inoranic membrane of carrier with washed with de-ionized water and with after the 50-100 ℃ of oven dry, it is standby to reduce to room temperature naturally;
Second step, the preparation of Si-doped TiO 2 colloidal sol
Titanium alkoxide and silicon alkoxide are mixed into 1 part of precursor material in the ratio of silicon molar content 5-50%, be dissolved in stir in 0.5-2 part absolute ethyl alcohol after, slowly add the mixed solution and the stirring of 0.1-1 part hydrochloric acid or nitric acid, 0.5-2 part absolute ethyl alcohol, 0.1-1 part water again, slowly hydrolysis obtains light yellow transparent Si-doped TiO 2 colloidal sol;
The 3rd step, the preparation of composite separating membrane of Si-doped TiO 2 nanotube
Inoranic membrane is immersed among this colloidal sol 1-30min, after the taking-up drying, be warming up to 400-700 ℃ of insulation 0.5-4h; Reduce to room temperature with 50-500 ℃/h then, preparation is finished.
6. use composite separating membrane of Si-doped TiO 2 nanotube as claimed in claim 1 to handle the application of water, it is characterized in that: when pending water passes through composite separating film, producing scope by compression pump or vavuum pump provides separation process needed driving force for the pressure reduction of 0.02-1.0MPa, water pollutant is carried out film to be separated, composite separating film is when ultra violet lamp simultaneously, titanium dioxide is activated, produce photohole-duplet, in course of reaction, continue bubbling air, film is held back or adsorbent generation redox reaction and degraded, and its treatment effeciency reaches 81-95% behind 2-4h.
7. use composite separating membrane of Si-doped TiO 2 nanotube according to claim 6 is handled the application of water, it is characterized in that: the water-treatment technology field that can be applicable to organic pollutant wastewater processing, dirty waste water advanced treatment recovery, drinking water disinfection, high purity water preparation and desalinization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101343220A CN100428984C (en) | 2006-11-17 | 2006-11-17 | Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101343220A CN100428984C (en) | 2006-11-17 | 2006-11-17 | Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1986037A true CN1986037A (en) | 2007-06-27 |
| CN100428984C CN100428984C (en) | 2008-10-29 |
Family
ID=38183061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101343220A Active CN100428984C (en) | 2006-11-17 | 2006-11-17 | Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100428984C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784633A (en) * | 2011-05-17 | 2012-11-21 | 王东宁 | Preparation method for photocatalyst TiO2 supporter and manufacturing method for photocatalyst air cleaner |
| CN105602942A (en) * | 2016-03-23 | 2016-05-25 | 王智勇 | Nucleic acid releaser and method for quickly extracting nucleic acids from dried blood spots |
| CN106745955A (en) * | 2016-11-24 | 2017-05-31 | 山东大学 | The filter and its operating method of a kind of photocatalysis membrana separation function coupling |
| CN106902645A (en) * | 2017-02-15 | 2017-06-30 | 山东工业陶瓷研究设计院有限公司 | A kind of preparation method of the super hydrophilic ceramic membrane with photocatalysis performance |
| CN109476512A (en) * | 2016-06-12 | 2019-03-15 | 美索过滤公司 | The composition and method of arsenic removal and heavy metal are removed from water |
| CN110013682A (en) * | 2019-05-05 | 2019-07-16 | 河北工业大学 | A kind of novel nano-titanium dioxide production procedure control device and method |
| CN110605030A (en) * | 2019-09-23 | 2019-12-24 | 大连理工大学 | Preparation method of thermal crosslinking membrane for maintaining membrane pore structure |
| CN111068525A (en) * | 2019-12-11 | 2020-04-28 | 天津科技大学 | Composite membrane with titanium dioxide nanorod array on surface, and preparation method and application thereof |
| CN113926441A (en) * | 2021-10-12 | 2022-01-14 | 北京林业大学 | Si-doped TiO2Nanorod-grafted photocatalytic coupling self-cleaning modified ceramic membrane and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6464881B2 (en) * | 1996-10-21 | 2002-10-15 | Orelis | Inorganic nanofiltration membrane and its application in the sugar industry |
| EP1468737A4 (en) * | 2002-01-21 | 2005-09-21 | Sumitomo Titanium Corp | Photocatalytic composite material and method for preparation thereof |
| CN1150980C (en) * | 2002-08-14 | 2004-05-26 | 清华大学 | Process for preparing photocatalytic TiO2 film used to clean water and air |
| CN1424282A (en) * | 2003-01-06 | 2003-06-18 | 华东理工大学 | Titania nano film containing rare earth and silica and production thereof |
| CN1206015C (en) * | 2003-03-11 | 2005-06-15 | 武汉理工大学 | Method for preparing porous ceramic material with titanium dioxide optical catalytic nano-coating for purifying air and water |
| CN1319634C (en) * | 2005-07-30 | 2007-06-06 | 大连理工大学 | Titanium dioxide nanometer pipe composite separating membrane, its preparation and use thereof |
-
2006
- 2006-11-17 CN CNB2006101343220A patent/CN100428984C/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784633A (en) * | 2011-05-17 | 2012-11-21 | 王东宁 | Preparation method for photocatalyst TiO2 supporter and manufacturing method for photocatalyst air cleaner |
| CN105602942A (en) * | 2016-03-23 | 2016-05-25 | 王智勇 | Nucleic acid releaser and method for quickly extracting nucleic acids from dried blood spots |
| CN109476512B (en) * | 2016-06-12 | 2021-11-09 | 美索过滤公司 | Composition and method for removing arsenic and heavy metals from water |
| CN109476512A (en) * | 2016-06-12 | 2019-03-15 | 美索过滤公司 | The composition and method of arsenic removal and heavy metal are removed from water |
| CN106745955A (en) * | 2016-11-24 | 2017-05-31 | 山东大学 | The filter and its operating method of a kind of photocatalysis membrana separation function coupling |
| CN106902645A (en) * | 2017-02-15 | 2017-06-30 | 山东工业陶瓷研究设计院有限公司 | A kind of preparation method of the super hydrophilic ceramic membrane with photocatalysis performance |
| CN106902645B (en) * | 2017-02-15 | 2019-11-12 | 山东工业陶瓷研究设计院有限公司 | A kind of preparation method of the super hydrophilic ceramic membrane with photocatalysis performance |
| CN110013682A (en) * | 2019-05-05 | 2019-07-16 | 河北工业大学 | A kind of novel nano-titanium dioxide production procedure control device and method |
| CN110013682B (en) * | 2019-05-05 | 2024-01-26 | 河北工业大学 | Novel nano titanium dioxide production flow control device and method |
| CN110605030A (en) * | 2019-09-23 | 2019-12-24 | 大连理工大学 | Preparation method of thermal crosslinking membrane for maintaining membrane pore structure |
| CN111068525A (en) * | 2019-12-11 | 2020-04-28 | 天津科技大学 | Composite membrane with titanium dioxide nanorod array on surface, and preparation method and application thereof |
| CN113926441A (en) * | 2021-10-12 | 2022-01-14 | 北京林业大学 | Si-doped TiO2Nanorod-grafted photocatalytic coupling self-cleaning modified ceramic membrane and preparation method thereof |
| CN113926441B (en) * | 2021-10-12 | 2023-11-21 | 北京林业大学 | Si doped TiO 2 Nanometer rod grafted photocatalysis coupling self-cleaning modified ceramic membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100428984C (en) | 2008-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100428984C (en) | Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application | |
| Iglesias et al. | Membrane-based photocatalytic systems for process intensification | |
| Ismail et al. | Mesoporous titania photocatalysts: preparation, characterization and reaction mechanisms | |
| Leong et al. | TiO2 based photocatalytic membranes: A review | |
| Zhang et al. | Fabrication of nanostructured TiO2 hollow fiber photocatalytic membrane and application for wastewater treatment | |
| US11571689B2 (en) | Synthesis strategy of supported transition metal carbides Fenton-like catalysts and application thereof | |
| CN101497003B (en) | Multifunctional photocatalysis composite ceramic separation membrane as well as preparation method and use thereof | |
| CN105800767B (en) | The structure of a kind of nanometer of mangaic acid copper spinelle catalytic film reactor and its application process in water process | |
| Ding et al. | Emerging heterostructured C 3 N 4 photocatalysts for photocatalytic environmental pollutant elimination and sterilization | |
| CN101952040A (en) | Co-doped titanium oxide foam and water disinfection device | |
| KR102438310B1 (en) | Hollow fiber type photocatalyst and manufacturing method thereof | |
| CN105887332A (en) | Preparation method of nitrogen-doped flexible TiO2-SiO2 nanofiber membrane with visible light catalytic function | |
| Nikazara et al. | Using TiO 2 supported on clinoptilolite as a catalyst for photocatalytic degradation of azo dye disperse yellow 23 in water | |
| CN106179291A (en) | Optically catalytic TiO 2 coating and preparation method thereof | |
| CN106179304A (en) | A kind of CeO possessing photo catalytic reduction performance2tiO2the preparation method of nano composite material | |
| CN111836785A (en) | Method and system for water treatment using ultrasonic action and/or photocatalytic reaction | |
| CN102125831B (en) | Method for preparing mesoporous Bi2O3/TiO2 nano photocatalyst | |
| CN104226320B (en) | The preparation method of vanadium boron codope titanium dioxide and nickel oxide composite photo-catalyst | |
| Otitoju et al. | Surface modification of PVDF membrane via layer-by-layer self-assembly of TiO2/V for enhanced photodegradation of emerging organic pollutants and the implication for wastewater remediation | |
| CN1319634C (en) | Titanium dioxide nanometer pipe composite separating membrane, its preparation and use thereof | |
| Ngo | Photocatalytic degradation of phenol in aqueous solutions using TiO2/SiO2 composite | |
| Lim et al. | Combined photocatalysis–separation processes for water treatment using hybrid photocatalytic membrane reactors | |
| CN116850796A (en) | Super-hydrophilic photocatalytic self-cleaning ceramic composite membrane and preparation method and application thereof | |
| CN115970724A (en) | Preparation method of ceramic membrane with catalytic ozonation function | |
| CN109694128A (en) | Method for treating high-concentration p-nitrophenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |